JPS61141785A - Flameproofing agent for cellulosic material - Google Patents

Abstract

PURPOSE:The titled cheap flameproofing agent with excellent thermal discoloration resistance, prolonged chemical stability and flameproofing effect evolving little smoke and exerting little metal corrosiveness when burnt, which is prepd. by incorporating a mixture compsn. obtd. by mixing boric acid with sodium phosphate in a specified proportion as an effective component. CONSTITUTION:20-100pts.wt. mixture compsn. obtd. by mixing 20-70wt% boric acid with 80-30wt% sodium phosphate of the formula (wherein x is 1.5-2.5) such as Na2HPO4 is, if necessary, compounded with another flameproofing agent such as guanidine phosphate, guanidine sulfamate, guanidine sulfate or guanylurea phosphate to obtain the titled flameproofing agent compsn. A treating stock consisting of a cellulosic material is given a high flameproofing effect by attachment of 8-15wt% said compsn.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention is directed to a cellulose-based material that has a high flame retardant effect, excellent heat discoloration resistance, and high solubility in water, making it suitable for treatment methods such as impregnation and spraying. The present invention relates to a flame retardant composition for materials.

``Prior art'' Conventionally, phosphorus compounds, nitrogen compounds, sulfur compounds, and boron have been used as flame retardants to impart flame retardancy to cellulose-based products that are mainly composed of cellulose, such as cloth, wood, paperboard, and wall covering materials. Compounds etc. are widely used. Specifically, guanidine phosphate, guanidine sulfamate, guanidine sulfate, guanidine borate, phosphorus guanylurea, polyphosphorus guanylurea, and the like are commonly used. These various inorganic acid salts of nitrogen-containing organic compounds are heat resistant (heat resistant to discoloration).
However, the stability of the hue over time in the atmosphere, the flame retardant effect, the amount of smoke generated during combustion, etc. are not fully satisfactory. In other words, 1 cellulose-based product to which these flame retardants have been added
When heated to a high temperature of 80 to 200°C or left in the air for a long period of time, discoloration such as yellowing is inevitable, which impairs the aesthetic appearance and reduces product value.

In addition, in order to achieve a practically sufficient flame retardant effect with the most commonly used guanidine sulfamate, it is necessary to apply approximately 18% by weight of the flame retardant to the treated material, which is difficult to achieve in terms of adhesion rate. It is difficult to say that it is an agent with excellent flame retardant effects.

Various ammonium phosphates, various condensed ammonium phosphates, ammonium sulfamate, heptammonium sulfate, boric acid,
In some cases, inorganic compounds such as borax are used alone or in combination.

Among them, ammonium dihydrogen phosphate and ammonium hydrogen phosphate have a high flame retardant effect, and are used alone or in combination with boric acid, borax, etc. (Japanese Patent Publication No. 46-45
Publication No. 245). Originally, it is widely known that these ammonium phosphate compounds have efflorescence properties, and products treated with these flame retardants deteriorate over time not only when subjected to heat treatment but also at room temperature. As a result, the composition components change, and as a result, the flame retardant effect changes over time, making it difficult to obtain reliable flame retardant products.

Usually, as a method for attaching a flame retardant to a piece of cloth, etc., a uniform transparent aqueous solution of the flame retardant is used, and treatment is carried out by impregnation or spraying.

Therefore, it is desired that the flame retardant for cellulosic materials has high solubility in water. When boric acid or borax, which has extremely low solubility in water, is blended into a flame retardant, the blending ratio is largely controlled by the solubility in water. For example,
-43245, ammonium phosphate 99
A mixed composition of ~80% by weight and 1 to 20% by weight of borax is used, and the blending ratio of borax is specified to be 20% by weight or less.

In the examples, the maximum blending ratio of borax is 13% by weight. This can be said to be an example in which the blending ratio of the flame retardant composition, which has a large effect on the flame retardant effect, is controlled by the solubility in water.

"Problems to be Solved by the Invention" As mentioned above, it has excellent thermal discoloration resistance and chemical stability over time, exhibits high flame retardancy with a small amount of adhesion, has high solubility in water, and has processing operations such as impregnation and spraying. There is a strong demand for the development of a flame retardant for cellulosic materials that simultaneously satisfies a variety of functions, such as being suitable for combustion, emitting little smoke during combustion, and being virtually non-corrosive to metals.

The present invention aims to provide such a flame retardant for cellulosic materials.

"Means and effects for solving the problem" In view of these circumstances, the present inventors have conducted extensive research and found that phosphorus with a specific composition among sodium phosphates has extremely low flame-preventing effect when used alone. When used alone, the flame retardant effect is small, and the solubility in water (at 20°C, solubility in water is 4).
．． We discovered that a new flame retardant composition that has a high flame retardant effect and extremely high solubility in water can be created by blending boric acid with extremely low 6 ft%) in a specific ratio. Completed the invention.

That is, the present invention utilizes boric acid and phosphorus monosiliium N & taHa-sP% having the following atomic ratio (1. is 1.5 to 2.5
The present invention provides a flame retardant composition for cellulose-based materials, characterized in that it contains as an active ingredient a mixed composition of 20 to 70:80 to 30 by weight.

The present invention will be explained in detail below.

The sodium phosphate of the flame retardant composition (1) of the present invention is
0-70780-30 preferably 75-50/25-5
It is characterized in that the active ingredient is a composition blended with 0. In the mixed composition, the above blending ratio is 20780
If the amount is below, the flame retardant effect will drop sharply, making it impossible to achieve the object of the present invention, which is to provide high flame retardant properties to cellulose-based materials with a low adhesion amount. Also that is 70
/30 or more, the solubility of the blended composition in water decreases rapidly, making it difficult to apply the flame retardant to cellulose materials by impregnation, spraying, etc.

Sodium phosphate, which is one component of the flame retardant composition of the present invention, is a compound with a specific composition having an atomic ratio represented by the composition formula (1), and is preferably disodium monohydrogen phosphate (
Na, HPO4) are used. A mixed composition of sodium phosphate Nζ and boric acid having an atomic ratio of 1≦z (t 5) does not have a sufficiently satisfactory solubility in water, regardless of the blending ratio of the two, and the mixture If the pH value of the water in which the composition is dissolved (solute concentration 5 wt% aqueous solution) is 55 or less, problems such as corrosion of the flame retardant dissolution tank; impregnating and spraying equipment, etc., and deterioration of the physical properties of the attached cellulose-based material, etc. cause

2,5 (sodium phosphate N with atomic ratio z≦3
A mixed composition consisting of azFIm-Cpo4 and boric acid in an arbitrary blending ratio has extremely low solubility in water and is not an advantageous composition in terms of operability in adhesion treatment to cellulose materials by impregnation, spraying, etc. In addition, if the pH value of the water in which the mixed composition is dissolved is 9.0 or more, the attached cellulose-based material may suffer from deterioration of physical properties such as hydrolysis over time. Furthermore, when the flame retardant treated product is ignited and burned, it leaves a large amount of residue, making it undesirable as a flame retardant. As mentioned above, the sodium phosphate used in the present invention is usually monohydrogen phosphate (IJ)
Most preferably, sodium dihydrogen phosphate, disodium monohydrogen phosphate and trisodium phosphoric acid may be used by blending them in an atomic ratio as shown in the compositional formula (1). Further, a product obtained by mixing and reacting caustic soda and phosphoric acid so as to have the atomic ratio of the composition formula (1) may be used, and the method for preparing sodium phosphate is not particularly limited.

As the flame retardant of the present invention, in addition to the mixed composition of sodium phosphate and boric acid, known flame retardants such as guanidine phosphate, guanidine sulfamino acid, guanidine sulfate, and guanylurea phosphate may be used in combination.

By blending and adding the flame retardant composition of the present invention, the disadvantages of known flame retardants, such as thermochromic properties and low flame retardant effects, can be improved, and more desirable properties as a flame retardant can be imparted.

The flame retardant composition of the present invention is usually about 20 to 10% of the total amount of flame retardant.
It may be contained and used in a proportion of 0% by weight. 20% by weight
At the following blending ratios, the flame retardant composition of the present invention cannot fully exhibit its excellent functions.

``Effects of the Invention'' The flame retardant of the present invention can be used in the form of an aqueous solution or powder, but it can be used in a general manner by taking advantage of the high solubility of the flame retardant in water and its high permeability into the material to be treated. A method in which the material to be treated is impregnated or sprayed in an aqueous solution and adhered thereto is widely applied. The flame retardant of the present invention can achieve a higher flame retardant effect when attached to the material to be treated in a weight ratio of 8 to 15%. In particular, when the flame retardant of the present invention is used alone, the normally required flame retardant effect can be achieved with a coating amount as low as 8 cm, resulting in extremely excellent flame retardant properties.

It can be said that it is a composition that has the ability to impart.

The flame retardant of the present invention is inexpensive, has an extremely high flame retardant effect, and can provide the desired flame retardant property with a low adhesion amount, making it an economically advantageous flame retardant. In addition, even when treated materials are heated at high temperatures, almost no discoloration is observed, and furthermore, no change in chemical composition is observed, and no deterioration in the flame-retardant effect is observed at all. The smoke emitted from the burning material treated with the flame retardant is as follows:
It is extremely small compared to Nozochi's general-purpose organic flame retardants, and it also has excellent practical functionality as it leaves almost no residue.

Furthermore, it is not corrosive to metals, etc., and hardly any changes in physical properties of treated materials are observed over time.

The flame retardant composition has high solubility in water and high permeability into the material to be treated, so it is highly practical and has the advantage of being able to quickly adhere to and treat thick paper products such as kraft paper and paperboard. It is a flame retardant.

"Examples" The present invention will be described below with reference to Examples, but the present invention is not particularly limited by the Examples.

Examples 1 to 9 Examples 1 to 3 are a combination of disodium monohydrogen phosphate and boric acid, and Example 4 is a combination of disodium monohydrogen phosphate 80
A combination of sodium phosphate and boric acid with a blending ratio of 2.2 moles of caustic soda and 1 mole of phosphoric acid in Examples 5 and 6. Combination of sodium and boric acid (
Actual case 5 is caustic soda 5! L1 parts by weight, 359 parts by weight of phosphoric acid.

Example 6 is a composition with a blending ratio of 30 parts by weight of boric acid, Example 6 is a composition with a blending ratio of 26 parts by weight of caustic soda, 29 parts by weight of phosphoric acid, and 45 parts by weight of boric acid. A flame retardant composition consisting of a combination of boric acid and guanidine sulfamate (Example 9 is monohydrogen phosphate), boric acid, and guanidine phosphate was blended in the weight ratio shown in Table 1 and dissolved in water. A uniform and transparent aqueous flame retardant solution with a predetermined concentration was prepared.

Method for attaching flame retardant P paper (Toyo P Paper &2) was immersed in the above aqueous flame retardant solution and then taken out. The treated paper is sandwiched between new door papers to remove excess soaking liquid.

After drying at 100°C for 2 hours, leave to cool in a desiccator.
It was subjected to the following tests.

Flame retardant adhesion rate - Weight of treated paper after chimney drying (100°C, 2 hours) B: Weight of P paper before drying (100°C, 2 hours) Flame retardant test: JXB A1322 ( 45° Metschel burner method)
Carbonization length and residue were measured according to the following. The amount of smoke emitted during combustion was also visually observed.

Heat resistance (thermochromic) test After heating for 10 minutes at 180"C in a constant temperature hot air dryer,
The value (whiteness) and b value were measured to evaluate love-chromaticity.

Corrosion test for metals Commercially available office clips (adhered oil-soluble components were removed with ethanol) were used as the metal material, and 10 clips were attached to a sheet of flame retardant treated paper. The product was left in an atmosphere with a humidity of 80 degrees for two months, and the presence or absence of rust was visually observed.

The solubility of the water-soluble flame retardant composition when dissolved in water (20°
C) was evaluated on a four-level scale.

◎Solute concentration a　o　C4 (vt) or higher was dissolved.

○　　　z　　50～40chi Δ　　　g　　　20～10% ×　　　　　　10% or less pH of flame retardant aqueous solution Solute concentration Swt pH value of aqueous solution The above evaluation test results are shown in Table 2.

Comparative Examples 1 to 6 Door paper was impregnated with the flame retardant composition shown in Table 3 in the same manner as in Examples 1 to 9, and the treated paper was subjected to an evaluation test in the same manner.

Table 3 Table 4 shows the evaluation test results.

Procedural amendment June 6, 1985 Mr. Manabu Shiga, Commissioner of the Patent Office 1 Display of the case 1982 Patent Request No. 260902 2 Name of the invention Flame retardant for cellulosic materials 3 Relationship with the amended case Patent application Toyo Soda Kogyo Co., Ltd. Patent Information Department Telephone number (585) 3311 4 Date of amendment order Voluntary 5 Subject of amendment Column for detailed explanation of the invention in document M 6 Contents of amendment (1) Specification, page 3, 12 Correct "compound" in the line to "compound is".

(2) On page 6, line 11 of the same page, amend "be below E" to "does not reach".

(3) In the 6th true, line 15 of the same sentence, [j that is greater than or equal to is corrected to be ``beyond.''

(4) Add "solubility in water" next to "mixture" on page 7, line 3.

:5) Delete "solubility in water" from line 4 on page 7.

(6) In the 4th line of page 7, "mono ni ni ni" is corrected to "monon ni."

7〉 “Aqueous solution)” on page 7, line 6 of the same is changed to “aqueous solution)”.
] Correct.

8) Correct ": impregnation," in page 7, 7h, to ", impregnation."

Claims (3)

[Claims] (1) Sodium phosphate Na_xH_■_-_xPO_4 consisting of boric acid and the following atomic ratio (x is 1.5
~2.5), weight ratio 20-70:80-30
A flame retardant composition for cellulosic materials, characterized in that it contains a mixed composition of as an active ingredient. (2) The flame retardant composition for cellulosic materials according to claim (1), wherein the sodium phosphate is disodium monohydrogen phosphate. (3) Weight ratio of boric acid and disodium monohydrogen phosphate: 2
The flame retardant composition for cellulosic materials according to claim (2), which contains as an active ingredient a mixed composition of 5-50:75-50.