JPS60108491A - Flame-retardant - Google Patents

Abstract

PURPOSE:A flame-retardant mainly for paper slightly coloring during heating and treatment, comprising a phosphate of ethylenediamine (condensate), hydrazine compound, boric acid compound, etc. CONSTITUTION:(A) 1pt.wt. reaction product of ethylenediamine (condensate) and phosphoric acid is blended with (B) (i) preferably >=0.1pt.wt. hydrazine compound and/or preferably 0.2-0.8pt.wt. boric acid or (ii) preferably >=0.1pt.wt. component i and phosphorous acid or its salt, and processed into a solution or slurry, to give the desired flame-retardant. The flame-retardant shows sufficiently even at 10wt% pickup ratio.

Description

[Detailed description of the invention] It is something to do.

Conventional flame retardants for paper include sul-7-amino acid/guanidine acid and the like. However, these flame retardants do not exhibit their effects unless added in large amounts, and there is a problem in that flame retardant-treated paper becomes colored when heated.

On the other hand, the polyethylene polyamine or ethylene diamine phosphate described in Japanese Patent Publication No. 49-52754 exhibits excellent flame retardancy, but when paper coated with the amine phosphate is heat-treated, its coloration is reduced. There were some notable drawbacks.

The present inventors have conducted various studies to solve the above-mentioned drawbacks of amine phosphates, and have found that amine phosphates can be supplemented with hydrazine compounds and/or boric acid compounds, or even formic acid, tinous acid, hypophosphorous acid, etc. It has been found that by mixing one kind of acid or its salt, it is possible to suppress coloring during heat treatment to a level that causes no practical problems, without reducing flame retardancy. The invention has been completed.

The amine phosphate in the present invention is ethylenediamine or its condensate, for example, 2N-(aH, aH
2NH') rVH (n-1 to 5 are good in terms of flame retardancy)
Group - (-1 (4) 2NH, HN (Ratook) Disappeared to 2N.

It is a product obtained by reacting one or more amines represented by phosphoric acid with phosphoric acid. Although the reaction ratio of amine and phosphoric acid is not particularly limited, it is preferable to adjust the pH to around 7 in terms of less influence on paper and high solubility in water.

Examples of the hydrazine compound used in the present invention include hydrazine hydrate, hydrazine sulfate, and hydrazine acetate. These may be used alone or in combination of two or more. The mixing amount of these hydrazine compounds is preferably α1 parts by weight or more per 1 part by weight of the amine phosphate.

In addition, as a boric acid compound, for example, boric acid, boric acid)
Examples include IJum and the like, which may be used alone or in combination of two or more. The amount of the boric acid compound mixed is preferably 0.2 parts by weight or more per 1 part by weight of the amine phosphate, but
If more than 8 parts by weight is mixed, the paper will harden and lose its texture.

Addition of formic acid, hypophosphorous acid, or a salt thereof has the effect of reducing the amount of hydrazine compound mixed, and when used together with a boric acid compound, coloring can be further suppressed.

The salt is preferably one having high solubility in water, such as a sodium salt, and the mixing amount thereof is preferably 0.1 part by weight or more per 1 part by weight of the amine phosphate.

The adhesion rate of the flame retardant is 10% compared to the conventional guanidine sulfamate, which has a coefficient of 18 or more, and still exhibits its effect.

This flame retardant can be produced as follows.

That is, one method is to dissolve or mix a hydrazine compound and/or a boric acid compound in an aqueous phosphoric acid solution or slurry of an amine to form a slurry, or to add formic acid, phosphorous acid, and primary phosphorus to the solution or slurry. Another method is to add an acid or its salt to form a liquid or slurry.Other methods are to collect amine phosphate crystals precipitated from a solvent such as water or alcohol, and after drying, form a solid such as hydrazine sulfate. It is made into a powder by mixing a hydrazine compound and/or a boric acid compound, or by further mixing with formic acid, a salt of 9-hypophosphorous acid, and these three types are in liquid, slurry, or powder form. No difference was observed in the effectiveness of these flame retardants.

The present invention will be specifically explained below using Examples.

Example 1 134 ml of water in a 500-flask. 75 wt % phosphoric acid was prepared, and while stirring, 49 g of an aqueous solution of ethylenediamine having a concentration of s O wt % was gradually added dropwise. Liquid temperature is 60°
The reaction was completed in about 20 minutes while cooling so as not to exceed C. This was added to hydrazine hydrate manufactured by Wako Pure Chemical Industries, Ltd.
NH, NH, .Hlo) 139 and boric acid (H3BO8) 399 manufactured by Kanto Kagaku Co., Ltd. were added.

259 portions of the resulting transparent liquid were taken, further diluted with 60% water, 5A Oki paper manufactured by Toyo Roshi Co., Ltd. was immersed in this, and then dried for 30 minutes in a dryer kept at 70°C. I let it happen. The Okigami was heated at 180°C and 200°C for 3 times each.
The mixture was heated for a minute and its colorability was observed. Furthermore, its flame retardant effect was also investigated.

The results are shown in Table-3.

Examples 2 to 6 Coloring properties and flame retardant effects were tested in the same manner as in Example 1, except that the flame retardant was adjusted as shown in Table 1. The results are shown in Table-3. A 50 wt% aqueous solution of the same amine was used in each case.

Example 7 In a 500-flask, 100 g of water and 1 g of 75 wt tyrinic acid were added.
While stirring, an aqueous solution of ethylenediamine 989 having a concentration of 50 wt% was gradually added dropwise.

The reaction was completed in about 30 minutes while cooling the solution so that the temperature did not exceed 60°C. After the precipitated amine phosphate crystals were filtered off, they were dried for 2 hours in a dryer maintained at 100°C. After dissolving 10 g of the obtained white crystals and 6 g of boric acid in 90 g of water, Okigami was treated and tested in the same manner as in Example 1. The results are shown in Table-3.

Examples 8-9. Comparative Example 1 10 g of the amine phosphate dried in Example 7 and a hydrazine compound in the ratio shown in Table 2.

The treatment was carried out in the same manner as in Example 7 except that the boric acid compound and the boric acid compound were dissolved in water. Thereafter, the P paper was treated and tested in the same manner as in Example 1. The results are shown in Table-3.

Table-2 (1) Book (NH2)2・H, so4 Manufactured by Wako Pure Chemical Industries, Ltd. Reagent special grade table-3 Patent applicant Toyo Soda Kogyo Co., Ltd.

Claims (1)

[Scope of Claims] A reaction product of ethylenediamine and/or one or more of its condensates and phosphoric acid, (a) a hydrazine compound and/or a boric acid compound, or (b) a hydrazine compound and/or a boric acid compound, and A flame retardant consisting of one or more types of formic acid, sulfuric acid, secondary hypophosphorous acid, or a salt thereof.