FI56995B - SHEET ANTENDBARA APPRETERADE PAPPER UTAN ELLER MED SLIPMASSAHALT OCH FOERFARANDE FOER DERAS APPRETERING - Google Patents

Description

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Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) P 23U6751-8 (71) Benckiser-Knapsack GmbH, Am Hafen 2, 6802 Ladenburg / Neckar,

Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (72) Klaus Sommer, Heidelberg, Federal Republic of Germany-Förbundsre-publiken Tyskland (DE) (7U) Oy Borenius ie Co Ab (5U) Finished flame retardant, wood-free finishing and containing paper - Sv & rt an-tändbara appreterade papper utan eller med slipmassahalt och förfa-rande för deras appretering

The present invention relates to flame retardant-free and chopped papers and to a method for finishing them. It is known that paper can be finished flame retardant with monoethanolamine, diethanolamine and triethanolamine salts of sulfamic acid (Amer. Paper Converter 23 (6) 11, 1949). . In particular, this finishing method has three drawbacks. Firstly, the stiffness of the treated papers is greatly reduced due to the plasticizing effect of these substances, and secondly, 20-40% addition rates are required to achieve some useful flame retardancy. It is further inconvenient that said amine salts of sulfamic acid cause discoloration in a very large number of papers.

Flame retardant finishing is especially necessary for decorative and packaging papers as well as cardboard, as they have a wide range of uses and, due to their easy flammability, constitute a hazard and cause of damage.

It has now been found that highly flame-retardant papers without the above-described shadows are obtained by applying to the paper aqueous solutions containing 25 56995 10-50% of the general formula NH2SO5H.H2N CnH2nNH2, H05SNH2 where n = 2 or 3 or by dipping and then drying at 80-120 °

Cissa. In this way, papers are obtained which contain at least 12% of alkanediamine disulfamate. Such compounds include, for example, 1,2-ethanediamine disulfamate, 1,2-propanediamine disulfamate and 1,3-propanediamine disulfamate. 1,2-Ethanediamine disulfamate has been shown to be most preferred.

Of course, much higher amounts of sulfamates can be easily added to the paper, although concentrations above 20% should be avoided because higher concentrations do not provide better performance but adversely affect the properties of the papers. An addition of 12% provides completely adequate flammability protection, but for safety reasons, the papers will be finished so that they will preferably contain 13-18% flame retardants.

For wood-containing papers, it has proved particularly advantageous to add to the paper not only alkanediamine disulfamates but also 2-5% hydroxylammonium sulphate or phosphate together with a sulphate solution. In this way, it is possible to completely prevent the yellowing that always occurs in papers containing more or less wood chips.

Equally good flame retardant properties are obtained with alkane diammonium phosphates, in particular 1,2-ethanediammonium phosphate.

However, when the water solubility of these products is low, it is much more difficult to add them. Most preferably, they can be added together with the sulfamates by adding 1,2-alkanediammonium phosphates in aqueous solutions in amounts of 2-10%. Furthermore, in the same manner and in the same amounts, further 1,2-ethanediammonium-his-hydroxymethane phosphinate, tetrakishhydroxymethane-phosphonium sulfate or phosphate or 1,2-aminoethanesulfonic acid can be added as well as mixtures thereof.

Said additives have only a minor effect on the stiffness and other properties of the paper.

56995 3 If desired, the stiffness may be improved in particular by the addition of tetrakishydroxymethanephosphonium salts as sulphates or phosphates. Analogous phosphonium salts obtained by the addition of glyoxal to phosphine may also be used for this purpose. The addition of these compounds also causes an improvement, albeit a slight, flame retardant effect, while at the same time almost completely preventing discoloration of the material containing little wood chips.

Solutions can be prepared either from solid alkanediamine sulfates by the addition of water or by adjusting the reaction product in solution of the corresponding amine and sulfamic acid to the desired concentration without isolating the pure product and using it directly for paper treatment.

Example 1:

A solution of 60 g of 1,2-ethanediamine in 75 ml of water is added dropwise with vigorous stirring to a slurry of 194 g of sulfamic acid in 225 ml of water, keeping the temperature of the mixture below 50 ° C by cooling. One surface of one square meter of 2 paper having a basis weight of 150 g / m 2 was sprayed evenly with one tenth of the obtained solution and dried with a heated roll. A paper containing about 14% of 1,2-> ethane-diamine sulfamate is obtained. Strips were cut from the treated paper and flamed for 5 seconds. The flamed paper strips went out no later than 2 seconds after the flame was removed.

Example 2;

A solution of 72 g of 1,2-ethanediamine in 150 ml of water is added dropwise with vigorous stirring and cooling with water to a slurry of 194 g of sulfamic acid in 250 ml of water. Immediately after the addition of the amine, neutralize with 75% phosphoric acid (about 26 g). The resulting solution was diluted to twice the volume and a 30 cm wide and 150 cm long paper web was wetted with this solution. After pressing and drying, it was found that 14% solids had been added to the paper. It behaved in the combustion experiments in the same way as the paper described in Example 1.

4 56995

Example 5: A solution of 78 g of 1,2-diaminopropane in 75 ml of water and 194 g of sulfamic acid in 200 ml of water was prepared as described in Example 1 and combined with a solution containing 8 g of tetrakis. hydroxymethanephosphonium sulfate in 10 ml of water. With the solution diluted to twice the volume, the paper specimens were treated by the immersion method, pressed and dried. After drying, a 12-15% addition of dry matter was observed and they went out after flameing within 1 second of removing the flame.

Example 4:

To a solution of 10 g of bis-hydroxymethanephosphinic acid in 200 ml of water was added portionwise 194 g of sulfamic acid. The mixture was neutralized by adding, with stirring and cooling, a 50% solution of 1,2-diaminoethane (about 150 g). Paper treated with this solution (addition of about 15%) is as flammable as the samples treated in Example 1.

Example 5:

A slurry containing 194 g of sulphamic acid in 300 ml of water is neutralized with a solution of 60 g of 1,2-diaminoethane or 78 g of 1,3-diaminopropane in 200 ml of water at a temperature below 50 ° C. To the resulting solution is added 16 g of hydroxylammonium sulphate. Wood-based test papers were prepared as in the previous examples and examined. The papers did not show any color defects after treatment with the material mixture and were self-extinguishing within 2 seconds after flame addition after 15% solids.

Example 6: 26 g of 1,2-aminoethanesulfonic acid and 25 g of tetrakishhydroxymethane-phosphonium phosphate or sulphate are dissolved in 250 ml of water. To this solution is added portionwise 194 g of sulphamic acid and neutralized by dropwise addition of about 60 g of 1,2-diaminoethane to 100 ml.

Claims (5)

5 56995 dissolved in water, keeping the temperature below 50 ° C. The paper strips are soaked in the solution by immersion, then pressed and dried. The samples were self-extinguishing with 15-18% solids additions. The papers thus finished meet the requirements of the T 461 OS 68 and ASTM D 777 test methods. Papers, finished or flame retardant, free of wood chips and containing at least 12% flame retardant, characterized in that the flame retardant is an alkanediamine disulphamate of the general formula NH2SO3H * H2N CnH2nNH2 · HO ^ SNHg, where n = 2 or 3. Flame retardant finished wood chips papers according to Claim 1, characterized in that they additionally contain 2-5% of hydroxylammonium sulphate or phosphate, Process for finishing papers according to Claim 1 or 2, characterized in that solutions containing 10 to 50% of alkanediamine disulphamate are added to the paper by spraying or dipping and then dried at 80 to 120 ° C. Process according to Claim 3, characterized in that 2-5% of hydroxylammonium sulphate or phosphate is added to the sulphate solution. Process according to Claim 3 or 4, characterized in that 2 to 10% of 1,2-ethanediammonium phosphate, 1,2-ethanediammonium bis-hydroxymethanephosphinate, tetrakis-hydroxymethanephosphonium sulphate or phosphate or 1,2-aminoethanesulphonic acid are added to the sulphamate solutions or mixtures thereof.