EP0822290B1 - Fireproof paper, especially printing paper and advertising support - Google Patents
Fireproof paper, especially printing paper and advertising support Download PDFInfo
- Publication number
- EP0822290B1 EP0822290B1 EP97401791A EP97401791A EP0822290B1 EP 0822290 B1 EP0822290 B1 EP 0822290B1 EP 97401791 A EP97401791 A EP 97401791A EP 97401791 A EP97401791 A EP 97401791A EP 0822290 B1 EP0822290 B1 EP 0822290B1
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- EP
- European Patent Office
- Prior art keywords
- paper
- dry weight
- flame retardant
- paper according
- base
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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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/34—Ignifugeants
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/07—Nitrogen-containing 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/10—Phosphorus-containing 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
- D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- 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
Definitions
- the invention relates to fireproof paper having a fire resistance level high, especially coated flame retardant print-write paper. She also relates to an advertising medium comprising it.
- the flame retardant salts are very numerous; one can refer for example to the chapter “Flame retardants for nonwovens” of the book “The Technical Needs: Nonwovens for Medical / surgical and Consumer Uses", TAPPI PRESS, 1986, edited by DF Durso.
- the main salts are ammonium salts, phosphorus or boron derivatives, halogenated products (brominated, chlorinated or fluorinated) such as ammonium bromides, ammonium phosphates, ammonium sulfates, sulfamates ammonium, borax, boric acid. These salts can be used as a mixture and sometimes in combination with urea.
- halogenated compounds For the halogenated compounds to be very effective, it is recommended to use them in synergy with antimony oxides; on burning they give off a hydrogen halide which combines with the antimony oxides to form an effective compound.
- These salts are generally applied to the surface of the paper.
- a flame resistant paper which is useful for manufacturing decorative laminated papers.
- This paper contains an incombustible filler which is preferably mica, possibly combined with vermiculite.
- This paper is not impregnated with a flame retardant salt and its level of flame resistance is not specifically mentioned.
- these fillers hydroxides or hydrates of alumina, magnesium hydroxides and antimony oxides are used in particular, but the latter are only effective when combined with halogenated, in particular chlorinated, compounds.
- the paper Due to the sensitivity of salts to humidity, the paper will have a stability weak dimensional, which will be detrimental in many applications. Indeed dimensional stability is very often sought and necessary, to avoid, for example in the case of printable papers, that the printing has flat or surface defects. It will be especially the case for poster papers.
- a disadvantage of flame retardant fillers is that, even when used in large quantities, it is not possible to reach a level as high in fire resistance as the classification level M1. Through elsewhere, it becomes difficult to incorporate high mass charge rates when of making a sheet of paper. In addition when the rate of charges increases, the mechanical characteristics of the paper, in particular the resistance tear and resistance to bending or stiffness decreases. On the other hand, from an economic point of view, it may be advantageous to replace cellulose fibers with fillers, which are less expensive than cellulose.
- halogenated compounds are those they must be used in synergy with antimony oxides, to form a product which has good fire resistance.
- the halogenated latexes halogenated polymers used in the form of a stable aqueous dispersion
- the chlorinated latexes used in the paper industry can be latexes of copolymers, one of the comonomers of which is vinyl chloride; in addition, very often one of the comonomers of vinyl chloride is vinyl acetate.
- a first object of the invention is to provide a fireproof paper having a high fire resistance, in particular being able to comply with the M1 classification.
- a second object of the invention is to provide fireproof paper, dimensionally stable, not very sensitive to humidity.
- a third object of the invention is to provide a printable flame retardant paper and in particular a flame retardant print-write paper coated at least on one side.
- Another object of the invention is to provide a flame-retardant advertising medium in particular such as a hanging poster or a flame-retardant display.
- the paper is preferably characterized by the fact that it comprises, in bulk, the mixture of cellulose fibers, fillers having properties of flame retardance and halogenated polymer, this mixture constituting the base support and that it comprises, on at least one of the faces of said support base, flame retardant salt.
- the paper is made from cellulose fibers. In addition, it may include other fibers such as artificial, synthetic or mineral fibers. These mineral fibers can be cut glass fibers or possibly have been incorporated in the form of glass wool or rock wool.
- the paper preferably includes a bonding agent which is added to the base mixture. It can also include dyes or colored pigments, opacifying agents, optical brighteners, fungistatic or bacteriostatic agents as well as other adjuvants commonly used in stationery such as anti-foaming agents, viscosity regulating agents.
- the halogenated polymer is a polymer chlorinated and preferably it comprises a monomer chosen from chloride of vinyl and vinylidene chloride.
- the fireproof paper according to the invention is characterized in that the chlorinated polymer is a copolymer, one of the comonomers of which is vinyl chloride, this monomer being present in an amount of at least 10% by dry weight in the copolymer. More particularly the chloride comonomer of vinyl is present at a rate of at least 30% by dry weight in the copolymer, preferably at a rate of at least 70%.
- chlorinated polymer use will advantageously be made of a vinyl chloride-vinyl acetate-ethylene copolymer chosen from the copolymers comprising these comonomers respectively in the proportions 70 - 20 - 10 or 30 - 60 - 10 by dry weight of the copolymer.
- the fireproof paper according to the invention is characterized in that the quantity of halogenated polymer is between 1 and 5 parts by dry weight per 100 parts of the basic mixture.
- the fireproof paper according to the invention is characterized in that the non-combustible filler having flame retardant properties is chosen from aluminum hydroxides, aluminum oxide hydrates, in particular oxide trihydrates aluminum, magnesium hydroxides, hydrated calcium carbonates, hydrated magnesium carbonates or mixtures thereof.
- antimony oxides are excluded, in particular because of their toxicity and moreover they are expensive.
- the composition of the paper according to the invention developed by the Applicant is remarkable in particular because despite the use of a halogenated latex, it makes it possible to achieve a high level of fire resistance without requiring the synergistic addition of an antimony oxide.
- aluminum hydroxides or alumina trihydrates will be used which have flame retardancy and also anti-smoke performance.
- Aluminum hydroxides [Al (OH) 3] form around 160 ° C alumina trihydrates (Al2O3, 3 H2O) which give off water vapor at high temperatures, this water vapor dilutes the gases emitted into presence of flames by the other constituents of the paper or of the product using this paper.
- the fillers, in particular aluminum hydroxides or alumina hydrates may have been surface treated to act on their physical properties or on the viscosity.
- the incombustible fillers with flame retardant effect are incorporated in quantities such that the ratio R of the said fillers to the cellulose fibers, by dry weight, is preferably between 1 and 3, the dry weight being expressed relative to a paper. dried at 100 ° C.
- the invention is also remarkable by the fact that the charge retention is very good (greater than 95%) when a vinyl latex is used.
- These fillers have an average particle size, determined with a laser particle size analyzer, of between 5 and 60 ⁇ m, preferably between 8 and 15 ⁇ m.
- the paper may include other fillers usually used in stationery and chosen so that they do not disturb the fire resistance, in particular the M1 classification.
- the flame retardant salt soluble or dispersible in an aqueous medium can be chosen from the salts mentioned above; preferably derivatives of phosphoric acid and more particularly an ammonium salt of these derivatives are used.
- the salt is preferably brought to the surface of the base support and in particular by means of a size press or an impregnator or by spraying. This salt is brought in a small quantity, at a rate preferably less than 8% and more more more preferably at a rate of between 1 and 6% by dry weight relative to the basic mixture. It is possible to add to the composition flame retardant salt of other compounds commonly used in the field of papers, in particular a sizing agent and a binder.
- a pigmented layer is deposited on the fireproof paper to improve its printability.
- This pigmented layer can be a layer conventionally used in the field of coated printing-writing papers; it is generally based on coating pigments (kaolin, calcium carbonate %) and water-soluble binders (starch, PVA ...) or binders in the form of polymers in stable aqueous dispersions (latex), and optionally d optical brighteners, tinting dyes, bonding agents.
- the layer may comprise a flame retardant salt or a flame retardant filler for an even better level of fire resistance, however the invention is remarkable in that it makes it possible to obtain a flame retardant coated printing-writing paper whose level of resistance to fire makes it possible to classify said coated paper in category M1 without the addition of a flame retardant salt in the layer.
- the pigmented layer is applied by any usual coating means such as air space, the so-called CHAMPION coating, coating by rotogravure, etc.
- the coated flame retardant paper is produced by depositing the pigmented layer on the base support. surface treated with flame retardant salt.
- Flame retardant paper can be coated or surfaced with a special composition to improve inkjet printing.
- the flame-retardant paper according to the invention in particular paper with the pigmented layer will have good printability, it may be printable in particular by offset printing, by screen printing, by gravure printing or by inkjet printing.
- the flame retardant paper comprises at least two papers as previously described and in accordance with the invention, laminated with the aid of an adhesive composition.
- the adhesive composition is not flame retardant.
- the invention is also remarkable in that it makes it possible to obtain coated, laminated and flame retardant paper whose level of fire resistance makes it possible to classify said laminated paper in category M1 without the addition of a flame retardant salt. the adhesive composition.
- This adhesive composition can be tinted or colored in particular in a dark or even black shade, for example by adding carbon black, so as to have a well opaque laminated paper.
- the fireproof paper obtained, with or without a pigmented printing printing layer and laminated or not, has a grammage of between 100 and 2000 g / m 2 , preferably between 200 and 1500 g / m 2 .
- the paper consists of several papers laminated or produced by other means such as being produced on a multijet paper machine.
- the interlayer paper is a paper mainly consisting of cellulose fibers and a wet strength agent, this paper being impregnated, for example using a size press, with a composition comprising a flame retardant salt.
- This salt can be chosen from those mentioned above; it is present in an amount of about 10 to 30% by dry weight relative to the interlayer.
- this interlayer has a grammage of between approximately 100 to 300 g / m 2 .
- This interlayer can be laminated between the two exterior papers using an adhesive composition which can be a white glue or a black glue.
- an adhesive composition which can be a white glue or a black glue.
- the invention also relates to the use of fireproof paper produced as described above, coated or uncoated, for manufacturing a paper advertising medium (hanging posters, displays in particular used for advertising at points of sale).
- the invention also relates to the fire-retardant paper advertising medium itself, this medium comprising said fire-resistant paper with the non-combustible charges; preferably it comprises two of said fireproof papers with non-combustible fillers which can be laminated; according to a particular case between said papers is laminated at least one interlayer paper as described above.
- the fireproof paper according to the invention in particular when the basic mixture has a high charge rate, is produced according to the process called double flocculation described in patent EP-B1-0 006390.
- the ratio R of flame retardant charges to cellulose fibers is 1.37 "dry" weight, the concept of dry weight being related to paper dried at 100 ° C (the flame retardant charges are hydrated, the water molecules being chemically linked to alumina, they are still linked to 100 ° C).
- the support obtained has a grammage of 320 g / m 2 and a thickness of 470 ⁇ m.
- the reaction to fire of the support paper obtained is tested with an electric burner according to the French standard AFNOR NF P 92-503 of December 1995, standard established in conjunction with the French decree exposed above.
- This support has a fire resistance which classifies it in category M2, therefore in a category lower than category M1.
- the support is impregnated by the flame retardant bath in a laboratory size press and then the treated support is dried at around 100 ° C.
- the recovery of the flame-retardant composition by the base support, by dry weight, is 10 g / m 2 .
- the reaction to fire of the paper obtained is tested with an electric burner as previously, it meets the fire classification M1 therefore in accordance with the invention.
- the degree of Cobb bonding (1 minute, water) is measured according to the standard. international ISO 535, it is 50.
- This layer is deposited at a rate of 25 g / m 2 by dry weight.
- the coated paper is tested with an electric burner as before; it meets the fire classification M1 therefore in accordance with the invention. Furthermore, its degree of Cobb bonding (1 minute, water) is measured according to the international standard ISO 535, it is 40 g / m 2 .
- Another sample is produced for which the adhesive composition is not a white glue but a black glue, it is an opacifying glue which contains carbon black.
- the different laminated papers obtained are fire tested as before; they meet the fire classification M1 therefore in accordance with the invention. Furthermore, their Cobb bonding degree (1 minute, water) according to the international standard ISO 535, is always 40 g / m 2 . It is checked that the paper coated before or after laminating prints well, in particular by screen printing and by offset.
- Example 1 Is carried out as in Example 1, a flame retardant paper according to the invention but the chlorinated polymer is a copolymer of vinyl chloride-vinyl acetate-crosslinkable ethylene comprising 30% by dry weight of vinyl chloride, 60% by weight dry vinyl acetate and 10% by dry weight of ethylene, it is stabilized by an anionic surfactant.
- the constituents of the paper are placed in the same proportions as in Example 1.
- This support has a fire resistance which classifies it in category M2, therefore in a category lower than category M1.
- the base support is impregnated with the same flame retardant bath as in Example 1, then dried at 100 ° C; the recovery of the flame retardant composition by the base support, by dry weight, is 10 g / m 2 . It contains 2.6% by dry weight of flame retardant salt compared to the basic support.
- the reaction to fire of the paper obtained is tested with an electric burner as above, it meets the fire classification M1 therefore in accordance with the invention.
- its degree of Cobb bonding (1 minute, water) is measured according to the international standard ISO 535, it is 80. Compared with Example 1, the bonding is less good, probably because of the higher content of vinyl acetate in chlorinated polymer which is hydrophilic.
- a pigmented printing-writing layer which has the composition of that of Example 1 is deposited on one side of the flame-retardant paper previously obtained. Likewise, this layer is deposited at a rate of 25 g / m 2 .
- the coated paper is fire tested; it is classified in category M1 therefore in accordance with the invention.
- its degree of Cobb bonding (1 minute, water) is measured according to the international standard ISO 535, it is 43 g / m 2 .
- a laminated sample is produced as in Example 1.
- a laminated sample is produced as in Example 1.
- a laminated sample is produced as in Example 1.
- a laminated sample is produced as in Example 1.
- the papers obtained are tested on fire as above. It is checked that the paper coated before or after laminating prints well, in particular by screen printing and by offset.
- the characteristics of the papers obtained at the various stages are given in Table 1.
- the grammage is determined according to the international standard ISO 536.
- the thickness is determined according to the international standard ISO 534.
- the degree of Cobb bonding is determined according to international standard ISO 535.
- the TABER stiffness is determined according to international standard ISO 2493.
- the tensile strength is determined according to the international standard ISO 1924/2.
- the whiteness is determined according to the international standard ISO 2470, at 457 nm.
- the BENDTSEN porosity is determined according to the international standard ISO 5636/3.
- the BENDTSEN roughness is determined according to French standard NF Q 03-049.
- the dimensional stability is determined on a PRUFBAU device which measures the elongation differences in% of a paper test piece 50 mm wide and 140 mm long, cut in the running direction of the paper machine or in the direction cross, between 65 and 15% relative humidity (RH) and 98 and 15% relative humidity.
- RH relative humidity
- a flame retardant paper according to the invention is produced as in Example 1 but the ratio R (fibers / fillers) is 1.93 and the content of chlorinated polymer is 2.90% of the basic mixture. The charge retention is very good, it is greater than 95%.
- the support is impregnated with the flame-retardant bath, then it is coated as in Example 1. Samples are laminated as in Example 1. The papers obtained are tested on fire as before; the papers obtained after treatment in a size press (impregnated, coated, laminated) all meet the M1 fire classification therefore in accordance with the invention. It is checked that the paper coated before or after laminating prints well, in particular by screen printing and by offset.
- a flame retardant paper in accordance with the invention is produced as in Example 1, but the ratio R (fibers / fillers) is 2.50 and the level of chlorinated polymer is 3.15% of the basic mixture. The charge retention is very good, it is greater than 95%.
- the support is impregnated with the flame retardant bath, it is coated as in Example 1.
- the papers obtained are tested on fire as before; the papers obtained after treatment in a size press (impregnated, coated, laminated) all meet the M1 fire classification therefore in accordance with the invention. It is checked that the paper coated before or after laminating prints well, in particular by screen printing and by offset.
- a base support impregnated industrially is impregnated as in step 1 of Example 3, its grammage being 260 g / m 2 , by varying the level of flame retardant salt according to the following rates: 6%, 8%, 10% and 15% to carry out Examples 6 to 9 respectively.
- the degree of bonding of each of the base supports thus treated is respectively 60, 70, 78 and 90 g / m 2 .
- a basic support is produced as in step 1 of Example 1, but the polymer used is a non-halogenated polymer, it is a styrene-butadiene copolymer used in the form of a stable aqueous dispersion.
- the polymer used is a non-halogenated polymer, it is a styrene-butadiene copolymer used in the form of a stable aqueous dispersion.
- a basic support is produced as in step 1 of Example 1 but without making a surface treatment with a flame retardant salt, the halogenated binder being moreover placed in large quantity, ie at a rate of 16%.
- the fire resistance of the paper it does not reach the M1 classification, the paper ignites completely, despite the high rate of halogenated polymer.
- a basic support is produced as in step 1 of Example 1 but without making a surface treatment with a flame retardant salt, the flame retardant filler being moreover put in large quantity, the filler / fiber ratio being 8.
- a basic support is produced as in step 1 of Example 1 with the surface treatment with a flame retardant salt, but the flame retardant filler is put in a small quantity, the filler / fiber ratio being 0.95.
- the dry recovery of the flame retardant impregnation composition is 11.1 g / m 2 . It contains 2.95% flame retardant salt by dry weight compared to the base support.
- a base paper is produced as in step 1 of comparative example 15 above 1 with the surface treatment with a flame retardant salt, the flame retardant filler being always in small quantity, the filler / fiber ratio being 0 , 95, but the recovery by fire retardant salt paper is doubled. (the dry recovery of the composition is 22.6 g / m 2 ). It contains 6% flame retardant salt by dry weight compared to the base support.
- a base paper is produced as in step 1 of Example 1 with the surface treatment with a flame retardant salt but the non-combustible charge is not a flame retardant charge, this charge is mica, the charge ratio / fibers also being 1.37.
- the paper ignites completely.
- An advertising medium of 750 g / m 2 is produced which consists of three jets of paper.
- the two outer jets are fireproof coated papers obtained according to Example 3.
- the intermediate jet is a paper mainly consisting of cellulose fibers and a wet strength agent, this paper being impregnated, for example using a size press, with a composition comprising a flame retardant salt.
- This salt can be that used to treat the support, it is present in an amount of about 20% by dry weight relative to the interlayer.
- This interlayer has a grammage of approximately 160 g / m 2 .
- This interlayer is laminated between the two exterior papers using an adhesive composition which can be a white glue or a black non-flame retardant glue and deposited at a rate of approximately 20 g / m 2 per side.
- the complex obtained is fire tested, it is classified M1.
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Abstract
Description
L'invention concerne un papier ignifugé ayant un niveau de résistance au feu élevé, notamment un papier d'impression-écriture ignifugé couché. Elle concerne ausi un support publicitaire le comportant.The invention relates to fireproof paper having a fire resistance level high, especially coated flame retardant print-write paper. She also relates to an advertising medium comprising it.
L'utilisation des papiers dans des lieux soumis à des critères de sécurité contre
l'incendie ou pour lesquels il est préférable qu'ils répondent à de tels critères, a
conduit à développer des papiers ignifugés avec des degrés plus ou moins
élévés de résistance au feu.
Il est important notamment que soient résistants au feu les papiers utilisés dans
les magasins comme les supports publicitaires en papier utilisés pour la publicité
sur les lieux de vente (souvent nommée sous sa forme abrégée PLV) qui servent
à confectionner des présentoirs pour le produit à promouvoir ou à faire des
affiches publicitaires suspendues.
En France est paru un arrêté du 30 juin 1983 modifié par l'arrêté du 28 août
1991 du Ministère de l'Intérieur et de la Décentralisation français, pris en
application du Code de la construction et de l'habitation, relatif à la sécurité
contre l'incendie et qui précise notamment comment étudier le comportement
au feu et classer les matériaux et éléments de construction .
Dans le cadre de l'invention, on s'intéresse à un papier ignifugé d'un niveau de
résistance au feu élevé c'est-à-dire ayant une réaction au feu permettant de le
classer dans la catégorie M1, selon le classement établi par l'arrêté français
mentionné ci-dessus.The use of papers in places subject to fire safety criteria or for which it is preferable that they meet such criteria, has led to the development of flame retardant papers with more or less high degrees of resistance to fire.
In particular, it is important that the fire-resistant papers used in stores, such as the paper advertising media used for point-of-sale advertising (often called in its abbreviated form POS), which are used to make displays for the product to be promoted, be resistant to fire. or to make hanging advertising posters.
In France a decree of June 30, 1983 was published, modified by the decree of August 28, 1991 of the French Ministry of the Interior and Decentralization, adopted in application of the Construction and Housing Code, relating to security against fire and which specifies in particular how to study fire behavior and classify building materials and elements.
In the context of the invention, we are interested in a fireproof paper with a high level of fire resistance, that is to say having a reaction to fire making it possible to classify it in category M1, according to the established classification by the French decree mentioned above.
On connait déjà des papiers ignifugés réalisés grâce à l'emploi de sels ignifugeants, solubles ou dispersables en milieu aqueux; par exemple dans la demande de brevet DE 2 948 974 on a décrit un papier imprégné d'une composition aqueuse ignifugeante contenant entre 20 et 50% d'un sel organique ignifugeant et en particulier des sels d'ammonium et de phosphates. We already know fireproof papers made thanks to the use of salts flame retardants, soluble or dispersible in an aqueous medium; for example in the patent application DE 2 948 974 a paper impregnated with a flame retardant aqueous composition containing between 20 and 50% of a salt organic flame retardant and in particular ammonium and phosphate salts.
Ces sels ignifugeants sont très nombreux; on peut se reporter par exemple au
chapitre "Flame retardants for nonwovens" du livre "The Technical Needs:
Nonwovens for Medical/surgical and Consumer Uses", TAPPI PRESS,1986,
édité par D.F. Durso.
Les principaux sels sont des sels d'ammonium, des dérivés du phosphore ou du
bore, des produits halogénés (bromés, chlorés ou fluorés) tels que les bromures
d'ammonium, les phosphates d'ammonium, les sulfates d'ammonium, les
sulfamates d'ammonium, le borax, l'acide borique. Ces sels peuvent être utilisés
en mélange et parfois en association avec de l'urée. Pour que les composés
halogénés soient très efficaces, il est recommandé de les utiliser en synergie
avec des oxydes d'antimoine; en brûlant ils dégagent un halogènure
d'hydrogène qui se combine avec les oxydes d'antimoine pour former un
composé efficace.
Ces sels sont appliqués en général à la surface du papier.These flame retardant salts are very numerous; one can refer for example to the chapter "Flame retardants for nonwovens" of the book "The Technical Needs: Nonwovens for Medical / surgical and Consumer Uses", TAPPI PRESS, 1986, edited by DF Durso.
The main salts are ammonium salts, phosphorus or boron derivatives, halogenated products (brominated, chlorinated or fluorinated) such as ammonium bromides, ammonium phosphates, ammonium sulfates, sulfamates ammonium, borax, boric acid. These salts can be used as a mixture and sometimes in combination with urea. For the halogenated compounds to be very effective, it is recommended to use them in synergy with antimony oxides; on burning they give off a hydrogen halide which combines with the antimony oxides to form an effective compound.
These salts are generally applied to the surface of the paper.
Par ailleurs dans la demande de brevet français FR 2 547 239 on a décrit un
papier résistant à la flamme utile pour fabriquer des papiers stratifiés décoratifs.
Ce papier comporte une charge incombustible qui est de préférence du mica en
association éventuellement avec de la vermiculite. Ce papier n'est pas imprégné
d'un sel ignifugeant et son niveau de résistance à la flamme n'est pas
mentionné précisemment.
On peut en effet aussi réaliser des papiers à caractère ignifuge en utilisant des
charges incombustibles, et notamment des charges qui ont en plus la
particularité d'avoir un effet de retardement de flamme avec éventuellement en
plus un effet antifumée. Parmi ces charges, on utilise notamment les
hydroxydes ou hydrates d'alumine, les hydroxydes de magnésium, des oxydes
d'antimoine mais ces derniers ne sont efficaces qu'associés avec des composés
halogénés en particulier chlorés.Furthermore, in French patent application FR 2 547 239, a flame resistant paper has been described which is useful for manufacturing decorative laminated papers. This paper contains an incombustible filler which is preferably mica, possibly combined with vermiculite. This paper is not impregnated with a flame retardant salt and its level of flame resistance is not specifically mentioned.
It is indeed also possible to produce papers with a fire-retardant nature using non-combustible fillers, and in particular fillers which have the additional feature of having a flame retardant effect with possibly also an antifume effect. Among these fillers, hydroxides or hydrates of alumina, magnesium hydroxides and antimony oxides are used in particular, but the latter are only effective when combined with halogenated, in particular chlorinated, compounds.
L'un des inconvénients des sels ignifugeants est leur sensibilité à l'humidité et à l'eau. Si on veut obtenir un niveau d'ignifugation élevé, il faut utiliser ces sels en grandes quantités, jusqu'à 10-20 % en poids sec par rapport à la masse du papier avant traitement.One of the disadvantages of flame retardant salts is their sensitivity to moisture and the water. If you want to obtain a high level of fireproofing, you must use these salts in large quantities, up to 10-20% by dry weight based on the mass of the paper before processing.
Du fait de la sensibilité des sels à l'humidité, le papier aura une stabilité dimensionnelle faible, ce qui sera préjudiciable dans de nombreuses applications. En effet la stabilité dimensionnelle est très souvent recherchée et nécessaire, pour éviter, par exemple dans le cas des papiers imprimables, que l'impression présente des défauts d'aplat ou d'état de surface. Ce sera notamment le cas pour les papiers pour affiches.Due to the sensitivity of salts to humidity, the paper will have a stability weak dimensional, which will be detrimental in many applications. Indeed dimensional stability is very often sought and necessary, to avoid, for example in the case of printable papers, that the printing has flat or surface defects. It will be especially the case for poster papers.
Du fait de cette sensibilité des sels à l'humidité, il sera également difficile d'avoir un bon collage du papier (au sens résistance à l'absorption d'eau selon la norme internationale ISO 535). Ce faible collage défavorisera une bonne imprimabilité du papier ainsi que le dépôt correct d'une couche à la surface du papier, comme par exemple d'une couche pigmentée usuellement appliquée aux papiers impression-écriture pour améliorer leur imprimabilité. En effet, la surface du papier étant trop absorbante, la couche sera trop enterrée dans le papier ou s'étalera de façon non uniforme.Because of this sensitivity of salts to humidity, it will also be difficult to have a good bonding of the paper (in the sense resistance to water absorption according to international standard ISO 535). This weak bonding will disadvantage a good printability of the paper as well as the correct deposition of a layer on the surface of the paper, such as a pigmented layer usually applied to print-write papers to improve their printability. Indeed, the surface paper is too absorbent, the layer will be too buried in the paper or will spread unevenly.
Un autre inconvénient des sels ignifugeants est qu'ils sont chers.Another disadvantage of flame retardant salts is that they are expensive.
Un inconvénient des charges avec effet à retardement de flamme est que, même employées en grandes quantités, il n'est pas possible d'atteindre un niveau aussi élevé à la résistance au feu que le niveau de classement M1. Par ailleurs, il devient difficile d'incorporer des taux élevés de charges en masse lors de la fabrication d'une feuille de papier. De plus lorsque le taux de charges augmente, les caractéristiques mécaniques du papier, notamment la résistance à ta déchirure et la résistance à la flexion ou la rigidité , diminuent. En revanche, d'un point de vue économique, il peut être avantageux de remplacer les fibres de cellulose par des charges, moins coûteuses que la cellulose. A disadvantage of flame retardant fillers is that, even when used in large quantities, it is not possible to reach a level as high in fire resistance as the classification level M1. Through elsewhere, it becomes difficult to incorporate high mass charge rates when of making a sheet of paper. In addition when the rate of charges increases, the mechanical characteristics of the paper, in particular the resistance tear and resistance to bending or stiffness decreases. On the other hand, from an economic point of view, it may be advantageous to replace cellulose fibers with fillers, which are less expensive than cellulose.
Un inconvénient des composés halogénés est qu'ils doivent être utilisés en
synergie avec des oxydes d'antimoine, pour former un produit qui a une bonne
résistance au feu.
Par ailleurs, les latex halogénés (polymères halogénés utilisés sous forme d'une
dispersion aqueuse stable), en particulier les latex chlorés utilisés dans le
domaine papetier peuvent être des latex de copolymères, dont l'un des
comonomères est le chlorure de vinyle ; de plus, bien souvent l'un des
comonomères du chlorure de vinyle est l'acétate de vinyle. Or, un inconvénient
des latex vinyliques est qu'ils ne permettent ni d'avoir une bonne rétention des
charges employées dans le domaine papetier, ni d'avoir un bon égouttage de la
feuille, ni de bonnes caractéristiques en partie humide, lors de la fabrication du
papier, même lorsqu'on fabrique le papier selon le procédé de double floculation
décrit dans le brevet EP-B-6390.
Un tel inconvénient est mentionné, par exemple, dans le brevet EP-B1-451 554.A disadvantage of halogenated compounds is that they must be used in synergy with antimony oxides, to form a product which has good fire resistance.
Furthermore, the halogenated latexes (halogenated polymers used in the form of a stable aqueous dispersion), in particular the chlorinated latexes used in the paper industry can be latexes of copolymers, one of the comonomers of which is vinyl chloride; in addition, very often one of the comonomers of vinyl chloride is vinyl acetate. However, a disadvantage of vinyl latexes is that they do not allow either to have a good retention of the fillers used in the paper industry, or to have a good drainage of the sheet, or good characteristics in the wet part, during the making paper, even when making paper according to the double flocculation process described in patent EP-B-6390.
Such a drawback is mentioned, for example, in patent EP-B1-451,554.
Un premier but de l'invention est de fournir un papier ignifugé ayant une
résistance élevée au feu, en particulier pouvant être conforme au classement
M1.
Un second but de l'invention est de fournir un papier ignifugé, stable
dimensionnellement, peu sensible à l'humidité.
Un troisième but de l'invention est de fournir un papier ignifugé imprimable et
en particulier un papier ignifugé impression-écriture couché au moins sur une
face.
Un autre but de l'invention est de fournir un support publicitaire ignifugé
notamment tel que affiche suspendue ou présentoir ignifugé.A first object of the invention is to provide a fireproof paper having a high fire resistance, in particular being able to comply with the M1 classification.
A second object of the invention is to provide fireproof paper, dimensionally stable, not very sensitive to humidity.
A third object of the invention is to provide a printable flame retardant paper and in particular a flame retardant print-write paper coated at least on one side.
Another object of the invention is to provide a flame-retardant advertising medium in particular such as a hanging poster or a flame-retardant display.
Au terme de nombreux essais de composés et de formulations de papiers, la Demanderesse a trouvé que l'on peut fabriquer un papier résistant au feu si on réalise un papier dont la composition synergique comprend :
- au moins des fibres de cellulose et au moins des charges incombustibles ayant des propriétés de retardement de flamme, le rapport en poids sec R charges/fibres étant compris entre 1 et 9,
- entre 1 et 15 parts en poids sec, pour 100 parts du mélange de base, d'au moins un polymère halogéné utilisé sous forme d'une dispersion aqueuse stable, ces trois composés constituant le mélange de base, et
- entre 0,1 et 10 %, en poids sec du mélange de base. d'au moins un sel ignifugeant soluble ou dispersable en milieu aqueux,
- at least cellulose fibers and at least incombustible fillers having flame retardancy properties, the dry weight ratio R fillers / fibers being between 1 and 9,
- between 1 and 15 parts by dry weight, per 100 parts of the base mixture, of at least one halogenated polymer used in the form of a stable aqueous dispersion, these three compounds constituting the base mixture, and
- between 0.1 and 10%, by dry weight of the basic mixture. at least one flame retardant salt soluble or dispersible in an aqueous medium,
De préférence le papier se caractérise par le fait qu'il comprend, en masse, le mélange des fibres de cellulose, des charges ayant des propriétés de retardement de flamme et du polymère halogéné, ce mélange constituant le support de base et qu'il comprend, sur au moins l'une des faces dudit support de base, le sel ignifugeant.The paper is preferably characterized by the fact that it comprises, in bulk, the mixture of cellulose fibers, fillers having properties of flame retardance and halogenated polymer, this mixture constituting the base support and that it comprises, on at least one of the faces of said support base, flame retardant salt.
Le papier est à base de fibres de cellulose. En outre il peut comporter d'autres
fibres comme des fibres artificielles, synthétiques ou des fibres minérales. Ces
fibres minérales peuvent être des fibres de verre coupées ou éventuellement
avoir été incorporées sous forme de laine de verre ou de laine de roche.
Le papier comporte de préférence un agent de collage qu'on ajoute au mélange
de base.
Il peut comporter aussi des colorants ou des pigments colorés, des agents
opacifiants, des azurants optiques, des agents fongistatiques ou
bactériostatiques ainsi que d'autres adjuvants utilisés habituellement en
papeterie comme des agents anti-mousse, des agents régulateurs de viscosité.The paper is made from cellulose fibers. In addition, it may include other fibers such as artificial, synthetic or mineral fibers. These mineral fibers can be cut glass fibers or possibly have been incorporated in the form of glass wool or rock wool.
The paper preferably includes a bonding agent which is added to the base mixture.
It can also include dyes or colored pigments, opacifying agents, optical brighteners, fungistatic or bacteriostatic agents as well as other adjuvants commonly used in stationery such as anti-foaming agents, viscosity regulating agents.
Selon un cas particulier de l'invention, le polymère halogéné est un polymère chloré et de préférence il comporte un monomère choisi parmi le chlorure de vinyle et le chlorure de vinylidène. According to a particular case of the invention, the halogenated polymer is a polymer chlorinated and preferably it comprises a monomer chosen from chloride of vinyl and vinylidene chloride.
De préférence, le papier ignifugé selon l'invention se caractérise par le fait que le polymère chloré est un copolymère dont l'un des comonomères est le chlorure de vinyle, ce monomère étant présent à raison d'au moins 10 % en poids sec dans le copolymère. Plus particulièrement le comonomère de chlorure de vinyle est présent à raison d'au moins 30 % en poids sec dans le copolymère, de préférence à raison d'au moins 70 %.Preferably, the fireproof paper according to the invention is characterized in that the chlorinated polymer is a copolymer, one of the comonomers of which is vinyl chloride, this monomer being present in an amount of at least 10% by dry weight in the copolymer. More particularly the chloride comonomer of vinyl is present at a rate of at least 30% by dry weight in the copolymer, preferably at a rate of at least 70%.
Comme polymère chloré on utilisera avantageusement un copolymère chlorure
de vinyle-acétate de vinyle-éthylène choisi parmi les copolymères comportant
ces comonomères respectivement dans les proportions 70 - 20 - 10 ou 30 - 60
- 10 en poids sec du copolymère.
De préférence le papier ignifugé selon l'invention se caractérise par le fait que la
quantité en polymère halogéné est comprise entre 1 et 5 parts en poids sec
pour 100 parts du mélange de base.As chlorinated polymer, use will advantageously be made of a vinyl chloride-vinyl acetate-ethylene copolymer chosen from the copolymers comprising these comonomers respectively in the proportions 70 - 20 - 10 or 30 - 60 - 10 by dry weight of the copolymer.
Preferably the fireproof paper according to the invention is characterized in that the quantity of halogenated polymer is between 1 and 5 parts by dry weight per 100 parts of the basic mixture.
De préférence le papier ignifugé selon l'invention se caractérise par le fait que la
charge incombustible ayant des propriétés de retardement de flamme est
choisie parmi les hydroxydes d'aluminium, les hydrates d'oxyde d'aluminium, en
particulier les trihydrates d'oxyde d'aluminium, les hydroxydes de magnésium,
les carbonates de calcium hydratés, les carbonates de magnésium hydratés ou
leurs mélanges.
De préférence les oxydes d'antimoine sont exclus, notamment à cause de leur
toxicité et par ailleurs ils sont chers. En effet la composition du papier selon
l'invention mis au point par la Demanderesse est remarquable notamment car
malgré l'emploi d'un latex halogéné, elle permet d'atteindre un niveau élevé de
résistance au feu sans nécessiter l'ajout synergique d'un oxyde d'antimoine.
On utilisera préférentiellement les hydroxydes d'aluminium ou les trihydrates
d'alumine qui ont des performances de retardement de flamme et aussi
d'antifumée. Les hydroxydes d'aluminium [Al(OH)3] forment vers 160°C des
trihydrates d'alumine (Al2O3, 3 H2O) qui dégagent de la vapeur d'eau aux
températures élevées, cette vapeur d'eau dilue les gaz émis en présence de
flammes par les autres constituants du papier ou du produit utilisant ce papier.
Les charges, notamment les hydroxydes d'aluminium ou les hydrates d'alumine
peuvent avoir été traitées en surface pour agir sur leurs propriétés physiques ou
sur la viscosité.
Plus particulièrement les charges incombustibles à effet de retardement de
flamme sont incorporées en quantités telles que le rapport R des dites charges
aux fibres de cellulose, en poids sec, soit de préférence compris entre 1 et 3, le
poids sec étant exprimé relativement à un papier séché à 100°C.
L'invention est aussi remarquable par le fait que la rétention des charges est
très bonne (supérieure à 95 %) lorsque l'on utilise un latex vinylique.
Ces charges ont une granulométrie moyenne, déterminée avec un granulomètre
au laser, comprise entre 5 et 60 µm, de préférence entre 8 et 15 µm.
Le papier peut comporter d'autres charges usuellement utilisées en papeterie et
choisies de façon à ce qu'elles ne perturbent pas la résistance au feu,
notamment le classement M1.Preferably the fireproof paper according to the invention is characterized in that the non-combustible filler having flame retardant properties is chosen from aluminum hydroxides, aluminum oxide hydrates, in particular oxide trihydrates aluminum, magnesium hydroxides, hydrated calcium carbonates, hydrated magnesium carbonates or mixtures thereof.
Preferably antimony oxides are excluded, in particular because of their toxicity and moreover they are expensive. Indeed, the composition of the paper according to the invention developed by the Applicant is remarkable in particular because despite the use of a halogenated latex, it makes it possible to achieve a high level of fire resistance without requiring the synergistic addition of an antimony oxide.
Preferably, aluminum hydroxides or alumina trihydrates will be used which have flame retardancy and also anti-smoke performance. Aluminum hydroxides [Al (OH) 3] form around 160 ° C alumina trihydrates (Al2O3, 3 H2O) which give off water vapor at high temperatures, this water vapor dilutes the gases emitted into presence of flames by the other constituents of the paper or of the product using this paper. The fillers, in particular aluminum hydroxides or alumina hydrates may have been surface treated to act on their physical properties or on the viscosity.
More particularly, the incombustible fillers with flame retardant effect are incorporated in quantities such that the ratio R of the said fillers to the cellulose fibers, by dry weight, is preferably between 1 and 3, the dry weight being expressed relative to a paper. dried at 100 ° C.
The invention is also remarkable by the fact that the charge retention is very good (greater than 95%) when a vinyl latex is used.
These fillers have an average particle size, determined with a laser particle size analyzer, of between 5 and 60 μm, preferably between 8 and 15 μm.
The paper may include other fillers usually used in stationery and chosen so that they do not disturb the fire resistance, in particular the M1 classification.
Le sel ignifugeant soluble ou dispersable en milieu aqueux peut être choisi parmi
les sels cités plus haut; de préférence on utilise des dérivés de l'acide
phosphorique et plus particulièrement un sel d'ammonium de ces dérivés.
Le sel est apporté de préférence à la surface du support de base et en
particulier au moyen d'une presse encolleuse ou d'une imprégnatrice ou par
pulvérisation.
Ce sel est apporté en faible quantité, à un taux de préférence inférieur à 8% et
plus plus prégérentiellement à un taux compris entre 1 et 6 % en poids sec par
rapport au mélange de base.
On peut ajouter à la composition du sel ignifugeant d'autres composés utilisés
habituellement dans le domaine des papiers, en particulier un agent de collage
et un liant. The flame retardant salt soluble or dispersible in an aqueous medium can be chosen from the salts mentioned above; preferably derivatives of phosphoric acid and more particularly an ammonium salt of these derivatives are used.
The salt is preferably brought to the surface of the base support and in particular by means of a size press or an impregnator or by spraying.
This salt is brought in a small quantity, at a rate preferably less than 8% and more more preferably at a rate of between 1 and 6% by dry weight relative to the basic mixture.
It is possible to add to the composition flame retardant salt of other compounds commonly used in the field of papers, in particular a sizing agent and a binder.
Selon un cas préféré de l'invention, le papier ignifugé pouvant être classé M1 se caractérise par le fait :
- qu'il comprend, en masse :
- des fibres de cellulose,
- des charges incombustibles ayant des propriétés de retardement de flamme choisies parmi les hydroxydes d'aluminium et/ou les hydrates d'alumine, en particulier des trihydrates d'alumine, leur granulométrie étant comprise entre 8 et 15 µm et le rapport R charges/fibres étant compris entre 1 et 3 en poids sec,
- entre 2 et 5 parts pour 100 parts du mélange de base, d'un copolymère
chlorure de vinyle-acétate de vinyle-éthylène utilisé sous forme d'une dispersion
aqueuse stable et comportant ces comonomères dans les proportions relatives
70 - 20 - 10 en poids sec, stabilisé par un surfactant anionique,
le mélange de ces trois composés (fibres, charges, polymère halogéné) constituant le mélange de base du support de base, la somme de leurs parts en poids sec faisant 100,
- et qu'il est imprégné entre 1 à 6 % en poids sec du mélange de base, d'un sel
d'ammonium d'un dérivé phosphorique comme sel ignifugeant,
le poids sec étant exprimé relativement à un papier séché à 100°C.
- that it includes, in mass:
- cellulose fibers,
- non-combustible fillers having flame retardancy properties chosen from aluminum hydroxides and / or alumina hydrates, in particular alumina trihydrates, their particle size being between 8 and 15 μm and the ratio R fillers / fibers being between 1 and 3 by dry weight,
- between 2 and 5 parts per 100 parts of the base mixture of a vinyl chloride-vinyl acetate-ethylene copolymer used in the form of a stable aqueous dispersion and comprising these comonomers in the relative proportions 70 - 20 - 10 by weight dry, stabilized by an anionic surfactant,
the mixture of these three compounds (fibers, fillers, halogenated polymer) constituting the basic mixture of the basic support, the sum of their parts by dry weight making 100,
- and that it is impregnated between 1 to 6% by dry weight of the basic mixture, of an ammonium salt of a phosphoric derivative as a flame retardant salt,
the dry weight being expressed relative to a paper dried at 100 ° C.
Selon un cas préféré de l'invention, on dépose sur le papier ignifugé une couche
pigmentée pour améliorer son imprimabilité.
Cette couche pigmentée peut être une couche classiquement utilisée dans le
domaine des papiers couchés d'impression-écriture; elle est à base en général
de pigments de couchage (kaolin, carbonate de calcium ...) et de liants
hydrosolubles (amidon, PVA ...) ou de liants sous forme de polymères en
dispersions aqueuses stables (latex), et éventuellement d'azurants optiques, de
colorants de nuançage, d'agents de collage.
En outre la couche peut comporter un sel ignifugeant ou une charge à
retardement de flamme pour un niveau de résistance au feu encore meilleur,
cependant l'invention est remarquable du fait qu'elle permet d'obtenir un papier
impression-écriture couché ignifugé dont le niveau de résistance au feu permet
de classer le dit papier couché dans la catégorie M1 sans l'ajout d'un sel
ignifugeant dans la couche.
La couche pigmentée est appliquée par tout moyen de couchage usuel comme
la lame d'air, le couchage dit CHAMPION, le couchage par héliogravure, etc ...
De préférence le papier ignifugé couché est réalisé en déposant la couche
pigmentée sur le support de base traité en surface par le sel ignifugeant.According to a preferred case of the invention, a pigmented layer is deposited on the fireproof paper to improve its printability.
This pigmented layer can be a layer conventionally used in the field of coated printing-writing papers; it is generally based on coating pigments (kaolin, calcium carbonate ...) and water-soluble binders (starch, PVA ...) or binders in the form of polymers in stable aqueous dispersions (latex), and optionally d optical brighteners, tinting dyes, bonding agents.
In addition, the layer may comprise a flame retardant salt or a flame retardant filler for an even better level of fire resistance, however the invention is remarkable in that it makes it possible to obtain a flame retardant coated printing-writing paper whose level of resistance to fire makes it possible to classify said coated paper in category M1 without the addition of a flame retardant salt in the layer.
The pigmented layer is applied by any usual coating means such as air space, the so-called CHAMPION coating, coating by rotogravure, etc. Preferably the coated flame retardant paper is produced by depositing the pigmented layer on the base support. surface treated with flame retardant salt.
Le papier ignifugé peut être couché ou surfacé avec une composition spéciale
permettant d'améliorer l'impression jet d'encre.
Le papier ignifugé selon l'invention, notamment le papier avec la couche
pigmentée aura de bonnes aptitudes à l'impression, il pourra être imprimable
notamment par impression offset, par sérigraphie, par impression héliogravure
ou encore par impression jet d'encre.
Selon un cas particulier de l'invention, le papier ignifugé comporte au moins
deux papiers tels que précédemment décrits et conformes à l'invention,
contrecollés à l'aide d'une composition adhésive. En particulier la composition
adhésive est non ignifugée.
L'invention est également remarquable du fait qu'elle permet d'obtenir un papier
couché, contrecollé et ignifugé dont le niveau de résistance au feu permet de
classer le dit papier contrecollé dans la catégorie M1 sans l'ajout d'un sel
ignifugeant à la composition adhésive.Flame retardant paper can be coated or surfaced with a special composition to improve inkjet printing.
The flame-retardant paper according to the invention, in particular paper with the pigmented layer will have good printability, it may be printable in particular by offset printing, by screen printing, by gravure printing or by inkjet printing.
According to a particular case of the invention, the flame retardant paper comprises at least two papers as previously described and in accordance with the invention, laminated with the aid of an adhesive composition. In particular, the adhesive composition is not flame retardant.
The invention is also remarkable in that it makes it possible to obtain coated, laminated and flame retardant paper whose level of fire resistance makes it possible to classify said laminated paper in category M1 without the addition of a flame retardant salt. the adhesive composition.
Cette composition adhésive peut être teintée ou colorée notamment dans une
nuance sombre voire noire, par exemple en ajoutant du noir de carbone, de
façon à avoir un papier contrecollé bien opaque.
On peut contrecoller un papier comportant une couche pigmentée sur l'une de
ces faces contre un papier non couché ou contre un autre papier couché sur
une face, les faces couchées étant à l'extérieur.
Le papier ignifugé obtenu, avec ou sans couche pigmentée d'impression écriture
et contrecollé ou non, a un grammage compris entre 100 et 2000 g/m2, de
préférence entre 200 et 1500 g/m2. Pour des grammages entre 400 et 2000
g/m2, le papier est constitué de plusieurs papiers contrecollés ou réalisés par
d'autres moyens comme d'être fabriqué sur une machine à papier multijets.This adhesive composition can be tinted or colored in particular in a dark or even black shade, for example by adding carbon black, so as to have a well opaque laminated paper.
One can laminate a paper having a pigmented layer on one of these faces against an uncoated paper or against another paper coated on one side, the coated faces being on the outside.
The fireproof paper obtained, with or without a pigmented printing printing layer and laminated or not, has a grammage of between 100 and 2000 g / m 2 , preferably between 200 and 1500 g / m 2 . For grammages between 400 and 2000 g / m 2 , the paper consists of several papers laminated or produced by other means such as being produced on a multijet paper machine.
On peut par ailleurs réaliser un papier ignifugé, notamment de fort grammage,
en assemblant trois papiers ou plus , les deux papiers extérieurs étant des
papiers couchés ignifugés tels que décrits ci-dessus et le ou les papiers
intercalaires étant composés comme ci-après.
Le papier intercalaire est un papier constitué principalement de fibres de
cellulose et d'un agent de résistance humide, ce papier étant imprégné, par
exemple à l'aide d'une presse encolleuse, d'une composition comportant un sel
ignifugeant. Ce sel pouvant être choisis parmi ceux cités précedemment; il est
présent en une quantité d'environ 10 à 30 % en poids sec par rapport à
l'intercalaire.
De préférence cet intercalaire a un grammage compris entre environ 100 à 300
g/m2.
Cet intercalaire peut être contrecollé entre les deux papiers extérieurs à l'aide
d'une composition adhésive qui peut être une colle blanche ou une colle noire.
L'intérêt d'utiliser cesdits papiers intercalaires est qu'ils permettent de conférer
une meilleure rigidité au complexe des différents papiers qu'en utilisant
seulement les papiers qui comportent les charges incombustibles. Ceci est
notamment intéressant pour fabriquer les supports publicitaires de PLV.It is also possible to produce a flame retardant paper, in particular of heavy grammage, by assembling three or more papers, the two outer papers being flame retardant coated papers as described above and the interlayer paper or papers being composed as below.
The interlayer paper is a paper mainly consisting of cellulose fibers and a wet strength agent, this paper being impregnated, for example using a size press, with a composition comprising a flame retardant salt. This salt can be chosen from those mentioned above; it is present in an amount of about 10 to 30% by dry weight relative to the interlayer.
Preferably, this interlayer has a grammage of between approximately 100 to 300 g / m 2 .
This interlayer can be laminated between the two exterior papers using an adhesive composition which can be a white glue or a black glue. The advantage of using these said intermediate papers is that they make it possible to impart better rigidity to the complex of the different papers than by using only the papers which contain the incombustible charges. This is particularly interesting for manufacturing POS advertising media.
L'invention concerne aussi l'utilisation d'un papier ignifugé réalisé comme décrit
précédemment, couché ou non couché, pour fabriquer un support publicitaire
en papier (affiches suspendues, présentoirs notamment utilisés pour la publicité
sur les lieux de vente).
L'invention concerne aussi le support publicitaire en papier ignifugé lui-même,
ce support comportant ledit papier ignifugé avec les charges incombustibles; de
préférence il comporte deux desdits papiers ignifugés avec les charges
incombustibles qui peuvent être contrecollés; selon un cas particulier entre
cesdits papiers est contrecollé au moins un papier intercalaire tel que décrit
précédemment.The invention also relates to the use of fireproof paper produced as described above, coated or uncoated, for manufacturing a paper advertising medium (hanging posters, displays in particular used for advertising at points of sale).
The invention also relates to the fire-retardant paper advertising medium itself, this medium comprising said fire-resistant paper with the non-combustible charges; preferably it comprises two of said fireproof papers with non-combustible fillers which can be laminated; according to a particular case between said papers is laminated at least one interlayer paper as described above.
De préférence, le papier ignifugé selon l'invention, notamment lorsque le mélange de base comporte un haut taux de charges, est réalisé selon le procédé dit de double floculation décrit dans le brevet EP-B1-0 006390.Preferably, the fireproof paper according to the invention, in particular when the basic mixture has a high charge rate, is produced according to the process called double flocculation described in patent EP-B1-0 006390.
L'invention sera mieux comprise à l'aide des exemples non limitatifs suivants :The invention will be better understood using the following nonlimiting examples:
On réalise sur formette de laboratoire, un papier ignifugé conforme à l'invention en réalisant un support de base par dispersion dans l'eau de la composition suivante :
- 41,1 parts en poids sec de fibres de cellulose raffinées à 25 °SR,
- 56,4 parts en poids sec de trihydrates d'alumine, comme charges incombustibles à effet de retardement de flamme, sa granulométrie moyenne, déterminée avec un granulomètre laser de la marque "MasterSizer X ", est de 10-12 µm,
- 2,5 parts en poids sec d'un polymère chloré, utilisé sous forme d'une
dispersion aqueuse stable qui est un copolymère de chlorure de vinyle- acétate
de vinyle- éthylène réticulable comportant 70% en poids sec de chlorure de
vinyle, 20 % en poids sec d'acétate de vinyle et 10% en poids sec d'éthylène,
stabilisé par un surfactant anionique;
la somme des parts en fibres de cellulose, de charges incombustibles à effet de retardement de flamme et en polymère chloré faisant 100 et constituant le mélange de base, - 0,04 part en poids sec d'un coagulant cationique (polyamide-amine-épichlorhydrine) pour les 100 parts du mélange de base,
- 0,12 part en poids sec d'un agent de collage (un dimère d'alkyl cétène) pour les 100 parts du mélange de base,
- 0,07 part en poids sec d'un agent floculant (polyacrylamide cationique) pour les 100 parts du mélange de base.
- 41.1 parts by dry weight of cellulose fibers refined at 25 ° SR,
- 56.4 parts by dry weight of alumina trihydrates, as non-combustible fillers with flame retardant effect, its average particle size, determined with a laser granulometer of the brand "MasterSizer X", is 10-12 μm,
- 2.5 parts by dry weight of a chlorinated polymer, used in the form of a stable aqueous dispersion which is a crosslinkable vinyl chloride-vinyl acetate-ethylene copolymer comprising 70% by dry weight of vinyl chloride, 20% by dry weight of vinyl acetate and 10% by dry weight of ethylene, stabilized by an anionic surfactant;
the sum of the shares of cellulose fibers, of noncombustible fillers with flame retardant effect and of chlorinated polymer making 100 and constituting the basic mixture, - 0.04 parts by dry weight of a cationic coagulant (polyamide-amine-epichlorohydrin) for 100 parts of the basic mixture,
- 0.12 part by dry weight of a sizing agent (an alkyl ketene dimer) per 100 parts of the basic mixture,
- 0.07 parts by dry weight of a flocculating agent (cationic polyacrylamide) for the 100 parts of the basic mixture.
Le rapport R des charges à retardement de flamme aux fibres de cellulose est de 1,37 en poids "sec", la notion de poids sec étant relative à un papier séché à 100°C (les charges à effet de retardement de flamme sont hydratées, les molécules d'eau étant chimiquement liées à l'alumine, elles le sont encore à 100°C).The ratio R of flame retardant charges to cellulose fibers is 1.37 "dry" weight, the concept of dry weight being related to paper dried at 100 ° C (the flame retardant charges are hydrated, the water molecules being chemically linked to alumina, they are still linked to 100 ° C).
Le support obtenu a un grammage de 320 g/m2 et une épaisseur de 470 µm.
La réaction au feu du papier support obtenu est testé au brûleur électrique selon
la norme française AFNOR NF P 92-503 de décembre 1995, norme établie en
liaison avec l'arrêté français exposé plus haut.
Ce support a une résistance au feu qui le classe dans la catégorie M2, donc
dans une catégorie inférieure à la catégorie M1.The support obtained has a grammage of 320 g / m 2 and a thickness of 470 μm.
The reaction to fire of the support paper obtained is tested with an electric burner according to the French standard AFNOR NF P 92-503 of December 1995, standard established in conjunction with the French decree exposed above.
This support has a fire resistance which classifies it in category M2, therefore in a category lower than category M1.
Par ailleurs on réalise un bain ignifugeant en diluant dans l'eau la composition suivante :
- 85 parts en poids sec d'un sel d'ammonium d'un dérivé de l'acide phosphorique comme sel ignifugeant,
- 13 parts en poids sec d'un polymère styrène-butadiène carboxylé comme liant,
- 2 parts en poids sec de carboxyméthylcellulose comme agent régulateur de la viscosité.
- 85 parts by dry weight of an ammonium salt of a phosphoric acid derivative as a flame retardant salt,
- 13 parts by dry weight of a carboxylated styrene-butadiene polymer as binder,
- 2 parts by dry weight of carboxymethylcellulose as a viscosity regulating agent.
On imprègne le support par le bain ignifugeant en presse encolleuse de laboratoire puis on sèche le support traité vers 100°C. La reprise de la composition ignifugeante par le support de base, en poids sec, est de 10 g/m2. The support is impregnated by the flame retardant bath in a laboratory size press and then the treated support is dried at around 100 ° C. The recovery of the flame-retardant composition by the base support, by dry weight, is 10 g / m 2 .
Il comporte 2,6 % en poids sec de sel ignifugeant par rapport au support de base.It contains 2.6% by dry weight of flame retardant salt compared to the support of based.
La réaction au feu du papier obtenu est testée au brûleur électrique comme précédemment, il répond au classement au feu M1 donc conforme à l'invention. Par ailleurs on mesure son degré de collage Cobb (1 minute, eau) selon la norme internationale ISO 535, il est de 50.The reaction to fire of the paper obtained is tested with an electric burner as previously, it meets the fire classification M1 therefore in accordance with the invention. In addition, the degree of Cobb bonding (1 minute, water) is measured according to the standard. international ISO 535, it is 50.
On dépose, à l'aide d'une barre de MEYER, sur l'une des faces du papier ignifugé précédemment obtenu, une couche pigmentée d'impression-écriture qui a la composition suivante :
- 45 parts en poids sec de kaolin comme pigments de couchage,
- 55 parts en poids sec de carbonate de calcium comme pigments de couchage,
- 10 parts en poids sec d'un polymère styrène-butadiène carboxylé comme liant,
- 6 parts en poids sec d'amidon enzymé comme autre liant,
- un azurant optique,
- un dispersant,
- un agent antimousse,
- de l'hydroxyde de sodium comme agent régulateur de pH.
- 45 parts by dry weight of kaolin as coating pigments,
- 55 parts by dry weight of calcium carbonate as coating pigments,
- 10 parts by dry weight of a carboxylated styrene-butadiene polymer as binder,
- 6 parts by dry weight of enzyme starch as other binder,
- an optical brightener,
- a dispersant,
- an anti-foaming agent,
- sodium hydroxide as a pH regulating agent.
Cette couche est déposée à raison de 25 g/m2 en poids sec.
Le papier couché est testé au brûleur électrique comme précédemment; il
répond au classement au feu M1 donc conforme à l'invention.
Par ailleurs on mesure son degré de collage Cobb (1 minute, eau) selon la norme
internationale ISO 535, il est de 40 g/m2.This layer is deposited at a rate of 25 g / m 2 by dry weight.
The coated paper is tested with an electric burner as before; it meets the fire classification M1 therefore in accordance with the invention.
Furthermore, its degree of Cobb bonding (1 minute, water) is measured according to the international standard ISO 535, it is 40 g / m 2 .
On contrecolle les faces non couchées de deux papiers couchés une face réalisés précédemment à l'aide d'une composition adhésive qui est une colle blanche à base de carbonate de calcium, d'amidon et de latex.We laminate the uncoated faces of two coated papers one side previously made using an adhesive composition which is an adhesive white based on calcium carbonate, starch and latex.
On réalise un autre échantillon pour lequel la composition adhésive n'est pas une colle blanche mais une colle noire, c'est une colle opacifiante qui comporte du noir de carbone.Another sample is produced for which the adhesive composition is not a white glue but a black glue, it is an opacifying glue which contains carbon black.
Les différents papiers contrecollés obtenus sont testés au feu comme
précédemment; ils répondent au classement au feu M1 donc conformes à
l'invention.
Par ailleurs leur degré de collage Cobb (1 minute, eau) selon la norme
internationale ISO 535, est toujours de 40 g/m2.
On vérifie que le papier couché avant ou après contrecollage s'imprime bien,
notamment par sérigraphie et par offset.The different laminated papers obtained are fire tested as before; they meet the fire classification M1 therefore in accordance with the invention.
Furthermore, their Cobb bonding degree (1 minute, water) according to the international standard ISO 535, is always 40 g / m 2 .
It is checked that the paper coated before or after laminating prints well, in particular by screen printing and by offset.
On réalise comme dans l'exemple 1, un papier ignifugé conforme à l'invention
mais le polymère chloré est un copolymère de chlorure de vinyle- acétate de
vinyle- éthylène réticulable comportant 30% en poids sec de chlorure de vinyle,
60 % en poids sec d'acétate de vinyle et 10% en poids sec d'éthylène, il est
stabilisé par un surfactant anionique.
Les constituants du papier sont mis dans les mêmes proportions qu'à l'exemple
1.
Ce support a une résistance au feu qui le classe dans la catégorie M2, donc
dans une catégorie inférieure à la catégorie M1.Is carried out as in Example 1, a flame retardant paper according to the invention but the chlorinated polymer is a copolymer of vinyl chloride-vinyl acetate-crosslinkable ethylene comprising 30% by dry weight of vinyl chloride, 60% by weight dry vinyl acetate and 10% by dry weight of ethylene, it is stabilized by an anionic surfactant.
The constituents of the paper are placed in the same proportions as in Example 1.
This support has a fire resistance which classifies it in category M2, therefore in a category lower than category M1.
Ensuite on imprègne le support de base avec le même bain ignifugeant qu'à
l'exemple 1, puis on le sèche à 100°C; la reprise de la composition ignifugeante
par le support de base, en poids sec, est de 10 g/m2.
Il comporte 2,6 % en poids sec de sel ignifugeant par rapport au support de
base.Then the base support is impregnated with the same flame retardant bath as in Example 1, then dried at 100 ° C; the recovery of the flame retardant composition by the base support, by dry weight, is 10 g / m 2 .
It contains 2.6% by dry weight of flame retardant salt compared to the basic support.
La réaction au feu du papier obtenu est testé au brûleur électrique comme
précédemment, il répond au classement au feu M1 donc conforme à l'invention.
Par ailleurs on mesure son degré de collage Cobb (1 minute, eau) selon la norme
internationale ISO 535, il est de 80.
Par rapport à l'exemple 1, le collage est moins bon, probablement à cause de la
teneur du polymère chloré plus élévée en acétate de vinyle qui est hydrophile.The reaction to fire of the paper obtained is tested with an electric burner as above, it meets the fire classification M1 therefore in accordance with the invention. In addition, its degree of Cobb bonding (1 minute, water) is measured according to the international standard ISO 535, it is 80.
Compared with Example 1, the bonding is less good, probably because of the higher content of vinyl acetate in chlorinated polymer which is hydrophilic.
On dépose sur l'une des faces du papier ignifugé précédemment obtenu une
couche pigmentée d'impression-écriture qui a la composition de celle de
l'exemple 1.
De même cette couche est déposée à raison de 25 g/m2.
Le papier couché est testé au feu; il est classé dans la catégorie M1 donc
conforme à l'invention.
Par ailleurs on mesure son degré de collage Cobb (1 minute, eau) selon la norme
internationale ISO 535, il est de 43 g/m2.A pigmented printing-writing layer which has the composition of that of Example 1 is deposited on one side of the flame-retardant paper previously obtained.
Likewise, this layer is deposited at a rate of 25 g / m 2 .
The coated paper is fire tested; it is classified in category M1 therefore in accordance with the invention.
In addition, its degree of Cobb bonding (1 minute, water) is measured according to the international standard ISO 535, it is 43 g / m 2 .
On réalise un échantillon contrecollé comme dans l'exemple 1.A laminated sample is produced as in Example 1.
On réalise un échantillon contrecollé comme dans l'exemple 1.A laminated sample is produced as in Example 1.
On teste la réaction au feu des papiers obtenus comme précédemment; ils sont
classés dans la catégorie M1 donc conformes à l'invention.
Par ailleurs on mesure leur degré de collage Cobb (1 minute, eau) selon la
norme internationale ISO 535, il est de 43 g/m2. The reaction to fire of the papers obtained as above is tested; they are classified in category M1 therefore in accordance with the invention.
In addition, their degree of Cobb bonding (1 minute, water) is measured according to the international standard ISO 535, it is 43 g / m 2 .
On vérifie que le papier couché avant ou après contrecollage s'imprime bien, notamment par sérigraphie et par offset.We check that the coated paper before or after laminating prints well, especially by screen printing and offset.
On réalise industriellement sur machine à papier à table plate un papier ignifugé conforme à l'invention en réalisant un support de base , selon le procédé de double floculation décrit dans le brevet EP-B-6390, en dispersant dans l'eau la compostion suivante :
- 41,1 parts en poids sec de fibres de cellulose raffinées à 25 ° SR,
- 56,4 parts en poids sec de trihydrates d'alumine, comme charges à effet de retardement de flamme, sa granulométrie moyenne est de 10-12 µm,
- 3,5 parts en poids sec d'un polymère chloré, qui est un copolymère de
chlorure de vinyle- acétate de vinyle- éthylène réticulable comportant 70% en
poids sec de chlorure de vinyle, 20 % en poids sec d'acétate de vinyle et 10%
en poids sec d'éthylène, stabilisé par un surfactant anionique,
la somme des parts en fibres de cellulose, de charges à effet de retardement de flamme et en polymère chloré fait 100 et constitue le mélange de base, - 0,04 part en poids sec d'un coagulant cationique pour les 100 parts du mélange de base,
- 0,12 part en poids sec d'un agent de collage (un dimère d'alkyl cétène) pour les 100 part du mélange de base,
- 0,075 part d'un agent floculant pour les 100 parts du mélange de base, 0,05 part étant introduite avant l'ajout du polymère chloré et 0,025 part après.
- 41.1 parts by dry weight of cellulose fibers refined at 25 ° SR,
- 56.4 parts by dry weight of alumina trihydrates, as fillers with flame retardant effect, its average particle size is 10-12 μm,
- 3.5 parts by dry weight of a chlorinated polymer, which is a crosslinkable vinyl chloride-vinyl acetate-ethylene copolymer comprising 70% by dry weight of vinyl chloride, 20% by dry weight of vinyl acetate and 10% by dry weight of ethylene, stabilized by an anionic surfactant,
the sum of the shares of cellulose fibers, of flame retardant fillers and of chlorinated polymer makes 100 and constitutes the basic mixture, - 0.04 part by dry weight of a cationic coagulant for the 100 parts of the basic mixture,
- 0.12 parts by dry weight of a sizing agent (an alkyl ketene dimer) for the 100 parts of the base mixture,
- 0.075 parts of a flocculating agent for 100 parts of the base mixture, 0.05 parts being introduced before the addition of the chlorinated polymer and 0.025 parts after.
Ce mélange est réalisé dans le cuvier de la machine à papier, l'agent floculant
est ajouté en continu.
Le rapport Charges à retardement de flamme sur Fibres de cellulose est de 1,37
en poids sec pour un papier séché à 100 °C.
Ensuite on imprègne le support de base avec le même bain ignifugeant qu'à
l'exemple 1, en presse encolleuse de la machine à papier puis on sèche; la
reprise de la composition ignifugeante par le support de base, en poids sec, est
de 10 g/m2.
Il comporte 2,85 % en poids sec de sel ignifugeant par rapport au support de
base.This mixing is carried out in the vat of the paper machine, the flocculating agent is added continuously.
The ratio of flame retardant charges on cellulose fibers is 1.37 by dry weight for paper dried at 100 ° C.
Then the base support is impregnated with the same flame retardant bath as in Example 1, in a size press of the paper machine and then dried; the recovery of the flame retardant composition by the base support, by dry weight, is 10 g / m 2 .
It contains 2.85% by dry weight of flame retardant salt relative to the base support.
La réaction au feu du papier obtenu est testée au brûleur électrique comme dans l'exemple 1.The reaction to fire of the paper obtained is tested with an electric burner as in example 1.
On dépose sur l'une des faces du papier ignifuge précédemment obtenu une
couche pigmentée d'impression-écriture qui a la composition de celle de
l'exemple 1. Cette couche est déposée à raison de 25 g/m2. On lisse le papier
couché pour obtenir un bel état de surface.
Le papier couché est testé au feu.Is deposited on one side of the flame retardant paper previously obtained a pigmented printing-writing layer which has the composition of that of Example 1. This layer is deposited at a rate of 25 g / m 2 . We smooth the coated paper to obtain a good surface finish.
The coated paper is fire tested.
On réalise un échantillon contrecollé comme dans l'exemple 1.A laminated sample is produced as in Example 1.
On réalise un échantillon contrecollé comme dans l'exemple 1.A laminated sample is produced as in Example 1.
On teste les papiers obtenus au feu comme précédemment.
On vérifie que le papier couché avant ou après contrecollage s'imprime bien,
notamment par sérigraphie et par offset.The papers obtained are tested on fire as above.
It is checked that the paper coated before or after laminating prints well, in particular by screen printing and by offset.
Les caractéristiques des papiers obtenus aux différentes étapes sont donnés
dans le tableau 1.
Le grammage est déterminé selon la norme internationale ISO 536.
L'épaisseur est déterminée selon la norme internationale ISO 534.
Le degré de collage Cobb est déterminé selon la norme internationale ISO 535.
La rigidité TABER est déterminée selon la norme internationale ISO 2493.
La résistance à la traction est déterminée selon la norme internationale ISO
1924/2.
La blancheur est déterminée selon la norme internationale ISO 2470, à 457 nm.
La porosité BENDTSEN est déterminée selon la norme internationale ISO
5636/3.
La rugosité BENDTSEN est déterminée selon la norme française NF Q 03-049.
La stabilité dimensionnelle est déterminée sur un appareil PRUFBAU qui mesure
les écarts d'allongements en % d'une éprouvette de papier de 50 mm de
largeur et de 140 mm de longueur, découpée dans le sens marche de la
machine à papier ou dans le sens travers, entre 65 et 15 % d'humidité relative
(HR) et 98 et 15 % d'humidité relative.The characteristics of the papers obtained at the various stages are given in Table 1.
The grammage is determined according to the international standard ISO 536.
The thickness is determined according to the international standard ISO 534.
The degree of Cobb bonding is determined according to international standard ISO 535. The TABER stiffness is determined according to international standard ISO 2493.
The tensile strength is determined according to the international standard ISO 1924/2.
The whiteness is determined according to the international standard ISO 2470, at 457 nm. The BENDTSEN porosity is determined according to the international standard ISO 5636/3.
The BENDTSEN roughness is determined according to French standard NF Q 03-049. The dimensional stability is determined on a PRUFBAU device which measures the elongation differences in% of a paper test piece 50 mm wide and 140 mm long, cut in the running direction of the paper machine or in the direction cross, between 65 and 15% relative humidity (RH) and 98 and 15% relative humidity.
On réalise un papier ignifugé conforme à l'invention comme dans l'exemple 1
mais le rapport R (fibres / charges) est de 1,93 et le taux de polymère chloré
est de 2,90 % du mélange de base. La rétention des charges est très bonne,
elle est supérieure à 95%.
On imprègne le support avec le bain ignifugeant, puis on le couche comme à
l'exemple 1. On fait des échantilllons contrecollés comme dans l'exemple 1.
On teste les papiers obtenus au feu comme précédemment; les papiers obtenus
après traitement en presse encolleuse (imprégnés, couchés, contrecollés)
répondent tous au classement au feu M1 donc conformes à l'invention.
On vérifie que le papier couché avant ou après contrecollage s'imprime bien,
notamment par sérigraphie et par offset.A flame retardant paper according to the invention is produced as in Example 1 but the ratio R (fibers / fillers) is 1.93 and the content of chlorinated polymer is 2.90% of the basic mixture. The charge retention is very good, it is greater than 95%.
The support is impregnated with the flame-retardant bath, then it is coated as in Example 1. Samples are laminated as in Example 1.
The papers obtained are tested on fire as before; the papers obtained after treatment in a size press (impregnated, coated, laminated) all meet the M1 fire classification therefore in accordance with the invention.
It is checked that the paper coated before or after laminating prints well, in particular by screen printing and by offset.
On réalise un papier ignifugé conforme à l'invention comme dans l'exemple 1
mais le rapport R (fibres / charges) est de 2,50 et le taux de polymère chloré
est de 3,15 % du mélange de base. La rétention des charges est très bonne,
elle est supérieure à 95%.
On imprègne le support avec le bain ignifugeant, on le couche comme à
l'exemple 1.
On fait des échantilllons contrecollés comme dans l'exemple 1.
On teste les papiers obtenus au feu comme précédemment; les papiers obtenus
après traitement en presse encolleuse (imprégnés, couchés, contrecollés)
répondent tous au classement au feu M1 donc conformes à l'invention.
On vérifie que le papier couché avant ou après contrecollage s'imprime bien,
notamment par sérigraphie et par offset.A flame retardant paper in accordance with the invention is produced as in Example 1, but the ratio R (fibers / fillers) is 2.50 and the level of chlorinated polymer is 3.15% of the basic mixture. The charge retention is very good, it is greater than 95%.
The support is impregnated with the flame retardant bath, it is coated as in Example 1.
We make laminated samples as in Example 1.
The papers obtained are tested on fire as before; the papers obtained after treatment in a size press (impregnated, coated, laminated) all meet the M1 fire classification therefore in accordance with the invention.
It is checked that the paper coated before or after laminating prints well, in particular by screen printing and by offset.
On imprègne un support de base réalisé industriellement comme dans l'étape 1
de l'exemple 3, son grammage étant de 260g/m2, en faisant varier le taux de
sel ignifugeant selon les taux suivants : 6%, 8%, 10% et 15% pour réaliser
respectivement les exemples 6 à 9.
Le degré de collage de chacun des supports de base ainsi traités est
respectivement de 60, 70, 78 et 90 g/m2.
On peut admettre qu'au delà d'un degré de collage Cobb de 80 g/m2, le papier
ne convient plus; en effet si on essaie de coucher le papier avec une couche
pigmentée, elle est trop enterrée dans le papier et par conséquent l'impression
ne sera pas bonne.
On peut donc mettre jusqu'à 10 % de sel en poids sec du support de base.A base support impregnated industrially is impregnated as in step 1 of Example 3, its grammage being 260 g / m 2 , by varying the level of flame retardant salt according to the following rates: 6%, 8%, 10% and 15% to carry out Examples 6 to 9 respectively.
The degree of bonding of each of the base supports thus treated is respectively 60, 70, 78 and 90 g / m 2 .
We can admit that beyond a Cobb bonding degree of 80 g / m 2 , the paper is no longer suitable; indeed if we try to coat the paper with a pigmented layer, it is too buried in the paper and therefore the impression will not be good.
We can therefore put up to 10% salt by dry weight of the base support.
On réalise un support de base comme dans l'étape 1 de l'exemple 1 mais le
polymère utilisé est un polymère non halogéné, c'est un copolymère styrène-butadiène
utilisé sous forme de dispersion aqueuse stable.
Lorsque l'on teste la résistance au feu du papier traité avec le sel ignifugeant, il
n'atteint pas le classement M1. A basic support is produced as in step 1 of Example 1, but the polymer used is a non-halogenated polymer, it is a styrene-butadiene copolymer used in the form of a stable aqueous dispersion.
When testing the fire resistance of paper treated with flame retardant salt, it does not reach the M1 classification.
On réalise un support de base comme dans l'étape 1 de l'exemple 1 mais sans
faire de traitement de surface avec un sel ignifugeant, le liant halogéné étant
par ailleurs mis en grande quantité, soit à un taux de 16 %.
Lorsque l'on teste la résistance au feu du papier, il n'atteint pas le classement
M1, le papier s'enflamme totalement, malgré le taux élevé de polymère
halogéné.A basic support is produced as in step 1 of Example 1 but without making a surface treatment with a flame retardant salt, the halogenated binder being moreover placed in large quantity, ie at a rate of 16%.
When testing the fire resistance of the paper, it does not reach the M1 classification, the paper ignites completely, despite the high rate of halogenated polymer.
On reprend le support de base de l'exemple 11 comparatif précédent mais on
fait un traitement de surface en presse encolleuse avec un sel ignifugeant selon
la composition de l'exemple 1.
Lorsque l'on teste la résistance au feu du papier, il répond au classement au feu
M1.The basic support of the preceding comparative example 11 is repeated, but a surface treatment is carried out in a size press with a flame retardant salt according to the composition of example 1.
When the fire resistance of the paper is tested, it responds to the fire classification M1.
On réalise un support de base comme dans l'étape 1 de l'exemple 1 mais sans
faire de traitement de surface avec un sel ignifugeant, la charge à retardement
de flamme étant par ailleurs mise en grande quantité, le rapport charges / fibres
étant de 8.
Lorsque l'on teste la résistance au feu du papier, il n'atteint pas le classement
M1 malgré la grande quantité de charges incombustibles.A basic support is produced as in step 1 of Example 1 but without making a surface treatment with a flame retardant salt, the flame retardant filler being moreover put in large quantity, the filler / fiber ratio being 8.
When testing the fire resistance of the paper, it does not reach the M1 classification despite the large quantity of non-combustible charges.
On reprend le support de base de l'exemple 13 comparatif précédent mais on
fait un traitement de surface en presse encolleuse avec le sel ignifugeant
comme dans l'exemple 1.
Lorsque l'on teste la résistance au feu du papier, il répond bien au classement
M1.The basic support of the preceding comparative example 13 is repeated, but a surface treatment is carried out in a size press with the flame retardant salt as in Example 1.
When testing the fire resistance of paper, it responds well to the M1 classification.
On réalise un support de base comme dans l'étape 1 de l'exemple 1 avec le traitement de surface avec un sel ignifugeant mais la charge à retardement de flamme est mise en faible quantité, le rapport charges / fibres étant de 0,95. La reprise sèche de la composition d'imprégnation ignifugeante est de 11,1 g/m2. Il comporte 2,95 % en sel ignifugeant en poids sec par rapport au support de base.A basic support is produced as in step 1 of Example 1 with the surface treatment with a flame retardant salt, but the flame retardant filler is put in a small quantity, the filler / fiber ratio being 0.95. The dry recovery of the flame retardant impregnation composition is 11.1 g / m 2 . It contains 2.95% flame retardant salt by dry weight compared to the base support.
Lorsque l'on teste la résistance au feu du papier, il n'atteint pas le classement M1, malgré le traitement de surface avec le sel ignifugeant.When testing the fire resistance of paper, it does not reach classification M1, despite the surface treatment with the flame retardant salt.
On réalise un papier de base comme dans l'étape 1 de l'exemple 15 comparatif
précédent 1 avec le traitement de surface avec un sel ignifugeant, la charge à
retardement de flamme étant toujours en faible quantité, le rapport charges /
fibres étant de 0,95, mais la reprise par le papier en sel ignifugeant est doublée.
(la reprise sèche de la composition est de 22,6 g/m2).
Il comporte 6 % en sel ignifugeant en poids sec par rapport au support de base.A base paper is produced as in step 1 of comparative example 15 above 1 with the surface treatment with a flame retardant salt, the flame retardant filler being always in small quantity, the filler / fiber ratio being 0 , 95, but the recovery by fire retardant salt paper is doubled. (the dry recovery of the composition is 22.6 g / m 2 ).
It contains 6% flame retardant salt by dry weight compared to the base support.
Lorsque l'on teste la résistance au feu du papier, il n'atteint pas le classement M1, malgré l'augmentation en sel ignifugeant.When testing the fire resistance of paper, it does not reach classification M1, despite the increase in flame retardant salt.
On réalise un papier de base comme dans l'étape 1 de l'exemple 1 avec le
traitement de surface avec un sel ignifugeant mais la charge incombustible
n'est pas une charge à retardement de flamme, cette charge est du mica , le
rapport charges / fibres étant aussi de 1,37.
Lorsque l'on teste la résistance au feu du papier, il n'atteint pas le classement
M1, le papier s'enflamme totalement.A base paper is produced as in step 1 of Example 1 with the surface treatment with a flame retardant salt but the non-combustible charge is not a flame retardant charge, this charge is mica, the charge ratio / fibers also being 1.37.
When testing the fire resistance of the paper, it does not reach the M1 classification, the paper ignites completely.
On réalise un support publicitaire de 750 g/m2 constitué de trois jets de papier. An advertising medium of 750 g / m 2 is produced which consists of three jets of paper.
Les deux jets extérieurs sont des papiers couchés ignifugés obtenus selon
l'exemple 3.
Le jet intercalaire est un papier constitué principalement de fibres de cellulose et
d'un agent de résistance humide, ce papier étant imprégné, par exemple à l'aide
d'une presse encolleuse, d'une composition comportant un sel ignifugeant. Ce
sel peut être celui utilisé pour traiter le support, il est présent en une quantité
d'environ 20 % en poids sec par rapport à l'intercalaire.
Cet intercalaire a un grammage d'environ 160 g/m2.
Cet intercalaire est contrecollé entre les deux papiers extérieurs à l'aide d'une
composition adhésive qui peut être une colle blanche ou une colle noire non
ignifugées et déposée à raison d'environ 20g/m2 par face.
Le complexe obtenu est testé au feu, il est classé M1.
Il a une rigidité TABER de 700 g.cm dans le sens marche et de 400 g.cm dans
le sens travers.
Il s'imprime bien en sérigraphie et par offset.
débit corrigé (cm3 / mn)
débit corrigé ( cm3 / mn)
The intermediate jet is a paper mainly consisting of cellulose fibers and a wet strength agent, this paper being impregnated, for example using a size press, with a composition comprising a flame retardant salt. This salt can be that used to treat the support, it is present in an amount of about 20% by dry weight relative to the interlayer.
This interlayer has a grammage of approximately 160 g / m 2 .
This interlayer is laminated between the two exterior papers using an adhesive composition which can be a white glue or a black non-flame retardant glue and deposited at a rate of approximately 20 g / m 2 per side.
The complex obtained is fire tested, it is classified M1.
It has a TABER stiffness of 700 g.cm in the running direction and 400 g.cm in the cross direction.
It prints well in screen printing and offset printing.
corrected flow (cm 3 / min)
corrected flow (cm 3 / min)
Claims (22)
- Fireproofed paper with increased fire resistance, especially in compliance with classification M1, characterized in that it comprises:at least cellulose fibres and at least incombustible fillers with flame retardant properties, the filler/fibre ratio by dry weight, R, being between 1 and 9,between 1 and 15 parts by dry weight, per 100 parts of the base mixture, of at least one halogenated polymer used in the form of a stable aqueous dispersion, these three components constituting the base mixture, andbetween 0.1 and 10% by dry weight, based on the base mixture, of at least one fireproofing salt soluble or dispersible in aqueous media, the dry weight being expressed relative to a paper dried at 100°C.
- Paper according to claim 1, characterized in that it comprises, in the bulk, a mixture of the cellulose fibres, the fillers with flame retardant properties and the halogenated polymer, this mixture forming a so-called base paper, and in that it comprises the fireproofing salt on at least one side of said base paper.
- Paper according to claim 1 or 2, characterized in that the halogenated polymer is a chlorinated polymer containing a monomer selected from vinyl chloride and polyvinylidene chloride.
- Paper according to claim 3, characterized in that the chlorinated polymer is a copolymer in which one of the comonomers is vinyl chloride, and in that this comonomer is present in the copolymer in an amount of at least 10% by dry weight.
- Paper according to claim 4, characterized in that the vinyl chloride comonomer is present in the copolymer in an amount of at least 30% by dry weight, preferably in an amount of at least 70%.
- Paper according to claim 4 or 5, characterized in that the chlorinated polymer is a vinyl chloride/vinyl acetate/ethylene copolymer.
- Paper according to claim 6, characterized in that the vinyl chloride/vinyl acetate/ethylene copolymer is selected from copolymers containing these comonomers in respective proportions of 70/20/10 or 30/60/10 by dry weight.
- Paper according to one of claims 1 to 7, characterized in that the amount of chlorinated polymer is between 1 and 5 parts by dry weight per 100 parts of the base mixture.
- Paper according to one of claims 1 to 8, characterized in that the filler with flame retardant properties is selected from aluminium hydroxides, aluminium oxide hydrates, particularly aluminium oxide trihydrates, magnesium hydroxides, hydrated calcium carbonates, hydrated magnesium carbonates and mixtures thereof.
- Paper according to one of claims 1 to 9, characterized in that the ratio by dry weight of fillers with a flame retardant effect to cellulose fibres, R, is between 1 and 3.
- Paper according to one of claims 1 to 10, characterized in that the fireproofing salt is an ammonium salt of a phosphoric acid derivative.
- Paper according to one of claims 1 to 11, characterized in that the fireproofing salt is in an amount of less than 8% by dry weight of the base mixture, preferably in an amount of between 1 and 6%.
- Paper according to claim 2, characterized in thatit comprises, in the bulk:cellulose fibres,incombustible fillers with flame retardant properties, selected from aluminium hydroxides and alumina hydrates, particularly alumina trihydrates, and with a particle size of between 8 and 15 µm, the filler/fibre ratio by dry weight, R, being between 1 and 3, andas the halogenated polymer, between 2 and 5 parts by dry weight, per 100 parts of the base mixture, of a vinyl chloride/vinyl acetate/ethylene copolymer in a stable aqueous dispersion containing these comonomers in respective proportions of 70/20/10 by dry weight, stabilized by an anionic surfactant, a mixture of these three components (fibres, fillers, halogenated polymer) constituting the base mixture of the base paper, and the sum of their parts by dry weight being 100, and in thatit comprises, on at least one side of said base paper, 1 to 6% by dry weight, based on the base mixture, of an ammonium salt of a phosphoric acid derivative as the fireproofing salt,
the dry weight being expressed relative to a paper dried at 100°C. - Fireproofed paper according to one of claims 1 to 13, characterized in that it carries a pigmented printing/writing coating on at least one side.
- Fireproofed paper, characterized in that it comprises at least two papers according to one of claims 1 to 14, pasted together with an adhesive composition.
- Fireproofed paper according to claim 15, characterized in that the papers are pasted together with a non-flame-retarded adhesive composition.
- Fireproofed paper according to claim 15 or 16, characterized in that it comprises at least one flame-retarded intercalated paper containing principally cellulose fibres and a wet strength additive, and in that it is impregnated with a fireproofing salt in an amount of between 10 and 30% by dry weight, based on the cellulose fibres.
- Fireproofed paper according to claim 17, characterized in that the intercalated paper has a weight of between 100 and 300 g/m2.
- Use of a fireproofed paper according to one of claims 1 to 18 for the manufacture of an advertising base paper.
- Advertising base paper made of fireproofed paper such as hanging poster paper or showcard paper, characterized in that it consists of at least one paper according to one of claims 1 to 18.
- Advertising base paper according to claim 20, characterized in that it comprises two fireproofed papers according to the claims, between which is pasted at least one intercalated paper containing cellulose fibres and a wet strength additive and impregnated with a fireproofing salt in an amount of between 10 and 30% by dry weight, based on the cellulose fibres, said intercalated paper having a weight of between 100 and 300 g/m2.
- Base paper according to claim 20 or 21, characterized in that it has a weight of between 200 and 2000 g/m2.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9609558 | 1996-07-30 | ||
FR9609558A FR2751996B1 (en) | 1996-07-30 | 1996-07-30 | FIREPROOF PAPER, ESPECIALLY PRINT-WRITING PAPER AND POSTER PAPER |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0822290A1 EP0822290A1 (en) | 1998-02-04 |
EP0822290B1 true EP0822290B1 (en) | 2003-05-28 |
Family
ID=9494616
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97401791A Expired - Lifetime EP0822290B1 (en) | 1996-07-30 | 1997-07-24 | Fireproof paper, especially printing paper and advertising support |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0822290B1 (en) |
AT (1) | ATE241730T1 (en) |
DE (1) | DE69722325T2 (en) |
FR (1) | FR2751996B1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2277131A1 (en) * | 1998-08-14 | 2000-02-14 | Schweitzer-Mauduit International, Inc. | Process for increasing the wet strength of porous plug wraps for use in smoking articles |
FR2853333B1 (en) * | 2003-04-01 | 2006-01-13 | Arjo Wiggins | PRIMARY GLASS SAIL |
CN102619139B (en) * | 2012-04-09 | 2014-02-26 | 天津商业大学 | Water-based halogen-free flame-retardant paper and preparation method thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GR65316B (en) * | 1978-06-20 | 1980-08-02 | Arjomari Prioux | Method for the preparation of fibrous leaf |
DE2948974C2 (en) * | 1979-12-05 | 1982-05-19 | PWA Kunststoff GmbH, 8201 Raubling | Process for the production of flame-retardant paper and fire retardants for carrying out the process |
DE3416940A1 (en) * | 1983-06-13 | 1984-12-13 | Mead Corp | PAPER WITH FLAME-RESISTANT INSERT AND LAMINATE PRODUCED WITH ITS USE |
-
1996
- 1996-07-30 FR FR9609558A patent/FR2751996B1/en not_active Expired - Fee Related
-
1997
- 1997-07-24 DE DE69722325T patent/DE69722325T2/en not_active Expired - Fee Related
- 1997-07-24 EP EP97401791A patent/EP0822290B1/en not_active Expired - Lifetime
- 1997-07-24 AT AT97401791T patent/ATE241730T1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
EP0822290A1 (en) | 1998-02-04 |
FR2751996A1 (en) | 1998-02-06 |
DE69722325D1 (en) | 2003-07-03 |
ATE241730T1 (en) | 2003-06-15 |
FR2751996B1 (en) | 1998-12-24 |
DE69722325T2 (en) | 2004-03-25 |
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