JPS6031877B2 - Method for producing flame retardant and smoke reducing compositions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a composition for oxidation and smoke reduction, and in particular a method for appropriately suppressing smoke emission during combustion of cellulose-based materials such as fibers, textiles, paper, and wood. It is an object of the present invention to provide a composition for combustion and smoke reduction.

From a disaster prevention perspective, combustible materials such as fibers, textiles, paper, and wood, used in buildings, interior parts for various wheels, and furniture, must be combusted at the same time as the key is ignited. There is a strong demand for switching to materials that can reduce the amount of smoke emitted.

The inventors have previously developed a composition for burning and reducing smoke that can meet the above requirements, and have filed a few patent applications (e.g., Hakamakasho 47-1 Rudo No. 705 [Japanese Patent Publication No. 51-35078; No. 861891], Hakama Fujisho No. 49-27157 [Special Publication No. 52-44157, Patent No. 91 $53], and Hakama Umaya Sho 50-1 Madara No. 244 [Special Publication No. 56-51196,
(Japanese Patent No. 1107316)) and achieved great results through its implementation.

However, as a result of continued research on these compositions for elutriation and smoke reduction, or actual implementation of elutriation and smoke reduction, the following problems need to be solved for the compositions for elutriation and smoke reduction. It turned out that there was a problem.

That is, [11] Although the smoke reduction effect on the above-mentioned materials is high, the isotou after combustion and extinguishing cannot be easily reduced; [21] The concentration of the treatment solution for the above-mentioned materials is approximately 3. It is relatively low, less than % by weight (at room temperature).

Regarding the above-mentioned problem of remaining ships, for example, Article 4-3 of the Fire Service Act states that
This is required to show an extremely small value in combustion tests for curtains, clothing, etc., as stipulated to be less than seconds.

On the other hand, when applying flame retardant and smoke-reducing treatments to the above-mentioned cellulose-based materials industrially, the composition for flame retardation and smoke reduction is generally made into an aqueous solution, and the article to be treated is immersed in it, or the solution is soaked in the aqueous solution. Since the aqueous solution is applied by spraying or painting, it is strongly desired that the aqueous solution be obtained in a wide range of concentrations so that it can be adapted to a wide range of purposes such as the degree of combustion and smoke reduction.

The inventors completed this invention as a result of intensive studies to meet these demands for compositions for flammability and smoke reduction. (excluding alkali metal salts) and 1 to 15 mole parts of alkali metal salts and/or ammonium salts of shelf acids.
After neutralizing the water-soluble reaction product with a basic neutralizing agent selected from ammonia and alkylamine using water as a solvent, an amino alcohol having 10 or less carbon atoms is added.
．． This is a method for producing a composition for combustion and smoke reduction, characterized in that 1 to 10 mole parts are added and reacted.

The scale burning and smoke reduction composition of this invention has been able to minimize the above-mentioned afterglow and the mechanism by which the concentration of the aqueous solution can be increased cannot necessarily be clearly demonstrated, but the following It can be explained as follows. Namely, the reaction products of acidic polyphosphates (excluding alkali metal salts) and shelf salts, the water-soluble reaction products obtained by neutralization with ammonia and alkylamines, and the amine/groups and hydroxyl groups of amino alcohols. It is thought that the carbon atoms form some kind of bond to increase their hydrophilicity, and that this acts as a negative catalyst for carbon combustion and significantly reduces the afterglow.

Furthermore, the composition for chick burning and bonito reduction according to the present invention has a very high aqueous solution concentration. The weight percentage of the components in the aqueous solution excluding water is usually 5% by weight or more. By further concentrating this, it is possible to increase the concentration as well as the solution viscosity. This is impossible except for amino alcohols, suggesting that the amino alcohols are reacting in some way.

In this invention, the acidic polyphosphoric acid metal salt refers to an acidic water-removal reaction between polyphosphoric acid described later or an acidic polyphosphate of an alkali metal or ammonium, and a metal salt that can be ion-sequestered by the polyphosphoric acid or acidic polyphosphate. It refers to a product that can exist relatively stably in the presence of water. Incidentally, when attempting to remove water by means such as evaporation in order to separate the acidic polyphosphate from the aqueous solution of the acidic polyphosphate in the present invention, a white solid is obtained, but this solid no longer exists. It is extremely poor in hydrophilicity and reactivity, and it is extremely difficult to use it as a raw material for the flame retardant and smoke reducing compositions targeted by the present invention. In addition, since the alkali metal polyphosphate has the effect of sequestering heavy metal ions other than the alkaline earth metal,
Alkali metal salts are excluded from the above-mentioned metal salts that can be sequestered. Here, polyphosphoric acid or acidic polyphosphates of alkali metals and ammonium are polyphosphoric acids such as pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, hexapolyphosphoric acid, trimetaphosphoric acid, polymetaphosphoric acid, and ultraphosphoric acid, and polyphosphoric acids such as sodium and potassium phosphoric acid of these acids. These are acidic salts of alkali metals and ammonium, and one or more of these may be used.

The commercially available polyphosphoric acid is usually synthesized by dehydration condensation of orthophosphoric acid, and is a mixture of the above-mentioned polyphosphoric acids such as pyrophosphoric acid, tripolyphosphoric acid, and tetrapolyphosphoric acid, and the component ratio is generally not specified. However, in the present invention, it goes without saying that this commercially available polyphosphoric acid can be used as the above-mentioned polyphosphoric acid, and is preferable because it can be obtained at low cost. The properties of commercially available polyphosphoric acids are generally expressed in terms of their content in terms of P2Q, and the higher the content, the higher the degree of condensation. In the present invention, when this commercially available polyphosphoric acid is used, the higher the P205 content is, the more preferable it is, and it is particularly desirable that the P205 content is 8% by weight or more.

The metal salt that can be ion-sequestered by polyphosphoric acid, etc. may be any salt of any metal as long as the metal ion can be sequestered by an aqueous solution of poly-IJ phosphoric acid, etc., but water-soluble salts are preferable. Calcium, magnesium, barium, zinc,
These are non-color-forming metal salts such as nitrates, sulfates, basic organic acid salts, or halides of metals that are originally colorless or light-colored ions such as zirconium and aluminum, and these are 1
A species or two or more species may be used.

Among these, in the case of amphoteric metals such as zinc and aluminum, metal oxyacids obtained by dissolving the hydroxide of the metal in an alkaline solution such as sodium hydroxide or ammonia;
Specifically, sodium zincate, ammonium aluminate, etc. can also be used. The molar ratio of the above ion-sequestering metal salt to these polyphosphoric acids or salts is 1:
The ratio is 0.1 to 1:1.8, particularly preferably 1:0.
The ratio is 2 to 1:1.5.

In addition, when using a condensed polyphosphoric acid such as polymetaphosphoric acid or ultraphosphoric acid, it is difficult to obtain a clear molecular weight, so in this invention, the molecular weight is calculated based on the average degree of polymerization.

Generally, polyphosphoric acid is often defined by the P2q content, and this value is closely related to the approximate degree of polymerization. Next, in this invention, the alkali metal salts and mono/and ammonium salts of shelf acids are sodium, potassium, and potassium salts of shelf acids, perstand acids, triside acids, tetrashelf acids, bentatake acids, and other polyshelf acids. It means an alkali metal salt or an ammonium salt such as.

These polyshelf acid ions are obtained in the form of mixed ions when a mixture of tetrashelf acid and tetrashelf acid is made into an aqueous solution. It is economically advantageous to use combinations of / and ammonium salts, especially sodium tetrasulfate and sulfates. The amount of the alkali metal salt and/or ammonium salt of shelf acids to be used is 1 to 15 parts by mole, particularly preferably 2 to 10 parts by mole, per 1 part by mole of the above-mentioned acidic polyphosphate metal salt. In addition, when using a combination of an alkali metal salt or/and ammonium salt of tetrabalic acid and a shelf acid, the ratio of the tetrabalic acid salt and the acidic polyphosphoric acid metal salts should remain the same as above, A good usage ratio is to use a combination of 1 to 4 mole parts of shelf acid per 1 mole part of tetrashelf acid. When the above-mentioned shelf acid salts are added to the above-mentioned acidic polyphosphate aqueous solution, a reaction usually occurs to form a gel-like precipitate.

Since the present invention relates to a composition for descaling and smoke reduction, the formation of such precipitates contaminates the flame retardant and smoke reduction treated product, which is extremely undesirable.
In the present invention, by using a basic neutralizing agent as described below, the precipitate once formed can be made into a clear aqueous solution again. Although the reason for this is not clear, it is probably because the acidic polyphosphate, the shelf salts, and this neutralizing agent form a kind of collar compound. Next, the neutralizing agent used in this invention includes one or more of ammonia, water-soluble alkylamines such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and triethylamine, cyanamide, dicyanamide, and aminoguanidine. are used, with highly basic ammonia and trimethylamine being particularly preferred. Note that there are many amines that react with acid residues, such as the amino alcohols described below, but other than the above-mentioned neutralizing agents, gels that are usually formed by the reaction of acidic polyphosphates and shelf salts as described above are known. The effect of eliminating precipitates and creating clarity is extremely poor. This neutralizing agent is added to neutralize the free acid in the reaction product of the above-mentioned polyphosphate metal salt and shelf salt, and to complete these neutralization reactions, but the main purpose is to As mentioned above, the purpose of the present invention is to eliminate the gel-like precipitate generated by the reaction between the acidic polyphosphate and the shelf salts to form a clear aqueous solution. In this case, the amount of the neutralizing agent used is as follows. The amount is in the range of 0.5 to 15 mole parts, particularly preferably 1 to 10 mole parts, based on 1 mole part of the total of the polyphosphoric acid and the metal salt ion-sequestered by the polyphosphoric acid. Furthermore, the amino alcohol used in the present invention includes carbon atoms of 10 or less, such as 2-aminoethanol, 2-(N-methylamino)ethanol, 2-(N-aminoethylami/)ethanol, and 2-amino/1-propanol. , 2-amino-
2-Methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2,3-diaminopropanol, 2-aminomethyl-1,2-pro/denediol, 2,2"-imidodiethanol, 2,2,2" −
Amino alcohols such as nitrilotriethanol, N-methyl-2,2-imidodiethanol, and amino alcohols derived from polyhydric alcohols such as glycerin, solpitol, mannitol, alkylolation such as N-hydroxyethyl-ethylenediamine, etc. These include polyamines, morpholines, etc. that are easily hydrolyzed by acids, alkalis, etc. and undergo ring formation to produce amino alcohols, and one type or two or more types of these can be used.

The number of carbon atoms in these amino alcohols is preferably 10 or less, as the elutriation and antifriction effects decrease as the number of carbon atoms increases. The amount of the amino alcohol used is 0.1 to 10 parts by mole, particularly preferably 0.3 to 7 parts by mole, per 1 part by mole of the acidic polyphosphate metal salt. That is, when the ratio of the amino alcohol used is outside the above range and is below the lower limit amount, the initial effects of the present invention, that is, extremely low afterlight after combustion flame and high concentration of the aqueous solution can be achieved. If the amount exceeds the upper limit, the scale combustion and smoke reduction effect of the kettle of this invention will be impaired. The reactions of the above-mentioned parts are carried out sequentially in the order of the respective components, and proceed sufficiently at room temperature, and are not particularly difficult. However, when polyphosphoric acids are used, it is preferable to first dilute them with water and cool them in a large amount of water bath or ice water bath to remove the heat of dilution. Furthermore, in order to complete the reaction of the above-mentioned components and obtain a good flame retardant and smoke reducing composition of the present invention, flooding is generally carried out for a certain period of time in order to improve the low temperature stability during storage. Desirably, the temperature in this case should not exceed 90 qo, particularly preferably 70 qo, and the holding time should preferably be 10 minutes or more and 5 hours or less.
Exceeding this temperature or exceeding this temperature for a long time is undesirable as it may cause precipitation due to thermal decomposition or the like. The pH of the final product aqueous solution obtained as described above is in the range of 5 to 9, but it is preferable to select and use a solution with a pH in the range of 8 to 8.5 depending on the flame retardant and smoke reduction treated product. There are cases.

An example of this is jute. The solution concentration of the composition for elutriation and smoke reduction according to the present invention is very high, usually 5% by weight or more in the aqueous solution of the total amount of raw materials used excluding water, and furthermore, it is By concentration it is also possible for this to be 10% by weight.

It is desirable to carry out such concentration under reduced pressure at a relatively low temperature of, for example, 40 to 60 q0 to prevent thermal decomposition. The composition for flammability and smoke reduction of the present invention is usually processed in an amount of 2 to 3 parts by weight based on the weight of the above-mentioned combustible material 10.

Although the flame-retardant and smoke-reducing composition of the present invention exhibits sufficient effects as a single component, it may be used in combination with other commercially available flame-retardant materials as described below depending on the purpose of use. For example, organic phosphorus compounds include organic scale compounds, organic nitrogen-containing phosphorus compounds, organic phosphorus sulfur compounds, halogen-containing organic phosphorous amide, and synthetic resins such as amino resin-phosphoric acid reaction products.Inorganic systems include ammonium carbonate and phosphoric acid. There are ammonium salts such as ammonium, ammonium tungstate, ammonium sulfamate, and ammonium bromide, and salts such as potassium carbonate, sodium phosphate, sodium molybdate, and sodium oxalate. Among these, when the purpose is to maintain the texture of the fibers, it is particularly preferable to use an organic type. Furthermore, many of these flame retardant materials are inorganic and can be used as pH adjusters.

Next, when using the flame retardant and smoke reducing composition of the present invention to treat fibers, paper, textiles, wood, etc., if necessary, thickeners such as starch, pork, CMC, synthetic rubber, etc. A binder, various surfactants, various fiber treatment agents, etc. can also be mixed.

The products to be treated in this invention include a wide variety of products such as cotton, rayon, linen, synthetic fibers, or blends thereof, paper such as shoji paper and wallpaper, plywood, fiberboard, pulp wood, wood chips, and synthetic resin sheets. The specific treatment method may be impregnation treatment, spray painting, coating method, etc.

As is clear from the Examples described later, the present invention can significantly reduce the afterglow during combustion of the product subjected to flammability reduction and smoke reduction, and can significantly contribute to improving safety. By increasing the solution concentration of the smoke composition, the concentration range in which it can be used can be widened, making it suitable for many purposes of use and helping to improve processing workability, which is of great industrial value.

The present invention will be specifically explained below with reference to Examples.

Example 1 Commercially available polyphosphoric acid (P24 content 82%) 79% (0.23
moles (numbers in parentheses below also indicate moles) of water 50
A solution of aluminum sulfate (JLSI product) 112 parts (0.18) dissolved in 500 parts of water was gradually added to a diluted polyphosphoric acid aqueous solution while cooling to about 30 parts. Continue praying for a minute.

Next, 490 g (1.28) of sodium tetrachloride and 150 g (2.42) g of sodium tetrachloride were added in this order, and the mixture was flooded to 50 g while continuing to stir.

At this time, cloudiness occurs. After keeping the temperature at about 500 m for 15 minutes, aqueous ammonia (NQ content 18%) was added for 20 min (0.2
Add 1). After confirming that the above cloudiness disappeared and the solution became clear, 2,2,2''-nitrilotriethanol 99
Add evening (0.66) and continue condensing for about 30 minutes until 60:00.
Flux the solution temperature to . The pH of this solution was 6.5, and the concentration was 50% (expressed as the weight percentage of the total amount of raw materials used in the aqueous solution excluding water; the same applies hereinafter). The obtained solution was diluted with water to a concentration of 20%, a rayon cloth with a basis weight of 150 yen was soaked in this for 20 seconds, and the squeezing rate was 1 using a squeezing roll.
00% dry.

The rayon cloth treated according to the present invention was subjected to a combustion test according to JISD1201 "Combustibility Test Method for Organic Materials for Automotive Interior", and as a result, it showed good values of oxygen index of 42 and smoke generation coefficient of 0.067.

Furthermore, when the afterlight of the same product was measured according to the test method in Article 4-3 of the Fire Service Act, it was 0 seconds. Example 2 Commercially available polyphosphoric acid (P205 content 82%) 120 min (0.
A solution of aluminum sulfate (JISI product) 135 (0.22) dissolved in 625' of water was gradually added to a diluted polyphosphoric acid aqueous solution while cooling in 625' of water. Then, the lantern worship continues for about 30 minutes.

Next, 800 g of sodium tetraside (2.1) and 2 g of shelf acid
Add 50 qo (4.04 qo) in this order, and continue pouring until 50 qo. At this time, cloudiness occurs. After keeping the temperature at about 50qo for 10 minutes, aqueous ammonia (N
120 min (1.27) of H3 content 18% and then 120 min (0.61) of a 30% aqueous solution of trimethylamine are added. When Takaazusa is continued, the cloudiness above disappears, and after confirming that it has become a clear solution, add 21 (2-aminoethylamino).
Add 57 mm (0.55 mm) of ethanol and continue stirring for about 30 minutes to bring the solution temperature to 60 mm. p of this solution
H'ma was 6.6 and the concentration was 50%. The obtained solution was diluted with water to a concentration of 20%, and a cotton cloth having a basis weight of 200 m/m was soaked in sand for two times, and then squeezed and dried with a squeezing roll to a squeezing rate of 90%. This invention-treated cotton cloth is JISD
1201 "Combustibility test method for organic materials used in automobile interiors" As a result of the combustion test, the oxygen index was 39 and the smoke production coefficient was 0.0.
It showed a good value of 63. In addition, regarding the same product, Fire Service Act 4
The afterglow was measured in accordance with the test method in Article 3 and was found to be 0 seconds. Example 3 Commercially available polyphosphoric acid (P205 content 85%) 213 days (0.
Aluminum sulfate (JISI No. 30) was added to an aqueous solution of polyphosphoric acid diluted with 1,050 ml of water while cooling it to 250 ml of aluminum sulfate (JISI product).
A solution prepared by dissolving 0.40% of water in 1050% of water was gradually added while stirring, and stirring was continued for about 3 minutes.

Next, 1070 ml of sodium tetrachloride (2.81) and 0 ml of sodium chloride (5.0 g) were added in this order, and the mixture was flooded to 50° C. while continuing to stir. At this time, cloudiness occurs. After maintaining the temperature at approximately 50°C for 8 minutes, aqueous ammonia (NH3
Add 237 (2.5%) (content 18%). After confirming that the cloudiness above disappears as the rope continues and the solution becomes clear, N,N'-bis(2-hydroxyethyl)ethylenediamine 215 liters (1.45) is added, and the rope is stirred for about 30 minutes. Continue to warm the solution to 60 qo. The pH of this solution is 6. & concentration was 50%. The resulting solution has a concentration of 20
A rayon cloth with a basis weight of 150 yen was soaked in this solution for 20 seconds, and then squeezed and dried with a squeezing roll to a squeezing rate of 95%. This invention-treated rayon cloth was
A combustion test was conducted according to ISD1201 "Combustibility test method for organic materials for automobile interiors", and the results showed good values, with an oxygen index of 4 and a smoke coefficient of 0.065.

Furthermore, when the afterlight of the same product was measured according to the test method in Article 4-3 of the Fire Service Act, it was 0 seconds. Example 4 Commercially available polyphosphoric acid (P205 content 82%) 120 min (0.
Sodium hexametaphosphate (0.24 g) was added to a polyphosphoric acid aqueous solution prepared by diluting 35) with 600 g of water while cooling it in the ground.
After adding an aqueous solution of 300% of water and mixing thoroughly, aluminum sulfate (JISI product) 395% (0%) was added.
．． A solution prepared by dissolving 64) in 900 ml of water is gradually added while stirring, and the stirring is continued for about 20 minutes.

Next, add in this order 620 μm (1.63) of sodium tetrashelate, 240 μm (1.26) of ammonium tetraserate, 280 μm (4.5) of tetrahydrochloric acid, and 85 μm of anhydrous sodium phosphate, and stir the rope. Continue heating until it reaches 500 ml. At this time, cloudiness occurs. After maintaining the temperature at about 50 qo for 9 minutes,
Ammonia water (NH3 content 18%) 180 minutes (3.2)
Add. After confirming that the cloudiness above disappears as the rope continues and the solution becomes clear, add 2-(2-aminoethylamino)ethanol 56 ml (0.0%) and continue the rope for about 20 minutes at 60°C. Flux the solution. The bait for this solution is 7.
2. The concentration was 50%. The concentration of the obtained solution is 20%.
A rayon cloth with a basis weight of 150 yen was soaked in this solution for 20 seconds, and then squeezed and dried using a squeezing roll to a squeezing rate of 95%.

The rayon cloth treated according to the present invention was subjected to a combustion test according to JISD1201 "Combustibility test method for organic materials used in automobile interiors", and as a result, it showed good values of oxygen index of 42 and smoke generation coefficient of 0.062.

In addition, when the residue of the same product was measured according to the test method in Article 4-3 of the Fire Service Act, it was 0 seconds. Example 5 The solution of the present invention obtained in Example 1 (concentration 50%) was further concentrated under reduced pressure to remove 95% of the water contained therein, thereby obtaining a very viscous liquid substance.

Claims (1)

[Claims] 1. Using water as a solvent, 1 mol part of acidic polyphosphate metal salts (excluding alkali metal salts) and 1 to 15 mol parts of alkali metal salts or/and ammonium salts of boric acids are reacted, and then this reaction solution is prepared. is neutralized with a basic neutralizing agent selected from ammonia and alkyl amines, and then 0.1 to 10 mole parts of an amino alcohol having 10 or less carbon atoms are added and reacted, and a method for producing a smoke reduction composition.