JPH02300400A - Fireproofing agent composition - Google Patents

Abstract

PURPOSE:To obtain the title composition effective for paper, cloth, wood, building material, etc., containing a reaction product of a metallic salt of sulfamic acid and formaldehyde as an active ingredient. CONSTITUTION:The aimed composition containing a reaction product of a metallic salt of sulfamic acid (preferably lithium sulfamate, sodium sulfamate, potassium sulfamate, calcium sulfamate or magnesium sulfamate) and formaldehyde as an active ingredient.

Description

[Detailed description of the invention] [Industrial application fields] FIELD OF THE INVENTION This invention relates to flame retardant compositions.

[Prior Art] Conventionally, flame retardants include guanidine sulfamate, methylolated guanidine sulfamate, etc. (for example,
Tokukai Akira! 1id-199094).

[Problems to be solved by the invention] However, this product is not sufficient in terms of quality; for example, when applied to paper and heated, the paper tends to become colored, and when applied to paper and heated, the tear strength decreases. The problem was that it was easy to occur.

Means for Solving Cram] The present inventors have found that the quality is sufficient, and for example, when applied to paper and heated, the paper is unlikely to be colored, and when applied to paper and heated, there is no decrease in tear strength. (As a result of intensive research to obtain a flame retardant, we have arrived at the present invention.

That is, the present invention is a flame retardant composition characterized by containing a formaldehyde reaction product (A) of a metal sulfamic acid salt as an active ingredient.

In the present invention, sulfamic acid metal salts are exemplified by sulfamic acid alkali metal salts such as lithium sulfamate, sodium sulfamate, and potassium sulfamate, calcium sulfamate, magnesium sulfamate, and barium sulfamate. Examples include alkaline earth metal salts of sulfamic acid, zinc sulfamate, aluminum sulfamate, and mixtures of two or more thereof. Among these, lithium sulfamate, sodium sulfamino acid, potassium sulfamate, calcium sulfamate, and magnesium sulfamate are preferred.

In the present invention, sulfamic acid metal salts can be prepared by dissolving or dispersing sulfamic acid in water and adding metal hydroxides, carbonates, or oxides to water; It can be easily prepared by dissolving or dispersing and adding sulfamic acid.

In the present invention, formaldehyde includes formalin (a 37% aqueous solution of formaldehyde) and formaldehyde generating substances such as paraformaldehyde. Formalin is preferred.

The reaction amount of formaldehyde is usually 0.1 to 70%, preferably 1M50% based on the weight of the reactants. If the reaction amount is less than 0.1%, paper coloring tends to occur <, 70
%, the flame retardant property itself may deteriorate.

Examples of formaldehyde reactants of sulfamate metal salts include formaldehyde reactants of calcium sulfamate (reaction mlB% of formaldehyde in the reactant)
, Formaldehyde reaction product of magnesium sulfamate (reaction amount of formaldehyde in the reaction product! 7%), Formaldehyde reaction product of potassium sulfamate (reaction amount of formaldehyde in the reaction product), Formaldehyde reaction product of sodium sulfamate (The reaction amount of formaldehyde in the reactant is 7%).

A formaldehyde reaction product of a sulfamic acid metal salt can be produced, for example, by the following method. For example, when a sulfamic acid metal salt is added to an aqueous formaldehyde solution, I)H is! -13 can be produced by reacting at 30 to 90°C for 1 to 5 hours.

The formaldehyde reaction product may contain unreacted sulfamic acid metal salts, sulfamic acid, formaldehyde reaction products of sulfamic acid, metal hydroxides, and the like.

In addition to the formaldehyde reaction product (A) of the sulfamic acid metal salt, the composition of the present invention can also contain other components as necessary. Examples include guanidine salt compounds (B) [hydroxyalkyl-substituted guanidine (methylolated guanidine sulfamate, etc.), guanidine salts (guanidine sulfamate, guanidine phosphate, guanidine hypophosphite, guanidine polyphosphate, guanidine borate, etc.) ), cyanogen-substituted guanidine (guanylurea phosphate, guanylurea polyphosphate, etc.), amino-substituted or amino group-containing substituted guanidine salts (aminoguanidine phosphate, etc.), ammonium salts of strong acids (C) (
ammonium sulfamate, ammonium sulfate, ammonium phosphate, ammonium borate, ammonium polyphosphate, etc.), dicyandiamides (D) (dicyandiamide, methylolated dicyandiamide, etc.), metal salts of strong acids (E) (lithium sulfamate, sodium sulfamate) , potassium sulfamate, calcium sulfamate, magnesium sulfamate, barium sulfamate,
Zinc sulfo-monomate, aluminum sulfo-monomate, potassium sulfate, calcium sulfate, magnesium sulfate, sodium sulfate, aluminum sulfate, sodium phosphate, calcium phosphate, sodium polyphosphate, sodium chloride, calcium chloride, sodium oxalate, etc.), etc.

When containing (B), (C), (D), (E), etc., (B) (B) (C) CD) (E) etc. may be mixed to produce the product, or (A ) May be added after production.

In the composition of the present invention, the content of the formaldehyde reactant (A) of the sulfamic acid metal salt is usually 1% or more, preferably 5% or more, based on the weight of the composition. ! %, sufficient performance may not be obtained.

In the composition of the present invention, the content of (B), (C), (D), and (E) can be selected without particular limitation within a range that satisfies the performance as a flame retardant. is usually 39% or less, preferably 95% or less.

The content of components (C), (D) and (E) is usually 95% or less, preferably 30% or less.

Preferably, the composition of the invention is used as an aqueous solution.

When dissolved, the concentration can be varied depending on the purpose of use. The concentration used is usually 0.5 to 60%, preferably 1 to 50%, based on the solid weight of the composition.

Substrates to which the composition of the present invention can be used include cellulosic materials such as paper (shoji paper, fusuma paper, wallpaper, paperboard, synthetic paper, etc.). It can also be used for fiber materials such as cloth, and building materials such as wood, plywood, and synthetic wood.

The amount of the composition of the present invention adhered to the substrate is usually 2 to 40%, preferably 3 to 35% in terms of solid weight.

The composition of the present invention may be applied to a substrate by any conventional method, such as by immersing the substrate in the composition of the present invention or its water diluted solution and then drying it, or by applying it using a size press. There are two methods: applying with a brush, and applying with a brush.

Further, the composition of the present invention can be used in combination with a sizing agent, a surface treatment agent such as starch, and other treatment agents.

[Example] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Parts in Examples and Comparative Examples indicate parts by weight.

Examples 1-4 10-3 in a mixture of sulfamic acid and water according to Table-1
After adding metal hydroxide at 0°C to create a sulfamic acid metal salt, formalin was added and the mixture was heated to 50°C at pH 5-9.
The reaction was carried out at ~70°C for 2 hours. This was used as the flame retardant compositions of Examples 1 to 4.

Comparative Example 1 Dicyandiamide and ammonium sulfamate were mixed according to Table 2 and reacted at +30-170''C for 3 hours.The flame retardant composition of Comparative Example 1 was prepared by adding water to this mixture.

Comparative Example 2 Dicyandiamide and ammonium sulfamate were mixed according to Table 2, and! The reaction was carried out at 30 to 170"C for 3 hours.Then, the above reactant was added to the water and formalin system, and the reaction was carried out at 50 to 70"C for 2 hours.This was used as the flame retardant composition of Comparative Example 2. .

Table 1 Table 2 Test Example 1 Using the flame retardant compositions of Examples 1 to 4 and Comparative Examples 1 to 2, paper was treated with the treatment liquid by the size press method and
After drying with an auto dryer controlled at 105° C., performance was evaluated using the following method. The results are shown in Table-3.

Coloration prevention property: Heated in an oven at 180'CX for 10 minutes and compared the degree of coloration.

Tear strength: Measured according to JIS-P-8116r paper tear strength test method after heat treatment in an oven at 180° C.

Flame retardancy: The carbonizing tool was measured according to JIS-Z-215Or "Flame retardant test for thin materials" (45@Metskel burner method).

Table 3 Anti-coloring property O: light yellow, △: yellow, ×: light brown Flame retardant: long carbonization It has further improved anti-coloration properties and tear strength when applied to paper and heated, compared to guanidine sulfamate (guanidine sulfamate, etc.).

Furthermore, when applied to paper, a material with soft stiffness is desired. Conventional flame retardants have not been sufficient, but the composition of the present invention is also superior in this respect.

Furthermore, when used as an aqueous solution, it is easily dissolved and has good compatibility with other processing agents, such as sizing agents, binders (starch, polyvinyl alcohol), and is quick to dissolve and has good workability.

Because it has the above effects, the composition of the present invention can be used for paper, cloth,
It is effective for many uses such as wood and various building materials.

It is also effective in flameproofing resins.

Claims (1)

[Claims] 1. A flame retardant composition containing a formaldehyde reaction product of a metal sulfamic acid salt as an active ingredient.