CA1217903A - Flame retardant paper and process for making it - Google Patents
Flame retardant paper and process for making itInfo
- Publication number
- CA1217903A CA1217903A CA000447777A CA447777A CA1217903A CA 1217903 A CA1217903 A CA 1217903A CA 000447777 A CA000447777 A CA 000447777A CA 447777 A CA447777 A CA 447777A CA 1217903 A CA1217903 A CA 1217903A
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- CA
- Canada
- Prior art keywords
- flame retardant
- weight
- agent
- paper
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
-
- 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
- D21H5/00—Special paper or cardboard not otherwise provided for
- D21H5/0002—Flame-resistant papers; (complex) compositions rendering paper fire-resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
- Machines For Manufacturing Corrugated Board In Mechanical Paper-Making Processes (AREA)
- Insulated Conductors (AREA)
- Glass Compositions (AREA)
Abstract
FLAME RETARDANT PAPER AND PROCESS FOR MAKING IT
ABSTRACT OF THE DISCLOSURE
The disclosure relates to flame retardant paper con-taining cellulose fibers which have been treated with an ammonium polyphosphate as a flame retardant agent. The paper contains more especially, as the flame retardant agent, a product made from a free-flowing ammonium poly-phosphate and a hardened, water-insoluble artificial resin encasing the individual ammonium polyphosphate particles.
ABSTRACT OF THE DISCLOSURE
The disclosure relates to flame retardant paper con-taining cellulose fibers which have been treated with an ammonium polyphosphate as a flame retardant agent. The paper contains more especially, as the flame retardant agent, a product made from a free-flowing ammonium poly-phosphate and a hardened, water-insoluble artificial resin encasing the individual ammonium polyphosphate particles.
Description
`` I 3 The present invention relates to flame retardant paper having improved flame retardant properties, and to a process for making it.
As disclosed in European Patent Application 00 59 850, published September 15, 1982, it is known that the combustibility of products consisting essentially of cellulose fibers, erg paper, can be reduced by means of pulverulent red phosphorus having its individual particles enveloped by a mailmen resign, the products containing the flame retardant agent in a proportion of 4 to 18 weight %, especially 7 to 13 weight %.
The use of red phosphorus as a flame retardant agent for products consisting predominantly of cellulose fibers is not fully satisfactory for the following two reasons. Under the action of oxygen and moisture, red phosphorus is subject to disk proportionation with the resultant formation of toxic hydrogen phosphide. In addition to this, cellulose fibers admixed with red phosphorus have unsatisfactory flame retardant properties only. These are adverse effects which cannot fully be obviated even in the event of phosphorus particles encased by a mailmen resin being used.
German Patent DEEPS 30 20 033 discloses a process for making difficulty inflammable or incombustible products based on fibrous materials, wherein the fibrous materials are made into an aqueous pulp, the pulp is admixed with boron-containing minerals, the mixture is admitted to a fleece-forming and fiber-dehydrating machine, dehydrated and dried. More specifically, the aqueous pulp with the boron-containing minerals therein is intimately mixed with a mineral acid and the mixture is allowed to ripen prior I., to processing it. Coolant is used as the ooron-cen-twining Monroe and sulfuric acid is used as ire acid.
so can be inferred from sample 4 in DEEPS 30 20 0~3, this onion process calls or the use of a rela4i~ely large proportion of flame retardant coolant. The reason for this resides in the fact that a good deal of boric acid (this is acid which is being formed on subjecting Cole-nix to treatment with sulfuric acid) becomes dlssol~Jed in the aqueous phase of the cellulose leer pulp and lost so that it cannot contribute to conferring lame retardant properties upon the fibrous feed material, On the other hand a good deal ox calcium sulfate, which is a by-pro-duct obtained upon processing calumniate with H2SO4J is I ranked in tune final product, affecting the uali~y of paper made therefrom.
German Patent Specification DE-AS 17 71 693 provides flame retardant paper containing cellulose fibers that 'nave been treated with a substantially water-insoluble ammonium polyphosohate ox the general formula H(n_m)~2(~4)mPnO3n+1 in which n stands for a whole number of about 20 to 400 and the ratio men presents an average value of 0.7 to 1.1, and m stands or a value of at most no Tune ammonium pox lyphosphave is used in a proportion of about 1 to eta I especially 3 to 15 weight ,6, based on the queen-Tut of fiber.
The flame no ardent paper disclosed in DOW 17 71 owe' is made by a standard process by admixing the aqueous sup-pension of cellulose fixers with the ammonium ~olyp.ios?'ra~e Lo APE) and with a polyalkylenimine as a retention agent although ammonium polypnosphate is known to be a Good flame retardant agent, it does not provide an optimum flame retardant effect upon incorporating it with paper by a wet process, In the process of DE AS 17 71 693, there is, in a manner analogous to the process of DIPS 30 20 033, a con-siderable discrepancy between the quantity of flame no-tardant agent added to the pulp and the quantity actually contained in the finished paper. As described in Example 23 of DE-AS 17 71 693, 30 weight oh PUP based on the it-brows material, is introduced into the pulp, whilst the -final paper just contains 18,4 weight %, the undesirable loss of ASP is obviously the result of a portion of the ASP used being dissolved in the aqueous phase of the pulp and thus prevented prom contributing to rendering the paper flame retardant.
German Potent Specification DEMOS 29 49 537 describes, independently of rendering paper flare re~ardantl a part-curate agent obviating the combustibility of polyurethane and polyurethane foams, the agent being based on free flow-in pulverulent ammonium polyphosphates of which the India visual particles are coated with a hardened, water into-lube polycondensation product of mailmen and formalde-Hyde Nothing has been disclosed in DEMOS 29 I 537 as no-guards incorporation of the agent into materials to be non-dewed flame retardant.
The present invention now provides a process for con-furring good flame retardant properties upon paper and more generally upon materials containing cellulose fibers, which avoids the adverse effects associated with the ~rlor processes discussed hereinabove, and more particularly per-mitt the loss of flame retardant agent normally accompany-in the incorporation of the agent into the cellulose giber material]. to be reduced. The term paper as used herein denotes cellulose-containing materials, erg, standard paper grades, paper board, card board, and the live, e.g. also corrugated boards as secondary products, The present invention relates more particular-lye to flame retardant paper containing cellulose fibers and having been treated with an ammonium polyphos~hate as a flame retardant agent, the paper containing as the flame retardant agent a product consisting of a) 75 to 99.5 weight % of a pulverulent, free flowing ammonium pol~hosphate of the general formula Ho T2(N~4)mPnO3n+1 in which n stands for a whole number with an average value of 20 to 800 and the ratio m/n is about 1, and b) 0.5 to 25 weight ox a hardened, ~ater-insoluble en-tickle resin encasing the individual ammonium holy-phosphate particles, in a proportion of about 5 to 30 weight %, based on the dry fibrous material.
The lame retardant agent should generally be used in the form of particles with a mean size ox about 0.01 to 0.5 mm and conveniently has an average degree of con-sensation n of 450 to 800, determined by the terminal group titration process (van Waxer, Grafter and McCullou~en, Anal. Chum. 26, page 1755 (1954))~ The artificial resin encasing the flame retardant agent preferably is a condemn-station product of examine and formaldehyde This product in its unhardened state, is e I. a powder of which a 50 ,b aqueous solution has a dynamic viscosity of 20 ma . sec., a pi value at 20C of So to So and a density at 20C of 1.21 to 1.225 g/ml.
The invention also relates to a process for making flame retardant paper, which comprises admixing an aqueous suspension consisting essentially of cellulose fibers with 5 to 30 weight oh based on the dry fibrous material, of a flame retardant agent consisting of a) 75 to 99.5 weight % of a pulverulent, free flowing ammonium polyphosphate of the general formula H(n_m)+2(NH4)m~nO3n~1 in which n stands for a whole number with an average value of about 20 to 800 and the ratio m/n is about 1, and b) 0.5 to 25 weight I of a hardened, water-insoluble artificial resin encasing the individual ammonium polyp phosphate particles and admitting the resulting mixture to a ~leece-forming and fiber-dehydrating machine, dehydrating the said mixture and drying it.
A preferred feature of the present process provides or a pi value of 3 to 9, preferably 4 to 8, to be establish-Ed in the aqueous suspension ox cellulose fibers by adding an acid, e.g. a mineral acid, or alkaline liquor thereto, prior to or after the addition of the flame retardant agent.
A further preferred feature of the present process provides for the flame retardant agent to be used in he form of a 1 to 20 weight % aqueous suspension and for this suspension to be introduced into an bout 0.5 to 5 eye I
suspension of cellulose fibers in water.
A still further preferred feature of the present pro-cuss provides for the aqueous suspension to be additionally ad-mixed with about 0.1 to 0.5 weight %, based on the dry fibrous material, of a dehydrating and retention agent and for the whole to be immediately thereafter admitted to the fleece-forming and fiber-dehydrating machine. A useful retention agent is, for example, an aqueous solution of a high molecular weight, cation-active polyamide having a density of about 1.05 g/cm3, a viscosity of 500 to 1500 ma . second (Brook field), and a pi of 6, and being water-soluble in cold water in whatever ratio.
The following statements are intended further to if lust rate the invention.
The ammonium polyphosphates on which the flame retardant agent of this invention is being based are commercially available products which can be produced e.g. by the process disclosed in Canadian Patent Application Serial No. 421 023 and which can be coated with a mailmen resin by the process disclosed in German Patent Specification DEMOS 29 49 537.
The flame retardant agent of this invention can be in-corporate with the pa performing material during a standard paper making process, e.g. in the wet stage, preferably to the paper suspension containing cellulose fibers, coming from the last purification stage. Apart from the addition of a known retention agent mentioned above, the invention provides for the fiber pulp to be additionally admixed with standard binders and fillers, if desired, The papers made in accordance with this invention have very good flame retardant properties and they comply with the .
requirements ox Classes 31 and 32 I Dl~-speci4ication (DIN
stands 40r German Industrial Standard) Lo 02 . As regards difficult sealability- in water, the present lame retardant agents compare favorably with the prior agents heretofore incorporated with paper. This beneficially influences awry mixing since -there is considerably 1QSS discrepancy than here-tougher between the quantity of lame retardant agent it-traduced into the cellulose fiber pulp and the airtight ox flame retardant agent actually contained in the taper produced.
The Wang Examples illustrate the invention, in which the following products were used.
1. Flame retardant agent A:
It is a difficultly water soluble ammonium polyphcsphate ox the formula (NH4P03)n, with a degree of condensation n I about 700. The a.~monium polyphosphate was made by the process described in US Patent Application Serial No. 464 982. It contains ~1.2 weight 6 phosphorus. The water-soluble portion ox the polyphosphate at 25C is 6 went %.
To determine the water-soluble portions, 10 g ammonium polyphosphate was suspended in 100 ml water and the suspension was stirred for 20 minutes at 25C. Next, the product portion not dissolved in the water was caused to sediment within 40 minutes, by centrifugation 5.0 ml ox the supernatant clear solution was petted into a previously weighed aluminum disk and evaporated in a drying cabinet at 120C. The water-soluble portion teas calculated from the quantity ox ev2porzticn residue.
As disclosed in European Patent Application 00 59 850, published September 15, 1982, it is known that the combustibility of products consisting essentially of cellulose fibers, erg paper, can be reduced by means of pulverulent red phosphorus having its individual particles enveloped by a mailmen resign, the products containing the flame retardant agent in a proportion of 4 to 18 weight %, especially 7 to 13 weight %.
The use of red phosphorus as a flame retardant agent for products consisting predominantly of cellulose fibers is not fully satisfactory for the following two reasons. Under the action of oxygen and moisture, red phosphorus is subject to disk proportionation with the resultant formation of toxic hydrogen phosphide. In addition to this, cellulose fibers admixed with red phosphorus have unsatisfactory flame retardant properties only. These are adverse effects which cannot fully be obviated even in the event of phosphorus particles encased by a mailmen resin being used.
German Patent DEEPS 30 20 033 discloses a process for making difficulty inflammable or incombustible products based on fibrous materials, wherein the fibrous materials are made into an aqueous pulp, the pulp is admixed with boron-containing minerals, the mixture is admitted to a fleece-forming and fiber-dehydrating machine, dehydrated and dried. More specifically, the aqueous pulp with the boron-containing minerals therein is intimately mixed with a mineral acid and the mixture is allowed to ripen prior I., to processing it. Coolant is used as the ooron-cen-twining Monroe and sulfuric acid is used as ire acid.
so can be inferred from sample 4 in DEEPS 30 20 0~3, this onion process calls or the use of a rela4i~ely large proportion of flame retardant coolant. The reason for this resides in the fact that a good deal of boric acid (this is acid which is being formed on subjecting Cole-nix to treatment with sulfuric acid) becomes dlssol~Jed in the aqueous phase of the cellulose leer pulp and lost so that it cannot contribute to conferring lame retardant properties upon the fibrous feed material, On the other hand a good deal ox calcium sulfate, which is a by-pro-duct obtained upon processing calumniate with H2SO4J is I ranked in tune final product, affecting the uali~y of paper made therefrom.
German Patent Specification DE-AS 17 71 693 provides flame retardant paper containing cellulose fibers that 'nave been treated with a substantially water-insoluble ammonium polyphosohate ox the general formula H(n_m)~2(~4)mPnO3n+1 in which n stands for a whole number of about 20 to 400 and the ratio men presents an average value of 0.7 to 1.1, and m stands or a value of at most no Tune ammonium pox lyphosphave is used in a proportion of about 1 to eta I especially 3 to 15 weight ,6, based on the queen-Tut of fiber.
The flame no ardent paper disclosed in DOW 17 71 owe' is made by a standard process by admixing the aqueous sup-pension of cellulose fixers with the ammonium ~olyp.ios?'ra~e Lo APE) and with a polyalkylenimine as a retention agent although ammonium polypnosphate is known to be a Good flame retardant agent, it does not provide an optimum flame retardant effect upon incorporating it with paper by a wet process, In the process of DE AS 17 71 693, there is, in a manner analogous to the process of DIPS 30 20 033, a con-siderable discrepancy between the quantity of flame no-tardant agent added to the pulp and the quantity actually contained in the finished paper. As described in Example 23 of DE-AS 17 71 693, 30 weight oh PUP based on the it-brows material, is introduced into the pulp, whilst the -final paper just contains 18,4 weight %, the undesirable loss of ASP is obviously the result of a portion of the ASP used being dissolved in the aqueous phase of the pulp and thus prevented prom contributing to rendering the paper flame retardant.
German Potent Specification DEMOS 29 49 537 describes, independently of rendering paper flare re~ardantl a part-curate agent obviating the combustibility of polyurethane and polyurethane foams, the agent being based on free flow-in pulverulent ammonium polyphosphates of which the India visual particles are coated with a hardened, water into-lube polycondensation product of mailmen and formalde-Hyde Nothing has been disclosed in DEMOS 29 I 537 as no-guards incorporation of the agent into materials to be non-dewed flame retardant.
The present invention now provides a process for con-furring good flame retardant properties upon paper and more generally upon materials containing cellulose fibers, which avoids the adverse effects associated with the ~rlor processes discussed hereinabove, and more particularly per-mitt the loss of flame retardant agent normally accompany-in the incorporation of the agent into the cellulose giber material]. to be reduced. The term paper as used herein denotes cellulose-containing materials, erg, standard paper grades, paper board, card board, and the live, e.g. also corrugated boards as secondary products, The present invention relates more particular-lye to flame retardant paper containing cellulose fibers and having been treated with an ammonium polyphos~hate as a flame retardant agent, the paper containing as the flame retardant agent a product consisting of a) 75 to 99.5 weight % of a pulverulent, free flowing ammonium pol~hosphate of the general formula Ho T2(N~4)mPnO3n+1 in which n stands for a whole number with an average value of 20 to 800 and the ratio m/n is about 1, and b) 0.5 to 25 weight ox a hardened, ~ater-insoluble en-tickle resin encasing the individual ammonium holy-phosphate particles, in a proportion of about 5 to 30 weight %, based on the dry fibrous material.
The lame retardant agent should generally be used in the form of particles with a mean size ox about 0.01 to 0.5 mm and conveniently has an average degree of con-sensation n of 450 to 800, determined by the terminal group titration process (van Waxer, Grafter and McCullou~en, Anal. Chum. 26, page 1755 (1954))~ The artificial resin encasing the flame retardant agent preferably is a condemn-station product of examine and formaldehyde This product in its unhardened state, is e I. a powder of which a 50 ,b aqueous solution has a dynamic viscosity of 20 ma . sec., a pi value at 20C of So to So and a density at 20C of 1.21 to 1.225 g/ml.
The invention also relates to a process for making flame retardant paper, which comprises admixing an aqueous suspension consisting essentially of cellulose fibers with 5 to 30 weight oh based on the dry fibrous material, of a flame retardant agent consisting of a) 75 to 99.5 weight % of a pulverulent, free flowing ammonium polyphosphate of the general formula H(n_m)+2(NH4)m~nO3n~1 in which n stands for a whole number with an average value of about 20 to 800 and the ratio m/n is about 1, and b) 0.5 to 25 weight I of a hardened, water-insoluble artificial resin encasing the individual ammonium polyp phosphate particles and admitting the resulting mixture to a ~leece-forming and fiber-dehydrating machine, dehydrating the said mixture and drying it.
A preferred feature of the present process provides or a pi value of 3 to 9, preferably 4 to 8, to be establish-Ed in the aqueous suspension ox cellulose fibers by adding an acid, e.g. a mineral acid, or alkaline liquor thereto, prior to or after the addition of the flame retardant agent.
A further preferred feature of the present process provides for the flame retardant agent to be used in he form of a 1 to 20 weight % aqueous suspension and for this suspension to be introduced into an bout 0.5 to 5 eye I
suspension of cellulose fibers in water.
A still further preferred feature of the present pro-cuss provides for the aqueous suspension to be additionally ad-mixed with about 0.1 to 0.5 weight %, based on the dry fibrous material, of a dehydrating and retention agent and for the whole to be immediately thereafter admitted to the fleece-forming and fiber-dehydrating machine. A useful retention agent is, for example, an aqueous solution of a high molecular weight, cation-active polyamide having a density of about 1.05 g/cm3, a viscosity of 500 to 1500 ma . second (Brook field), and a pi of 6, and being water-soluble in cold water in whatever ratio.
The following statements are intended further to if lust rate the invention.
The ammonium polyphosphates on which the flame retardant agent of this invention is being based are commercially available products which can be produced e.g. by the process disclosed in Canadian Patent Application Serial No. 421 023 and which can be coated with a mailmen resin by the process disclosed in German Patent Specification DEMOS 29 49 537.
The flame retardant agent of this invention can be in-corporate with the pa performing material during a standard paper making process, e.g. in the wet stage, preferably to the paper suspension containing cellulose fibers, coming from the last purification stage. Apart from the addition of a known retention agent mentioned above, the invention provides for the fiber pulp to be additionally admixed with standard binders and fillers, if desired, The papers made in accordance with this invention have very good flame retardant properties and they comply with the .
requirements ox Classes 31 and 32 I Dl~-speci4ication (DIN
stands 40r German Industrial Standard) Lo 02 . As regards difficult sealability- in water, the present lame retardant agents compare favorably with the prior agents heretofore incorporated with paper. This beneficially influences awry mixing since -there is considerably 1QSS discrepancy than here-tougher between the quantity of lame retardant agent it-traduced into the cellulose fiber pulp and the airtight ox flame retardant agent actually contained in the taper produced.
The Wang Examples illustrate the invention, in which the following products were used.
1. Flame retardant agent A:
It is a difficultly water soluble ammonium polyphcsphate ox the formula (NH4P03)n, with a degree of condensation n I about 700. The a.~monium polyphosphate was made by the process described in US Patent Application Serial No. 464 982. It contains ~1.2 weight 6 phosphorus. The water-soluble portion ox the polyphosphate at 25C is 6 went %.
To determine the water-soluble portions, 10 g ammonium polyphosphate was suspended in 100 ml water and the suspension was stirred for 20 minutes at 25C. Next, the product portion not dissolved in the water was caused to sediment within 40 minutes, by centrifugation 5.0 ml ox the supernatant clear solution was petted into a previously weighed aluminum disk and evaporated in a drying cabinet at 120C. The water-soluble portion teas calculated from the quantity ox ev2porzticn residue.
2. Fly retardant agent 3:
Flame retardant agent B differs prom flame retardant aver I
PA in that the India dual ammonium polyphospha'e particle are provided with a hardened, water-insoluble coating of pol~fcondensed mailmen arid formaldehyde. Flame no tardant agent B was made by the process disclosed in German Patent Specification DEMOS 29 I 5~7.
The agent contained 29.5 weight 96 phosphorus end less than 0.5 weight % was water-soluble at 25C.
Flame retardant agent B differs prom flame retardant aver I
PA in that the India dual ammonium polyphospha'e particle are provided with a hardened, water-insoluble coating of pol~fcondensed mailmen arid formaldehyde. Flame no tardant agent B was made by the process disclosed in German Patent Specification DEMOS 29 I 5~7.
The agent contained 29.5 weight 96 phosphorus end less than 0.5 weight % was water-soluble at 25C.
3. Flame retardant agent C:
It is an ammonium pol~hosphate which contains 32.8 weight US phosphorus and of Russia 21 weight % is water-soluble at 25C. The product is commercially available under the designation PHOSCHECX POW (this is a register-Ed Trade Mark of Monsanto Chemical Coup., St. Louis, Us
It is an ammonium pol~hosphate which contains 32.8 weight US phosphorus and of Russia 21 weight % is water-soluble at 25C. The product is commercially available under the designation PHOSCHECX POW (this is a register-Ed Trade Mark of Monsanto Chemical Coup., St. Louis, Us
4. Flame retardant agent D:
This is water-insoluble, stabilized red phosphorus en-capsuled in a melamine/formaldehyde-resin by the process disclosed in German Patent DYES 26 55 739. It contains about 54.3 weight b phosphorus and about 6 weight %
melamine/formaldehyde resin.
This is water-insoluble, stabilized red phosphorus en-capsuled in a melamine/formaldehyde-resin by the process disclosed in German Patent DYES 26 55 739. It contains about 54.3 weight b phosphorus and about 6 weight %
melamine/formaldehyde resin.
5. Retention agent:
To is an aqueous solution of a high molecular weight, cation-active polyamide. The agent is commercially available under the designation LAUREATE 8298 (this is a registered Trade Mark of BASS ~TIr.NGESELL~CY~FT
Ludwigshafen, Federal Republic of Germany).
The retention agent is a clear yellow liquid l~hlch has a density of about 1.05 gym 2 viscosity of KIWI to 1500 ma . sea (Brook ilk) and a pi of about 6. It is water-soluble in whatever ratio.
example 1 550 ml of a 1 weight I, aqueous pulp of waste paper (group A-4 of the list of European 'taste Paper Standard Grades - CEPAC l981 -) with a fineness of grinding ox Lo-50 SO was treated with sulfuric acid of about 5 % strengths as to establish a pi of 4.5, admixed with 1.70 g of flame retardant agent B, which was an about 5 weight ,6 aqueous suspension, and the whole was stirred for 5 minutes. The pi which had meanwhile increased to 4.6 assay corrected to 4.5 by the addition of further sulfuric acid of about 5 strength. Next, 25 ml of an 0.05 weight QUEUE aqueous solution of the retention agent was added and the mixture was jilter-Ed using a porcelain suction filter 25 cm in diameter, with a lowdown paper titter. The resulting sheet was dried initially for 2 minutes on the suction filter and then or 1 hour in a drying cabinet at 105C.
Next, the surface weight and phosphorus content were determined on the dried paper specimen and the burn-up test was effected on the paper specimen conditioned over 24 hours at 2~C and I I relative atmospheric moisture. The test results obtained are indicated in Tables 1 and 2 hereinafter.
Examples 2 to (Invention) The procedure was as in Example 1 save that the pH-values and quantities ox flame retardant agent B were varied The test results obtained are indicated in Tables 1 and 2 herein-after.
Examples 10 -to 12 (Comparative Examples) The procedure was as in Example 1 save that flame no-tardant agent A was used in different concentrations.
The test results obtained are indicated in Tables 1 arid 2 errantry.
Examples 13 to 15 (comparative Employs) The procedure was as in Example 1 save that lame retardant agent C was used in different concentrations.
The test results obtained are indicated in Tables 1 and 2 hereinafter.
Examples 16 to 18 (comparative Examples) The procedure was as in Example 1 save that flame retardant agent D was used in different concentrations.
The test results obtained are indicated in Tables 1 and 2 hereinafter.
summarized in Table 1 are the analytical data deter-mined or the various paper specimens and summarized in Table 2 are the burn-up test results or the various paper specimens. The (+) sign in Table 2 indicates that the specimen"successfull~J passed" the burn-up test of DIN-specification 4102, whilst the (-) sign indicates that the specimen "failed". The values indicated fur the concentra-lion ox the lame retardant agent in Tale 1, in the column headed "calculated", are based on the weighed dry paper specimen. All values indicated in Tables 1 and 2 are average values determined in each particular case on three paper specimens.
As shown in Tables 1 and 2, considerably less lame retardant agent than in the prior paper making methods (comparative papers) is lost in the present paper making preseason addition to this and in clear contrast with the comparative paper specimens, the papers jade in accordance with this invention co~lplv with the requirements OX classes I By and By ox DIN-specif-cation ~102.
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To is an aqueous solution of a high molecular weight, cation-active polyamide. The agent is commercially available under the designation LAUREATE 8298 (this is a registered Trade Mark of BASS ~TIr.NGESELL~CY~FT
Ludwigshafen, Federal Republic of Germany).
The retention agent is a clear yellow liquid l~hlch has a density of about 1.05 gym 2 viscosity of KIWI to 1500 ma . sea (Brook ilk) and a pi of about 6. It is water-soluble in whatever ratio.
example 1 550 ml of a 1 weight I, aqueous pulp of waste paper (group A-4 of the list of European 'taste Paper Standard Grades - CEPAC l981 -) with a fineness of grinding ox Lo-50 SO was treated with sulfuric acid of about 5 % strengths as to establish a pi of 4.5, admixed with 1.70 g of flame retardant agent B, which was an about 5 weight ,6 aqueous suspension, and the whole was stirred for 5 minutes. The pi which had meanwhile increased to 4.6 assay corrected to 4.5 by the addition of further sulfuric acid of about 5 strength. Next, 25 ml of an 0.05 weight QUEUE aqueous solution of the retention agent was added and the mixture was jilter-Ed using a porcelain suction filter 25 cm in diameter, with a lowdown paper titter. The resulting sheet was dried initially for 2 minutes on the suction filter and then or 1 hour in a drying cabinet at 105C.
Next, the surface weight and phosphorus content were determined on the dried paper specimen and the burn-up test was effected on the paper specimen conditioned over 24 hours at 2~C and I I relative atmospheric moisture. The test results obtained are indicated in Tables 1 and 2 hereinafter.
Examples 2 to (Invention) The procedure was as in Example 1 save that the pH-values and quantities ox flame retardant agent B were varied The test results obtained are indicated in Tables 1 and 2 herein-after.
Examples 10 -to 12 (Comparative Examples) The procedure was as in Example 1 save that flame no-tardant agent A was used in different concentrations.
The test results obtained are indicated in Tables 1 arid 2 errantry.
Examples 13 to 15 (comparative Employs) The procedure was as in Example 1 save that lame retardant agent C was used in different concentrations.
The test results obtained are indicated in Tables 1 and 2 hereinafter.
Examples 16 to 18 (comparative Examples) The procedure was as in Example 1 save that flame retardant agent D was used in different concentrations.
The test results obtained are indicated in Tables 1 and 2 hereinafter.
summarized in Table 1 are the analytical data deter-mined or the various paper specimens and summarized in Table 2 are the burn-up test results or the various paper specimens. The (+) sign in Table 2 indicates that the specimen"successfull~J passed" the burn-up test of DIN-specification 4102, whilst the (-) sign indicates that the specimen "failed". The values indicated fur the concentra-lion ox the lame retardant agent in Tale 1, in the column headed "calculated", are based on the weighed dry paper specimen. All values indicated in Tables 1 and 2 are average values determined in each particular case on three paper specimens.
As shown in Tables 1 and 2, considerably less lame retardant agent than in the prior paper making methods (comparative papers) is lost in the present paper making preseason addition to this and in clear contrast with the comparative paper specimens, the papers jade in accordance with this invention co~lplv with the requirements OX classes I By and By ox DIN-specif-cation ~102.
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Claims (11)
We ClAIM
1. Flame retardant paper containing cellulose fibers and having been treated with an ammonium polyphosphate as a flame retardant agent, the paper containing as the flame retardant agent a product consisting of a) 75 to 99 5 weight % of a pulverulent, free-flow-ing ammonium polyphosphate of the general formula H(n-m)+2(NH4)mPn03n+1 in which n stands for a whole number with an average value of 20 to 800 and the ratio m/n is about 1, and b) 0.5 to 25 weight % of a hardened, water-inso-luble artificial resin encasing the individu-al ammonium polyphosphate particles, in 2 proportion of 5 to 30 weight %, based on the dry fibrous material.
2. Flame retardant paper as claimed in claim 1, wherein the flame retardant agent consists of particles with a mean size of 0.01 to 0.05 mm.
3. Flame retardant paper as claimed in claim 1, wherein n stands for a whole number with an average value of 450 to 800.
4. Flame retardant paper as claimed in claim 1, wherein the hardened, water-insoluble artificial resin is a polycondensation product of melamine and formalde-hyde.
5. Flame retardant paper as claimed in claim 1, wherein the polycondensation product in its unhardened state is a powder of which a 50 % aqueous solution has a dynamic viscosity of 20 mPa second, pH value at 20°C of 8.8 to 9.8 and a density at 20°C of 1.21 to 1.225 g/cm3.
6. Process or making flame retardant paper as claimed in claim 1, which comprises: admixing an aqueous sus-pension consisting essentially of cellulose fibers with 5 to 30 weight %, based on the dry fibrous material, of a flame retardant agent consisting of a) 75 to 99.5 weight % of a pulverulent, free-flow-ing ammonium polyphosphate of the general formula H(n_m)+2(NH4)mPnO3n+1 in which n stands for a whole number with an average value of 20 to 800 and the ratio m/n is about 19 and b) 0.5 to 25 weight % of a hardened, water-inso-luble artificial resin encasing the individu-al ammonium Polyphosphate particles, and ad-mitting the resulting mixture to a fleece-form-ing and fiber-dehydrating machine, dehydrating the said mixture and drying it.
7. Process as claimed in claim 6, wherein the aqueous suspension is additionally admixed with 0.1 to 0.5 weight %, based on the dry fibrous material, of a dehydrating and retention agent and immediately there-after admitted to the fleece-forming and fiber-dehy-drating machine.
8. Process as claimed in claim 7, wherein the retention agent is an aqueous solution of a high molecular weight, cationactive polyamine having a density of about 1.05 g/cm3 a viscosity of 500 to 1500 mPa. se-cond (Brookfield), and a pH of 6, and being water-soluble in cold water in whatever ratio.
9. Process as claimed in claim 6, wherein a pH value of 3 to 9 is established in the aqueous suspension of cellulose fibers by adding an acid or alkaline liquor thereto, prior to or after the addition of the flame retardant agent.
10. Process as claimed in claim 6, wherein a pH-value of 4 to 8 is established in the aqueous suspension of cellulose fibers by adding an acid or alkaline liquor thereto prior to or after the addition of the flame-retardant agent.
11. Process as claimed in claim 6, wherein the flame-re-tardant agent is added in the form of a 1 to 20 weight % aqueous suspension to a 0.5 to 5 weight %
suspension of cellulose fibers in water.
suspension of cellulose fibers in water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833311770 DE3311770A1 (en) | 1983-03-31 | 1983-03-31 | FLAME-RESISTANT PAPER AND A METHOD FOR THE PRODUCTION THEREOF |
| DEP3311770.5 | 1983-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1217903A true CA1217903A (en) | 1987-02-17 |
Family
ID=6195212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000447777A Expired CA1217903A (en) | 1983-03-31 | 1984-02-17 | Flame retardant paper and process for making it |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0121162B1 (en) |
| JP (1) | JPS59187698A (en) |
| AT (1) | ATE22947T1 (en) |
| CA (1) | CA1217903A (en) |
| DE (2) | DE3311770A1 (en) |
| DK (1) | DK120684A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0320000A (en) * | 1989-06-15 | 1991-01-29 | Noda Corp | Inorganic board for architecture |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH524713A (en) * | 1967-06-28 | 1972-06-30 | Monsanto Co | Non-textile product containing cellulose fibers, in particular paper, and process for the production thereof |
| JPS499727B1 (en) * | 1969-06-30 | 1974-03-06 | ||
| JPS5914511B2 (en) * | 1976-11-18 | 1984-04-04 | 丸菱油化工業株式会社 | A flame retardant that provides a coating film with good transparency. |
| JPS5610582A (en) * | 1979-07-07 | 1981-02-03 | Otsuka Chem Co Ltd | Flame retarder and flame-retardant treatment |
| DE2949537A1 (en) * | 1979-12-08 | 1981-06-11 | Hoechst Ag, 6000 Frankfurt | PARTICULATE AGENT FOR PREVENTING THE FLAMMABILITY OF FLAMMABLE SUBSTANCES |
| IT1137409B (en) * | 1981-03-05 | 1986-09-10 | Saffa Spa | SELF-EXTINGUISHING PAPER MATERIALS |
-
1983
- 1983-03-31 DE DE19833311770 patent/DE3311770A1/en not_active Withdrawn
-
1984
- 1984-02-17 CA CA000447777A patent/CA1217903A/en not_active Expired
- 1984-02-28 DK DK120684A patent/DK120684A/en not_active Application Discontinuation
- 1984-03-15 AT AT84102843T patent/ATE22947T1/en not_active IP Right Cessation
- 1984-03-15 DE DE8484102843T patent/DE3460993D1/en not_active Expired
- 1984-03-15 EP EP84102843A patent/EP0121162B1/en not_active Expired
- 1984-03-28 JP JP59058561A patent/JPS59187698A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE3311770A1 (en) | 1985-01-17 |
| EP0121162A3 (en) | 1984-11-28 |
| DK120684A (en) | 1984-10-01 |
| EP0121162B1 (en) | 1986-10-15 |
| ATE22947T1 (en) | 1986-11-15 |
| EP0121162A2 (en) | 1984-10-10 |
| JPS59187698A (en) | 1984-10-24 |
| DE3460993D1 (en) | 1986-11-20 |
| DK120684D0 (en) | 1984-02-28 |
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