JP2013104058A - Powdery flame retardant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powdery flame retardant composition centered on a sulfate salt, which is safer and cheaper and conventionally useful and practicable as a general-purpose product to solve such a problem that many of flame retardants contain phosphorus (P), boron (B), halogens (F, Cl, Br, I and the like) in their components, and these derive and generate hazardous materials during combustion and pose a large problem on the social environment and the human health.SOLUTION: A flame retardant (pH of the 10% aqueous solution is 5 to 9) is obtained which contains 30 to 80 wt.% of a sulfate salt, and 10 to 50 wt.% of an alkali salt such as sulfaminic acid and a sulfamate salt by paying attention to a water-soluble sulfate salt (particularly NH4, K, Na, Mg), selecting sulfamic acid which has a good chemistry as a chemical synthesis method, and carefully examining the contents under the limited condition advantageous in pH, compatibility, formation of a double salt, buffer action and cost and featuring high safety.

Description

The present invention improves the flame retardancy of woven and non-woven fabrics, other sheet processed products and molded products by chemical processing, and consequently contributes to safe fire prevention measures.

In particular, it eliminates the presence of water, which is a drawback of aqueous materials, forms a powdery product by dry method, and can freely expand the range of water and other compounding work on site, making it easy to use as a general-purpose product It is intended to provide a form that can be easily processed into a solid or kneaded product.

The flame retardant composition is generally dissolved or dispersed in water or some kind of solvent (solvent). On the other hand, in recent fires such as buildings and buildings, the loss of precious lives and the risk of occurrence of secondary and tertiary disasters due to temperature rise ignition of harmful components inherent in the building are more than the original fire itself. In addition, along with the design and construction of buildings, the emergence of more rational and simple construction methods is desired.

Problems to be Solved by the Invention

Among these flame retardants, substances that cause further environmental pollution and natural destruction, especially halogen-based and phosphorus-based substances, will be abolished in spite of their practicality. This is a critical condition imposed on the parties as a matter that is attracting attention as an urgent theme and is also related to the future rise and fall of flame retardants.

Specifically, phosphorus (polyphosphate, organic phosphorus, phosphate, etc.), halogen (F, Cl, Br, I), alkali agent (Ca, Mg, Al), ceramic (dolomite) , Zeolite, bentonite, quartz, etc.), boron-containing materials, organic polymers (naphthalene, tevilon, amino acids, etc.), etc. It is necessary to take measures against the onset of lung cancer and emphysema from such raw material powders.

As a fact, the present inventors filed a liquid flame retardant on September 21, 2009, and based on the historically highly useful sulfate, examined the physical properties in detail, and unexpectedly. We reviewed the sex and got one result.

Means for solving the problem

In order to solve all the problems exposed to the inside and outside of these flame retardants, the present invention examines substances that have been apt to be neglected in the past, and as a condition essential to the configuration of the present invention, legal measures (PRTR) Etc.), work environment (Occupational Safety and Health Act), water pollution (Water Pollution Control Act), in addition to reducing carcinogenesis and other diseases, overcoming non-toxicity of raw materials, at least at room temperature and humidity of 60% RH The present inventors have found a composition that is stable for 6 months or more, and have reached the present invention.

Among all the conditions included in the present invention, the component is easily soluble in water (20% or more), and the pH is 4 to 10 (preferably pH 5 to 9) in a 10% aqueous solution, that is, neutral. This pH setting does not cause condensation, ignition, foaming, odor, appearance change, decomposition, etc. within the range of distribution when the present invention is commercialized, and this has a flame retardant effect superior to conventional ones. Considering to serve. In particular, ammonia and amine odors, which are representative of bad odors, must be avoided because they are particularly concerned with ammonium salts.

The present invention is to adjust the combination of a salt, an acid and a neutralizing agent, which are common in the past, and to exhibit a sufficient flame retardant effect.

If it is a solid acid other than sulfamic acid and a sulfate, the pH of the aqueous solution cannot be set within the target.
This is because the sulfate (ammonia) is weakly acidic, resulting in a double salt with sulfamic acid. As a result, the pH can be set to 4 to 9, and sulfamic acid with extremely high flame retardancy is partially mixed. This is because a salt is formed into a solution. Regarding the physiological study of sulfamic acid, US ANTHONY. M.M. Reference may be made to AMBROSE (vol25, No1, JOURNAL OF INDUSTRIAL HYGIENEMS TOXISOLOY).

The most important point of the present invention is to focus on how well the conventional sulfate salt can be used with sulfamic acid, as well as its low harm to safety and water quality. The sulfamic acid has advantages and disadvantages, that is, it is hardly soluble in water, and the fire prevention effect possessed by its salt has been put into practical use.

BEST MODE FOR CARRYING OUT THE INVENTION

The specific conditions of the present invention are summarized as follows: (1) Sulfate ((NH ₄ ) ₂ SO ₄ , K ₂ SO ₄ , Na ₂ SO ₄ , MgSO _4, etc.) 30-80 w%, (2) Sulfamic acid (NH ₂ SO ₃ H) 10-50 w%, (3) sodium bicarbonate, soda ash, potash ash, silicate (Na, K), sesqui carbonate 10-40 w%, (4) as required Surfactant (especially anionic AOS, AS, AES, soap, nonionic higher alcohol, alkyl glucoside, etc.) is included in an amount of 0.2 to 5 w%, and (2) + (3) is 30 to 80 w% ( The salt of sulfamic acid itself is also acceptable), (1)> (2) + (3), and the pH is set in the range of 5-9.

Of particular note in the completion process of the present invention is the behavior of sulfamic acid and its salts. Sulfamic acid itself is poorly water-soluble, and when it is allowed to stand, it tends to solidify and become water-insoluble. However, if this is neutralized with an alkali salt and formulated so as to reach the sulfamate, both water solubility and stability will be greatly improved, and in the presence of sulfate (pH is neutral to acidic) Both of the sulfamate and sulfate are successfully dissolved, and the sulfate-sulfamic acid combined double salt is formed by absorbing the sulfamate into the sulfate and being close to neutrality. The flame retardant effect suitable for That is, if only sulfate is increased in a mischievous manner, or if the ratio of sulfamate exceeds the sulfate, the stability of the solution is deteriorated and the balance of various components is lost and separated. The meaning of defining the conditions for this combination is a point that demonstrates the unexpectedness of the present invention.

Specifically, it is clear that the non-flammable factors are calculated by 10% for sulfate (NH ₄ ) and 5% for sulfamate (Na). In fact, with cellulose (10 g / m ² ), when a certain amount of fire is added to each, sulfate is 2 to 3 seconds until ignition, and sulfamate is 2 to 3 seconds. When the pH is kept at approximately neutral 7.2, it takes 8 to 12 seconds. In other words, it is difficult to ignite, and it is digested immediately after ignition. Incidentally, 15% sulfate is around 5 seconds, 15% sulfamate (not completely aqueous) is 4 to 5 seconds, and the definition of the mixture and pH contributes to the effect. That is, both are achieved only when a complete aqueous solution is reached.

The best conditions are 50-60 w% ammonium sulfate, 15-25 w% sulfamic acid, 5-25 w% soda ash (or sodium bicarbonate, sodium silicate, sulfate, silicate), and a 10% aqueous solution with a pH of 6-6 8. If 0.2 to 5 w% of AOS, AS, etc. (or higher alcohols with 9 to 12 moles of EO added, nonionics such as fatty acid alkanolamides) are added in an amount of 0.2 to 5 w%, this increases penetrating power and absorbability, and is treated. The flame retardant effect on the body is improved.

Since the composition of the present invention is premised on a powder form, the composition of the present invention possesses characteristics that can be freely blended only by single blending with a ribbon mixer or a turning mixer. Also, do not use fire or explosives, avoid complete sealing over time and distribution (because a small amount of CO ₂ gas is generated), and keep it in place by adding a gas vent and a gas barrier.

The flame retardant of the present invention is a substantially neutral aqueous powder, sometimes gypsum, titanium white, zinc sulfate, quartz, bentonite, zeolite, calcium carbonate, alumina, diatomaceous earth, activated white clay, colloidal silica (Aerosil), cyclodextrin , Cellulose compounds, polysaccharides, carbon fibers, FRP powder, etc., may be added for dehumidification and stabilization, fire prevention improvement, appearance improvement, etc.

Effects of the present invention

The effects brought about by the present invention are diverse as follows. (1) Excellent in safety and stability, raw material supply, handling, storage and delivery. (2) Although it is a mixture of an acid and an alkali, there is no explosion, abnormal foaming, heat generation, swelling, no odor emission due to chemical change, no solidification or discoloration in appearance, and it can be stored for 6 months or more at room temperature. (3) In the unlikely event, if it is drained as an aqueous solution, it is a neutral salt, so there will be no aftercare or trouble. (4) Since it is a powder body, it can be blended according to various substances and their purposes.

For example, titanium white, barium sulfate, mica, cerium oxide, fluorescent agent, phosphorescent agent, EL powder, noble metal (gold, etc.) powder, pigment, bengara, chlorophyll by improving fire prevention, whiteness, and moisture absorption. , Decorated with malachite green (combined with CVL), light emitting element (Ga, In, As, Tl, etc.), etc., plastic powder (PVC, PA, PS, PVA, PVP, melamine, etc.), polymer (acrylic, poly, etc.) Sugar, cyclodextrin, cellulose polymer, etc.) can be added, and powdered ClO ₂ , polyphenols, molecular sieves, activated carbon, silicone derivatives, bentonite, dolomite, zeolite, etc. can be added as appropriate for deodorizing purposes.

Further, the composition of the present invention itself is diluted with water as it is in a non-surfactant fully automatic washing machine detergent, chemical fertilizer, deodorant, glass or mirror cleaning agent, etc. ( It also has an effect that can be applied (sometimes with the addition of alcohol). Next, an example is given and it demonstrates concretely including a significant difference with a conventional product.

実施例１の試作品に対して以下のテストを実施した。A prototype was produced as in Example 1 [Table 1] below, and a significant difference in the effect between the present invention and the conventional product was confirmed.

The following test was performed on the prototype of Example 1.

PH of 1,10% aqueous solution (20 ° C.) [Table 2]

2. Appearance change with time (in a 0.1 mm thick PE bag and left at room temperature for 6 months) [Table 3]
Evaluation is as follows. ◎: Almost no change ○: Slightly (partially) solidified (small granular)
X: Large solidification, stickiness

Speed when making 3,30% aqueous solution (20 ° C) [Table 4]
Evaluation is as follows. ◎: Fast solubility (within 1 minute), aqueous solution is almost transparent ○: Cloudy and slightly precipitated ×: Cloudy and crystallized product is generated

4, Combustion test (simple method) [Table 5]
[Target fabric]
a: Rayon (26 g / m ² )
b: 65% polyester / 35% cotton (51 g / m ² )
[Test method: A]
The evaluation of igniting a sample by directly contacting a flame with a lighter is as follows. ◎: Although it is ignited, it disappears immediately. ○: It burns sequentially, but it disappears. ×: As a result, it burns out [Test method: B]
The evaluation of holding the sample 30mm above the flame of the candle is as follows. ◎: Although it is ignited, it disappears immediately. ○: It burns sequentially, but disappears. ×: Burns out as a result [sample preparation]
For both types of fabrics, each aqueous solution is treated with impregnation for 180 seconds, pressing and drying (ironing). The concentration of the aqueous solution in [Table 1] is prepared in two ways of 20% and 40% in each test situation.

[Discussion]
When the sulfate, which is the most important point of the present invention, and sulfamic acid and its salt are balanced, a synergistic effect can be obtained as described above. The three conditions of the present invention, when the main component is sulfate or sulfamate, the pH is 5 to 9, and the sulfamate itself is contained at 20 w% or more. The results clearly prove this confirmation.

実施例２の試作品に対して以下のテストを実施した。A prototype was produced as in Example 2 [Table 6] below, and the effect of the present invention was proved.

The following test was performed on the prototype of Example 2.

PH of 1,10% aqueous solution (20 ° C.) [Table 7]

2, Appearance change with time (in a 0.1 mm thick PE container and left at room temperature for 6 months) [Table 8]
Evaluation is as follows. ◎: Almost no change ○: Slightly (partially) solidified (small granular)
X: Large solidification, stickiness

Speed when making 3,20% aqueous solution (20 ° C) [Table 9]
Evaluation is as follows. ◎: Fast solubility (within 1 minute), aqueous solution is almost transparent ○: Cloudy and slightly precipitated ×: Cloudy and crystallized product is generated

4, Combustion test (Test method conforms to JIS L-1091) [Table 10]
[Target fabric]
a: Cotton (46 g / m ² )
b: 65% polyester / 35% cotton (40 g / m ² )
c: 80% acrylic / 20% cotton (96 g / m ² )
[passing grade]
All the following items pass if they meet the standard value (rounded up after the decimal point)
Carbonization area: 30 cm ² or less Residual flame time: within 3 seconds Residual time: within 5 seconds Carbonization distance: 20 cm or less at the longest distance [sample preparation]
In each of the three kinds of fabrics, each aqueous solution is treated with impregnation for 180 seconds, pressing, and drying (ironing). The concentration of the aqueous solution in [Table 6] is prepared in two ways of 30% and 50% in each test situation.

The specific conditions of the present invention are summarized as follows: (1) 30 to 70 % by weight of sulfate ((NH ₄ ) ₂ SO ₄ , K ₂ SO ₄ , Na ₂ SO ₄ , MgSO _4, etc.), (2) sulfamine 10-30 w% of acid (NH ₂ SO ₃ H), (3) 10-30 w% of sodium bicarbonate, soda ash, potash ash, silicate (Na, K), sesquicarbonate, etc. (4) Also necessary Accordingly, a surfactant (particularly anionic AOS, AS, AES, soap, nonionic higher alcohol, alkyl glucoside, etc.) is included in an amount of 0.2 to 5 w%, and (2) + (3) is 30 to 70 %. It is w% (a salt of sulfamic acid itself is acceptable), (1)> (2) + (3), and pH is set in the range of 5-9.

実施例１の試作品に対して以下のテストを実施した。A prototype was produced as in Example 1 [Table 1] below, and a significant difference in the effect between the present invention and the conventional product was confirmed.

The following test was performed on the prototype of Example 1.

実施例２の試作品に対して以下のテストを実施した。A prototype was produced as in Example 2 [Table 6] below, and the effect of the present invention was proved.

The following test was performed on the prototype of Example 2.

Claims (2)

(1) 30-80 w% of sulfate (Na, K, NH ₄ , Mg, alkanolamine (E, P))
(2) 10-50 w% of sulfamic acid (Na, K, NH ₄ , alkanolamine (E, P) produced by (3) or salt itself)
(3) 10-40 w% of alkali salts (carbonate, sesquicarbonate, silicate, etc.)
(2) + (3) is 30-80 w%, and (1)> (2) + (3), so that the pH of this 10% aqueous solution is 5-9 (2 ) And (3) adjusted powdery flame retardant composition. The flame retardant composition of [Claim 1] contains 0.2 to 5 w% of an aqueous surfactant and is adjusted so that the pH of a 10% aqueous solution at 20 ° C is 5 to 9 Fuel composition.