Phosphorus-containing flame retardant formulation for cellulose-containing moldings

Abstract

The invention relates to a phosphorus-containing flame retardant formulation for cellulose-containing moldings, comprising from 0.1 to 99.9% by weight of a resin of an organic nitrogen compound and from 0.1 to 99.9% by weight of a phosphorus-containing flame retardant.

1 . A phosphorus-containing flame retardant formulation for a cellulose-containing material, comprising 
 from 0.1 to 99.9% by weight of at least one resin of an organic nitrogen compound and    from 0.1 to 99.9% by weight of at least one phosphorus-containing flame retardant.    
     
     
         2 . The phosphorus-containing flame retardant formulation as claimed in  claim 1 , wherein the at least one phosphorus-containing flame retardant comprises at least one particulate phosphorus-containing flame retardant.  
     
     
         3 . The phosphorus-containing flame retardant formulation as claimed in  claim 2 , wherein the at least one particulate phosphorus-containing flame retardant comprises a phosphinic salt of the formula (I) diphosphinic salt of the formula (II) a polymer of the phosphinic salt, a polymer of the diphosphinic salt or a mixture thereof,  
       
         
           
           
               
               
           
         
         wherein  
         R 1  and R 2  are identical or different and are C 1 -C 6 -alkyl, linear or branched, or aryl; R 3  is C 1 -C 10 -alkylene, linear or branched, C 6 -C 10 -arylene, -alkylarylene, or -arylalkylene; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li or a protonated nitrogen base; m is from 1 to 4; n is from 1 to 4; x is from 1 to 4.  
       
     
     
         4 . The phosphorus-containing flame retardant formulation as claimed in  claim 3 , wherein R 1  and R 2  are identical or different and are C 1 -C 6 -alkyl, linear or branched, or phenyl.  
     
     
         5 . The phosphorus-containing flame retardant formulation as claimed in  claim 3 , wherein R 1  and R 2  are identical or different and are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, or phenyl.  
     
     
         6 . The phosphorus-containing flame retardant formulation as claimed in  claim 3 , wherein R 3  is methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene; n-dodecylene; phenylene; naphthylene; methylphenylene, ethylphenylene, tert-butylphenylene, methyl-naphthylene, ethylnaphthylene, tert-butylnaphthylene; phenylmethylene, phenyl-ethylene, phenylpropylene, or phenylbutylene.  
     
     
         7 . The phosphorus-containing flame retardant formulation as claimed in  claim 2 , having from 4.4 to 82.3% by weight of the at least one resin of an organic nitrogen compound and from 95.6 to 17.7% by weight of the at least one particulate phosphorus-containing flame retardant.  
     
     
         8 . The phosphorus-containing flame retardant formulation as claimed in  claim 1 , having a thermal stability extending to 200-500° C.  
     
     
         9 . The phosphorus-containing flame retardant formulation as claimed in  claim 2 , wherein the solubility of the at least one particulate flame retardant is from 0.001 to 15% by weight in water, in organic solvents or a mixture thereof.  
     
     
         10 . The phosphorus-containing flame retardant formulation as claimed in  claim 2 , wherein the median particle size d 50  of the at least one particulate flame retardant is from 1 nm to 5 mm.  
     
     
         11 . The phosphorus-containing flame retardant formulation as claimed in  claim 1 , wherein the at least one phosphorus-containing flame retardant is at least one non-particulate phosphorus-containing flame retardant.  
     
     
         12 . The phosphorus-containing flame retardant formulation as claimed in  claim 11 , wherein the at least one non-particulate phosphorus-containing flame retardant comprises a phosphinic acid a phosphinic salt of the formula (I) a diphosphinic acid a diphosphinic salt of the formula (II) a polymer of the phosphinic acid, a polymer of the phosphinic salt, a polymer of the diphosphinic acid, a polymer of the diphosphinic salt and mixtures thereof,  
       
         
           
           
               
               
           
         
         wherein  
         R 1  and R 2  are identical or different and are C 1 -C 6 -alkyl, linear or branched, or aryl; R 3  is C 1 -C 10 -alkylene, linear or branched, C 6 -C 10 -arylene, -alkylarylene, or -arylalkylene, M is Na, K, or H, and  
         m is 1;  
         n is 1;  
         x is 1.  
       
     
     
         13 . The phosphorus-containing flame retardant formulation as claimed in  claim 11  further comprising an aluminum compound, titanium compound, zinc compound, tin compound, zirconium compound or a mixture thereof.  
     
     
         14 . (canceled)  
     
     
         15 . A phosphorus-containing flame retardant formulation comprising a two-component phosphorus-containing flame retardant formulation of from 0.1 to 99.9% by weight of a component A and from 0.1 to 99.9% by weight of a component B, where component A is from 0.1 to 99.9% by weight of at least one resin of an organic nitrogen compound and from 0.1 to 99.9% by weight of at least one non-particulate phosphorus-containing flame retardant, and component B is a metal compound selected from the group consisting of an aluminum compound, titanium compound, zinc compound, tin compound, zirconium compound and mixtures thereof.  
     
     
         16 . The phosphorus-containing flame retardant formulation as claimed in  claim 15 , having from 68.9 to 94.2% by weight of a component A and from 31.1 to 5.83% by weight of a component B, wherein component A is from 93.7 to 12.9% by weight of the at least one resin of an organic nitrogen compound and from 6.3 to 87.1% by weight of the at least one non-particulate phosphorus-containing flame retardant.  
     
     
         17 . The phosphorus-containing flame retardant formulation as claimed in  claim 15 , having from 68.9 to 87.9% by weight of a component A and from 31.1 to 12.1% by weight of a component B, wherein component A is from 93.7 to 1.5% by weight of the at least one resin of an organic nitrogen compound and from 6.3 to 98.5% by weight of the at least one non-particulate phosphorus-containing flame retardant.  
     
     
         18 . A phosphorus-containing flame retardant formulation comprising a two-component phosphorus-containing flame retardant formulation having from 0.1 to 99.9% by weight of a component C and from 0.1 to 99.9% by weight of a component D, wherein component C is from 0.1 to 99.9% by weight of at least one resin of an organic nitrogen compound and from 0.1 to 99.9% by weight of a compound selected from the group consisting of an aluminum compound, titanium compound, zinc compound, tin compound, zirconium compound and mixtures thereof, and component D is at least one non-particulate phosphorus-containing flame retardant.  
     
     
         19 . The phosphorus-containing flame retardant formulation as claimed in  claim 18 , having from 13.3 to 95.6% by weight of a component C and from 86.7 to 4.4% by weight of a component D, where component C is composed of from 9.6 to 67.5% by weight of the at least one resin of an organic nitrogen compound and from 90.4 to 32.5% by weight of the metal compound.  
     
     
         20 . The phosphorus-containing flame retardant formulation as claimed in  claim 18 , having from 22.3 to 86.8% by weight of a component C and from 77.7 to 13.2% by weight of a component D, where component C is composed of from 51.5 to 67.5% by weight of the at least one resin of an organic nitrogen compound and from 48.5 to 32.5% by weight of the metal compound.  
     
     
         21 . A phosphorus-containing flame retardant comprising a three-component phosphorus-containing flame retardant formulation having from 0.1 to 99.9% by weight of a component E, at least one resin of an organic nitrogen compound, from 0.1 to 99.9% by weight of a component D, at least one non-particulate phosphorus-containing flame retardant, and from 0.1 to 99.9% by weight of a component B, a metal compound selected from the group consisting of an aluminum compound, titanium compound, zinc compound, compound, zirconium compound and mixtures thereof.  
     
     
         22 . The phosphorus-containing flame retardant formulation as claimed in  claim 21  having from 1 to 65% by weight of component E, from 4 to 87% by weight of component D, and from 12 to 32% by weight of component B.  
     
     
         23 . The phosphorus-containing flame retardant formulation as claimed in  claim 21 , having from 11 to 59% by weight of component E, from 13 to 78% by weight of a component D and from 12 to 38% by weight of a component B.  
     
     
         24 . The phosphorus-containing flame retardant formulation as claimed in  claim 21 , wherein the at least one resin of an organic nitrogen compound is a resin and/or a condensate of a carbonyl compound with an organic nitrogen compound.  
     
     
         25 . The phosphorus-containing flame retardant formulation as claimed in  claim 21 , wherein the at least one resin of an organic nitrogen compound is a dicyandiamide resin composed of 1 mol of dicyandiamide and from 1 to 10 mol of formaldehyde.  
     
     
         26 . The phosphorus-containing flame retardant formulation as claimed in  claim 11 , wherein the solubility of the at least one non-particulate flame retardant is from 20 to 100% by weight in water organic solvents or a mixture thereof.  
     
     
         27 . A process for the preparation of a phosphorus-containing flame retardant formulation as claimed in at  claim 2 , comprising the steps of mixing at least one organic nitrogen compound, formaldehyde and, optionally, at least one solvent at from 10 to 300° C. for from 0.1 to 100 h, to form a mixture, and incorporating into the mixture at least one mono- or polyfunctional amines, and also amine and at least one particulate phosphorus-containing flame retardant and, optionally, a metal compound selected from the group consisting of aluminum compounds, titanium compounds, zinc compounds, tin compounds, zirconium compounds or a mixture thereof.  
     
     
         28 . A process for preparation of a phosphorus-containing flame retardant formulation as claimed in  claim 15 , comprising the steps of, for preparation of component A, mixing dicyandiamide, formaldehyde, and solvent, and optionally at least one mono- or polyfunctional amine at from 10 to 300° C. for from 0.1 to 100 h, and adding the at least one non-particulate phosphorus-containing flame retardant to form a mixture, and mixing the metal compound into the mixture.  
     
     
         29 . A process for preparation of a phosphorus-containing flame retardant formulation as claimed in  claim 18 , comprising the steps of, for preparation of component C, mixing dicyandiamide, formaldehyde, and solvent, and optionally at least one mono- or polyfunctional amine at from 10 to 300° C. for from 0.1 to 100 h, to form a mixture, adding the metal compound to the mixture and mixing the at least one non-particulate phosphorus-containing flame retardant.  
     
     
         30 . A process for preparation of a phosphorus-containing flame retardant formulation as claimed in  claim 21 , comprising the steps of, for preparation of component E, mixing dicyandiamide, formaldehyde, and solvent, and optionally at least one mono- or polyfunctional amine at from 10 to 300° C. for from 0.1 to 100 h, adding the at least one non-particulate phosphorus-containing flame retardant to form a mixture, and mixing the metal compound into the mixture.  
     
     
         31 . The process as claimed in  claim 27 , further comprising the step of adjusting the pH by mixing at least one pH modifier at from 10 to 300° C. for from 0.1 to 100 h.  
     
     
         32 . A flame retardant cellulose containing material comprising a phosphorus-containing flame retardant formulation as claimed in  claim 1 .  
     
     
         33 . A process for providing flame retardancy to paper, cardboard or paperboard comprising the step of adding a phosphorus-containing flame retardant formulation as claimed in  claim 2  to the fiber suspension of the paper, cardboard or paperboard during engine sizing.  
     
     
         34 . A process for providing flame retardancy to paper, cardboard, or paperboard, comprising the step of adding a phosphorus-containing flame retardant formulation of  claim 11  to the fiber suspension of the paper, cardboard or paperboard during engine sizing.  
     
     
         35 . A process for providing flame retardancy to paper, cardboard, or paperboard comprising the step of adding a phosphorus-containing flame retardant formulation of  claim 15  to the fiber suspension of the paper, cardboard or paperboard during engine sizing.  
     
     
         36 . A process for providing flame retardancy to paper, cardboard, or paperboard, comprising the step of adding a phosphorus-containing flame retardant formulation of  claim 18  to the fiber suspension of the paper cardboard or paperboard during engine sizing.  
     
     
         37 . A process for providing flame retardancy to paper, cardboard, or paperboard, comprising the step of adding a phosphorus-containing flame retardant formulation of  claim 21  to the fiber suspension of the paper, cardboard or paperboard during engine sizing.  
     
     
         38 . A process for providing flame retardancy to a textile comprising the step of applying a phosphorus-containing flame retardant formulation of  claim 1  in the form of an impregnating solution to the textile.  
     
     
         39 . The process as claimed in  claim 38 , wherein the impregnating solution is applied immersion or by spray-application onto the textile.  
     
     
         40 . A process for providing flame retardancy to wood comprising the steps of introducing the wood into an impregnating system, exposing the wood for at least 20 minutes to a pressure of 50 mbar, impregnating the wood at a pressure of 16 bar for from 1 to 10 hours with an impregnating solution comprising a phosphorus-containing flame retardant formulation of  claim 1 .  
     
     
         41 . A method for providing flame retardancy to wood comprising the step of coating the wood via by a dipping process, spraying process, or spreading process, with a coating component comprising a phosphorus-containing flame retardant formulation of  claim 1 .  
     
     
         42 . A flame-retardant cellulose-containing molding comprising: 
 from 0.01 to 90% by weight of cellulose    from 0.01 to 90% by weight of at least one resin of an organic nitrogen compound    from 0.01 to 90% by weight of at least one non-particulate phosphorus-containing flame retardant, and    from 0.01 to 90% by weight of a metal compound selected from the group consisting of an aluminum compound, titanium compound, zinc compound, tin compound, zirconium compound and mixtures thereof.    
     
     
         43 . A flame-retardant cellulose-containing molding comprising: 
 from 0.01 to 90% by weight of cellulose    from 0.01 to 90% by weight of at least one resin of an organic nitrogen compound, and    from 0.01 to 90% by weight of at least one particulate phosphorus-containing flame retardant.    
     
     
         44 . A flame-retardant cellulose-containing molding comprising: 
 from 1 to 50% by weight of cellulose    from 1 to 30% by weight of dicyandiamide-formaldehyde resin, and    from 1 to 50% by weight of at least one particulate phosphorus-containing flame retardant.    
     
     
         45 . A flame-retardant cellulose-containing molding comprising: 
 from 1 to 50% by weight of cellulose    from 1 to 30% by weight of melamine-formaldehyde resin, and    from 1 to 50% by weight of at least one particulate phosphorus-containing flame retardant.    
     
     
         46 . The phosphorus-containing flame retardant formulation as claimed in  claim 2 , having from 18.8 to 69.9% by weight of the resin of an organic nitrogen compound and from 81.2 to 30.1% by weight of the particulate phosphorus-containing flame retardant.  
     
     
         47 . The phosphorus-containing flame retardant formulation as claimed in  claim 1 , having a thermal stability extending to 250-400° C.  
     
     
         48 . The phosphorus-containing flame retardant formulation as claimed in  claim 2 , wherein the solubility of the particulate flame retardant is from 0.1 to 9.9% by weight in water in organic solvents or a mixture thereof.  
     
     
         49 . The phosphorus-containing flame retardant formulation as claimed in  claim 2 , wherein the median particle size d 50  of the particulate flame retardant is from 1 to 20 μm.  
     
     
         50 . The phosphorus-containing flame retardant formulation as claimed in  claim 11 , having from 4.4 to 82.3% by weight of the at least one resin of an organic nitrogen compound and from 95.6 to 17.7% by weight of the at least one non-particulate phosphorus-containing flame retardant.  
     
     
         51 . The phosphorus-containing flame retardant formulation as claimed in  claim 11 , having from 18.8 to 69.9% by weight of the at least one resin of an organic nitrogen compound and from 81.2 to 30.1% by weight of the at least one non-particulate phosphorus-containing flame retardant.  
     
     
         52 . The phosphorus-containing flame retardant formulation as claimed in  claim 21 , wherein the at least one resin of an organic nitrogen compound is selected from the group consisting of urea, substituted urea derivatives, thiourea, guanidine, substituted guanadine derivatives, biguanide, melamine, substituted melamine derivatives, condensates of melamine and higher-level-condensation products thereof, melamine-phenol systems, benzoguanamine, acetoguanamine, urethanes, cyanamide, dicyandiamide, aniline, sulfonamide, biuret, allantoin, tolyltriazole, benzotriazole, 2-amino-4-methylpyrimidine, hydantoin, substituted hydantoin derivatives, malonamide amidine, ethylenebis-5-triazone, glycine anhydride, and mixtures thereof.  
     
     
         53 . The phosphorus-containing flame retardant formulation as claimed in  claim 1 , wherein the at least one resin of an organic nitrogen compound is a dicyandiamide resin composed of 1 mol of dicyandiamide and from 1 to 10 mol of formaldehyde.  
     
     
         54 . The phosphorus-containing flame retardant formulation as claimed in  claim 1 , wherein the at least one resin of an organic nitrogen compound is a dicyandiamide resin composed of 1 mol of dicyandiamide and from 1 to 4 mol of formaldehyde.  
     
     
         55 . The phosphorus-containing flame retardant formulation as claimed in  claim 1 , wherein the at least one resin of an organic nitrogen compound is selected from the group consisting of urea, substituted urea derivatives, thiourea, guanidine, substituted guanadine derivatives, biguanide, melamine, substituted melamine derivatives, condensates of melamine and higher-level-condensation products thereof, melamine-phenol systems, benzoguanamine, acetoguanamine, urethanes, cyanamide, dicyandiamide, aniline, sulfonamide, biuret, allantoin, tolyltriazole, benzotriazole, 2-amino-4-methylpyrimidine, hydantoin, substituted hydantoin derivatives, malonamide amidine, ethylenebis-5-triazone, glycine anhydride, and mixtures thereof.  
     
     
         56 . The phosphorus-containing flame retardant formulation as claimed in  claim 21 , wherein the at least one resin of an organic nitrogen compound is a dicyandiamide resin composed of 1 mol of dicyandiamide and from 1 to 4 mol of formaldehyde.  
     
     
         57 . A process for the preparation of a phosphorus-containing flame retardant formulation as claimed in at  claim 11 , comprising the steps of mixing at least one organic nitrogen compound, formaldehyde and, optionally, at least one solvent at from 10 to 300° C. for from 0.1 to 100 h, to form a mixture, and incorporating into the mixture at least one mono- or polyfunctional amine and at least one non-particulate phosphorus-containing flame retardant and, optionally, a metal compound selected from the group consisting of aluminum compounds, titanium compounds, zinc compounds, tin compounds, zirconium compounds or a mixture thereof.  
     
     
         58 . The process as claimed in  claim 31 , wherein the pH is adjusted from between 8 to 13.  
     
     
         59 . The process as claimed in  claim 28 , further comprising the step of adjusting the pH by mixing at least one pH modifier at from 10 to 300° C. for from 0.1 to 100 h.  
     
     
         60 . The process as claimed in  claim 59 , wherein the pH is adjusted from between 8 to 13.  
     
     
         61 . The process as claimed in  claim 29 , further comprising the step of adjusting the pH by mixing at least one pH modifier at from 10 to 300° C. for from 0.1 to 100 h.  
     
     
         62 . The process as claimed in  claim 61 , wherein the pH is adjusted from between 8 to 13.  
     
     
         63 . The process as claimed in  claim 30 , further comprising the step of adjusting the pH by mixing at least one pH modifier at from 10 to 300° C. for from 0.1 to 100 h.  
     
     
         64 . The process as claimed in  claim 63 , wherein the pH is adjusted from between 8 to 13.  
     
     
         65 . The flame retardant cellulose containing material as claimed in  claim 32 , wherein the cellulose containing material is selected from the group consisting of paperboard, textiles and wood.  
     
     
         66 . Flame retardant paper, cardboard, or paperboard made in accordance with the process of  claim 33 .  
     
     
         67 . Flame retardant paper, cardboard, or paperboard made in accordance with the process of  claim 34 .  
     
     
         68 . Flame retardant paper, cardboard, or paperboard made in accordance with the process of  claim 35 .  
     
     
         69 . Flame retardant paper, cardboard, or paperboard made in accordance with the process of  claim 36 .  
     
     
         70 . Flame retardant paper, cardboard, or paperboard made in accordance with the process of  claim 37 .  
     
     
         71 . A flame retardant textile made in accordance with the process of  claim 38 .  
     
     
         72 . Flame retardant wood made in accordance with the process of  claim 40 .  
     
     
         73 . Flame retardant wood made in accordance with the process of  claim 41.