JPH1060447A - Flame retarder composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retarder composition for a cellulosic material capable of supplying into a marker in as state of a highly concentrated aqueous solution or an aqueous dispersion irrespective of modifying (methylolation, etc.) with formalin, low in fire retardancy, coloring and deterioration of paper strength after heat-treating. SOLUTION: This flame retarder composition is composed of an aqueous solution or an aqueous dispersion containing (A) at least one kind of salt selected from a guanidine salt, an ammonium salt and a metallic salt of groups I to III elements of at least one kind of an inorganic acid selected from sulfamic acid, phosphoric acid, polyphosphoric acid, boric acid and sulfuric acid and (B) at least one kind of a water-soluble polymer selected from a polystyrene sulfonic acid-based water-soluble polymer a polyvinyl alcohol-based polymer a polyoxyalkylene-based water-soluble polymer, a polyacrylamide-based water-soluble polymer, a polycarboxylic acid-based water-soluble polymer and a cellulosic water-soluble polymer as essential components and an amount of the component B is 0.05-10wt.% based on the weight of the component A, and the content of the component A is >=40wt.% based on whole weight of the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame retardant composition for a cellulosic material. More specifically, the present invention relates to a non-formalin-based flame retardant composition having excellent flame retardancy and less coloring after heating and little deterioration in paper strength.

[0002]

2. Description of the Related Art Conventionally, as a flame retardant used for a cellulosic material such as paper products, a mixture of guanidine sulfamate and methylolated guanidine sulfamate (for example, JP-A-60-199094), guanidine sulfamate and formalin Reaction products (for example,
No. 1-29993) and those obtained by reacting a mixture of ammonium sulfamate and dicyandiamide with formalin (for example, JP-A-4-45148). All of these are modified with formalin (mainly methylol) to increase water solubility, and are usually supplied to the market at a product concentration of 40% by weight or more.

As a method not using formalin, there is a conventional method using guanidine sulfamate, which has a concentration of 40% by weight even in an aqueous solution.
And a weight of 40% cannot be secured depending on storage conditions. Further, the heat resistance (whiteness) of the treated paper, which is one of the important properties as a flame retardant composition, is poor. Also,
Melt reaction product of sulfamic acid and urea (Japanese Patent Laid-Open No. 62-12 / 1987)
No. 9383) and an alkylene oxide adduct of guanidine sulfamate (Japanese Patent Application Laid-Open No. 2-70793). These compounds have an aqueous solution concentration of 40% by weight.
Although the above can be ensured, there is a problem that the whiteness of the treated paper is reduced.

In order to prevent the whiteness of treated paper from decreasing, a metal salt of sulfamic acid (JP-A-55-7808) is used.
No. 1, Kaikai 62-129381, JP-A 62-129
382) and alkylene oxide adducts of metal sulfamate (Japanese Patent Application Laid-Open No. 2-289199). These are one of the important properties of a flame retardant composition in treated paper. There is a problem that strength is reduced.

[0005]

In recent years, as concerns about the environment have increased, problems with residual formalin in flame-retarded paper products have been pointed out. There is a strong need for flame retardants. However, if no formalin is used, 4
The product concentration of 0% by weight is the limit, and it is difficult to secure 40% by weight depending on storage conditions. In addition, those with enhanced water solubility have the heat resistance of treated paper (especially whiteness and strength).
And it was very difficult to satisfy all of these. An object of the present invention is to provide a non-formalin-based flame retardant composition which can secure a product concentration of 40% by weight or more even without using formalin at all, is excellent in flame retardancy, and has little coloring and paper strength deterioration after heating. Is to do.

[0006]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventor has found that by using a specific inorganic acid salt and a specific water-soluble polymer in a specific weight ratio, a high concentration can be obtained. It has been found that an aqueous flame retardant composition can be obtained, and the present invention has been achieved. That is, the present invention relates to at least one kind of salt selected from guanidine salt, ammonium salt and metal salt of Group I to III of at least one kind of inorganic acid selected from sulfamic acid, phosphoric acid, polyphosphoric acid, boric acid and sulfuric acid. A) and a polystyrenesulfonic acid-based water-soluble polymer, a polyvinyl alcohol-based water-soluble polymer, a polyoxyalkylene-based water-soluble polymer, a polyacrylamide-based water-soluble polymer, a polycarboxylic acid-based water-soluble polymer, and a cellulose-based water-soluble polymer. Consisting of an aqueous solution or an aqueous dispersion containing, as an essential component, at least one water-soluble polymer (B) selected from water-soluble polymers, and the amount of (B) is from 0.05 to 10% by weight of (A). It is a flame retardant composition characterized in that it is 10% by weight and the content of (A) is at least 40% by weight based on the total amount of the composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a salt of an inorganic acid (A)
Guanidine salts and ammonium salts of one or more inorganic acids selected from sulfamic acid, phosphoric acid, polyphosphoric acid, boric acid, and sulfuric acid; metals of Groups I to III of the periodic table (lithium, sodium, potassium, beryllium, zinc) , Magnesium, calcium, barium, aluminum and the like). Of these, preferred are guanidine sulfamate, calcium sulfamate and magnesium sulfamate, and more preferred are mixtures of guanidine sulfamate with calcium and / or magnesium sulfamate.

The above-mentioned guanidine salt of an inorganic acid is, for example, in the case of guanidine sulfamate, a mixture of ammonium sulfamate and dicyandiamide in a molar ratio of usually (1-3): 1, preferably (1.4-1.8): 1. By ratio, usually 12
It is obtained by performing a molten salt reaction at a reaction temperature of 0 to 200 ° C, preferably 140 to 180 ° C. Guanidine salts of other inorganic acids can be obtained in a similar manner.

In the reaction product, in addition to guanidine sulfamate as a main component, for example, unreacted ammonium sulfamate, dicyandiamide, and a small amount of by-products such as ammonium imidobissulfamate and guanidine imidobissulfamate. May be included.

In the above reaction, if the molar ratio of the ammonium salt of the inorganic acid is less than 1, the content of water-insoluble substances such as melamine and ammeline increases, and the water solubility of the final product decreases and the flame retardancy decreases. However, if it exceeds 3, a large amount of unreacted inorganic acid ammonium salt remains, which causes coloration and strength deterioration during heating of the cellulosic material.

Further, calcium sulfamate, magnesium sulfamate and the like can be obtained by a usual neutralization reaction. That is, it is obtained by reacting sulfamic acid or ammonium sulfamate with calcium hydroxide and magnesium sulfamate in equivalent amounts.

To obtain a blend of guanidine sulfamate (a1) and calcium sulfamate and / or magnesium sulfamate (a2), the above-mentioned guanidine sulfamate and calcium sulfamate and / or magnesium sulfamate are blended. It can also be obtained by neutralizing sulfamic acid or ammonium sulfamate with guanidine carbonate and calcium hydroxide and / or magnesium hydroxide so as to have respective mixing ratios.

The weight ratio of (a1) and (a2) is usually (10-90) :( 90-10), preferably (50-90).
80): (50-20), more preferably (60-7)
0): (40 to 30). If the ratio of (a1) is less than 10, the strength of the treated paper will decrease, and if it exceeds 90, the whiteness of the treated paper will decrease, and in any case, it cannot be used.

The water-soluble polymer (B) used in the present invention includes a polystyrenesulfonic acid-based water-soluble polymer, a polyvinyl alcohol-based water-soluble polymer, a polyethylene oxide-based water-soluble polymer, and a polyacrylamide-based water-soluble polymer. And a polycarboxylic acid-based water-soluble polymer, a cellulose-based derivative, and a mixture of two or more thereof, and preferably a polystyrenesulfonic acid-based water-soluble polymer, a polyvinyl alcohol-based water-soluble polymer, and a mixture thereof.

Examples of the water-soluble polystyrene sulfonic acid-based polymer include sodium polystyrene sulfonate, ammonium polystyrene sulfonate, sodium polystyrene sulfonate-maleic acid copolymer, sodium polystyrene sulfonate-acrylic acid copolymer, and sodium polystyrene sulfonate. -Acrylic acid ester copolymer, sodium polystyrene sulfonate-acrylamide copolymer, and the like, and preferred are sodium polystyrene sulfonate and ammonium polystyrene sulfonate. The weight average molecular weight of the polystyrenesulfonic acid-based water-soluble polymer is usually 5,000 to 1,000,000.
00, preferably 10,000 to 500,000.

If the weight average molecular weight is less than 5,000, a sufficient dispersing effect cannot be obtained, and a sediment is generated in the obtained dispersion with the passage of time, and the composition becomes nonuniform.
If it exceeds 000, the viscosity of the dispersion becomes very high,
Handling becomes difficult.

As the polyvinyl alcohol polymer,
Saponification degree 65-100 mol%, polymerization degree 100-5,000
Of unmodified polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, sulfonic acid group-modified polyvinyl alcohol, cyanoethyl group-modified polyvinyl alcohol,
Non-ionic group modified polyvinyl alcohol and the like,
Preferably, the degree of saponification is 70 to 90 mol%, and the degree of polymerization is 300 to
1,000 unmodified polyvinyl alcohol.

If the degree of saponification of the polyvinyl alcohol-based polymer is less than 65 mol% and the degree of polymerization is less than 100, a sufficient dispersing effect cannot be obtained. The product becomes non-uniform and the degree of polymerization is 5,
If it exceeds 000, the viscosity of the dispersion becomes very high and handling becomes difficult.

In the present invention, the compounding amount of (B) with respect to (A) is usually 0.05 to 10% by weight, preferably 0.5 to 10% by weight.
~ 5.0% by weight. If it is less than 0.05% by weight, a sufficient dispersing effect cannot be obtained, and the stability of the dispersion is poor. If it exceeds 10% by weight, the viscosity of the dispersion becomes high and handling becomes difficult when used. Further, (A) in the composition
Is usually at least 40% based on the total amount of the composition.
% By weight, preferably at least 60% by weight. 40
When the content is less than the weight percentage, the transportation cost and storage cost per active ingredient become high, and the industrial value becomes low.

As a method for obtaining the flame retardant composition of the present invention, a method of adding a finely pulverized (A) to an aqueous solution of (B) to obtain a partial dispersion; Adding and dissolving (B) to obtain a partial dispersion;
(A) and (B) are converted into an aqueous solution at a high temperature, and cooled to partially precipitate (A) to obtain a partial dispersion; furthermore, the precipitated (A) is wet-pulverized into fine particles to obtain a partial dispersion. And a method for obtaining the same; however, the method is not particularly limited.

In preparing the flame retardant-treated paper, the flame retardant composition of the present invention may contain other known flame retardant components, if necessary. Examples of the other known flame retardant components include guanidine salts (guanidine sulfamate, guanidine sulfate, guanidine phosphate, guanidine borate, etc.); cyano-substituted guanidine salts (guanylurea sulfamate, etc.); Containing substituted guanidine salts (such as aminoguanidine sulfamate); ammonium salts of strong acids (such as ammonium sulfamate and ammonium sulfate); compounds containing amino groups (such as dicyandiamide, melamine and hexamethylenetetramine); metal salts of strong acids (such as magnesium sulfamate) Is mentioned. Preferred among these are guanidine salts and amino group-containing compounds.

If necessary, the flame retardant composition of the present invention may be used in combination with a sizing agent, a surface treating agent such as starch, and other treating agents.

The flame retardant composition of the present invention is usually used as an aqueous solution or dispersion. The concentration can be arbitrarily selected depending on the purpose of use, but is usually 0.5 to 60% by weight in terms of solid content weight.

The substrate to which the flame retardant composition of the present invention is applied includes, for example, cellulosic materials such as paper products (shoji paper, fusuma paper, wallpaper, paperboard, synthetic paper, etc.).
It can also be used for flame-retardant processing of textile materials such as cloth and also building materials such as wood, plywood and synthetic wood.

The amount of the flame retardant composition of the present invention adhered to the substrate is usually 5 to 40% by weight, preferably 8 to 25% by weight in terms of solid weight.

The method of applying the flame retardant composition of the present invention to a substrate may be a conventional method, for example, a method of immersing the substrate in the composition of the present invention or a water diluent thereof followed by drying, Examples thereof include a method of applying with a size press, a coater or the like, and a method of applying with a brush.

[0027]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. In the following,% indicates% by weight.

The performance was evaluated by the following method. Coating amount: Adhesion amount (%) of flame retardant active ingredient based on the weight of base paper. Flame retardancy: Measure carbonization length (cm) according to JIS Z 2150 (45 ° Meckelburner method). Heat resistance (whiteness): Hunter whiteness (%) was measured after heat treatment in an oven at 200 ° C. for 3 minutes. Heat resistance (tear strength): After heat treatment in an oven at 200 ° C. for 3 minutes, the tear strength (g) was measured according to JIS P8116. Stability over time: The flame retardant active ingredient adjusted to 60% was stored at 0 ° C. and 40 ° C., respectively.
One month and three months later, the presence or absence of sediment was observed. Evaluation criteria ○: no sediment, ×: sediment generated

Production Example 1 [Production Example of (A)] 84 g of dicyandiamide and 200 g of ammonium sulfamate were mixed and reacted at 130 to 170 ° C. for 3 hours. After cooling, crushed and guanidine sulfamate (A
-1) was obtained.

Production Example 2 [Production Example of (A)] 84 g of dicyandiamide and 171 g of ammonium sulfamate were mixed and reacted at 130 to 170 ° C. for 3 hours. After cooling, crushed and guanidine sulfamate (A
-2) was obtained.

Production Example 3 [Production Example of (A)] 94 g of sulfamic acid and 37 g of calcium hydroxide were added to water 2
50 g of the solution was subjected to a neutralization reaction to obtain a 25% aqueous solution of calcium sulfamate (A-3).

Production Example 4 [Production Example of (A)] 94 g of sulfamic acid and 29 g of magnesium hydroxide were added to 225 g of water and neutralized to obtain a 25% aqueous solution of magnesium sulfamate (A-4).

Examples 1 to 5 (A-1) to (A-4) obtained in Production Examples 1 to 4, sodium polystyrene sulfonate [manufactured by Sanyo Chemical Industries, Ltd .; Chemistat SA-9], and polyvinyl alcohol [ Nippon Gosei Co., Ltd .; Gohsenol GL-05] were blended at the ratios shown in Table 1. This was heated to 60 ° C. to 70 ° C. to dissolve uniformly, and water was distilled off under reduced pressure so as to obtain an active ingredient of 60%. After cooling, the precipitated crystal was pulverized with a wet pulverizer. A dispersion having an average particle size of 0.3 μm to 3 μm was obtained. These compositions are further combined with water with active ingredient 1
Dilute to 8%, process on paper by size press method, 100 ℃
After drying with an auto dryer adjusted to ~ 105 ° C, performance evaluation was performed. Table 2 shows the daily stability of each of the dispersions and the results of performance evaluation of the treated paper.

Comparative Example 1 84 g of dicyandiamide and 200 g of ammonium sulfamate were mixed and reacted at 130 to 170 ° C. for 3 hours. Next, the reaction product and 158 g of water were added to 81 g of formalin (a 37% aqueous solution of formaldehyde), and
The mixture was heated at 0 to 70 ° C. for 2 hours to obtain an aqueous solution of the comparative flame retardant composition containing 60% of the active ingredient. This composition was diluted with water to 18% of the active ingredient, processed into paper in the same manner as in Example 1, and evaluated for performance. Table 2 shows the daily stability of the 60% aqueous solution and the results of performance evaluation of the treated paper.

Comparative Example 2 84 g of dicyandiamide and 200 g of ammonium sulfamate were mixed and reacted at 130 to 170 ° C. for 3 hours. Next, 189 g of water was added, and the mixture was heated at 50 to 70 ° C. for 2 hours to obtain an aqueous solution of a comparative flame retardant composition having an active ingredient of 60%. Dilute this composition with 18% of the active ingredient in water,
The paper was processed in the same manner as in Example 1 to evaluate the performance.
Table 2 shows the daily stability of the 60% aqueous solution and the results of performance evaluation of the treated paper.

Comparative Example 3 (A-3) obtained in Production Example 3 was heated to 60 ° C. to 70 ° C.
Water was distilled off under reduced pressure to obtain a dispersion containing 60% of the active ingredient.
This composition was diluted with water to 18% of the active ingredient, processed into paper in the same manner as in Example 1, and evaluated for performance. Table 2 shows the daily stability of the dispersion and the results of performance evaluation of the treated paper.

Comparative Example 4 (A-4) obtained in Production Example 4 was heated to 60 ° C. to 70 ° C.
Water was distilled off under reduced pressure to obtain a dispersion containing 60% of the active ingredient.
This composition was diluted with water to 18% of the active ingredient, processed into paper in the same manner as in Example 1, and evaluated for performance. Table 2 shows the daily stability of the dispersion and the results of performance evaluation of the treated paper.

Comparative Example 5 (A-1) 60 g of Production Example 1 and (A-3) 1 of Production Example 3
The mixture was heated to 60 ° C. to 70 ° C., and water was distilled off under reduced pressure to obtain a 60% dispersion of the active ingredient. This composition was diluted with water to 18% of the active ingredient, processed into paper in the same manner as in Example 1, and evaluated for performance. Table 2 shows the daily stability of the dispersion and the results of performance evaluation of the treated paper.

[0039]

[Table 1]

[0040]

[Table 2] Note) * 1: The value in parentheses in the heat resistance column indicates the hunter whiteness before the heat treatment. * 2: Daily stability at 40 ° C in the upper row and daily stability at 0 ° C in the lower row in the column of daily stability.

[0041]

The flame retardant composition of the present invention has the following effects as compared with conventional flame retardants, and is extremely useful especially as a flame retardant for cellulosic materials such as paper products. (1) Since formalin is not used, it is safe in handling, and there is no concern about residual formalin in flame-retardant products. (2) Despite being not formalin-denatured, high-concentration liquefaction is possible, so that transportation costs and storage costs can be reduced. (3) The long-term storage stability is extremely good even in a high-concentration dispersion state of about 60% by weight.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location D06M 13/438 D06M 15/00 15/00 D21H 1/34 A D21H 19/10 D06M 13/40

Claims (4)

[Claims] 1. Sulfamic acid, phosphoric acid, polyphosphoric acid,
At least one salt (A) selected from a guanidine salt, an ammonium salt, and a group I-III metal salt of at least one inorganic acid selected from boric acid and sulfuric acid, and a polystyrenesulfonic acid-based water-soluble polymer, polyvinyl Alcohol-based water-soluble polymer, polyoxyalkylene-based water-soluble polymer,
An aqueous solution or an aqueous dispersion containing, as an essential component, at least one water-soluble polymer (B) selected from a polyacrylamide-based water-soluble polymer, a polycarboxylic acid-based water-soluble polymer, and a cellulose-based water-soluble polymer. Become
The amount of (B) is 0.05 to 10% by weight based on the weight of (A), and the content of (A) is at least 40% by weight based on the total amount of the composition. Flame retardant composition. 2. The composition according to claim 1, wherein (A) is a guanidine salt of an inorganic acid obtained by reacting an ammonium salt of an inorganic acid with dicyandiamide in a molar ratio of (1-3): 1. (A) comprises guanidine sulfamate (a1) and calcium sulfamate and / or magnesium sulfamate (a2);
The weight ratio of (1) and (a2) is (10-90) :( 90: 1)
The composition according to claim 1, which is 0). 4. The method according to claim 1, wherein (B) has a weight average molecular weight of 5,000 or more.
The polystyrene sulfonic acid-based water-soluble polymer of 1,000,000 and / or the polyvinyl alcohol-based water-soluble polymer having a degree of saponification of 65 to 100 mol% and a degree of polymerization of 100 to 5,000. Composition.