JPH0624718A - Slightly soluble ammonium polyphosphate compound, its production and resin containing the same - Google Patents

Abstract

PURPOSE:To provide a neutral, insoluble ammonium polyphosphate compound and to produce a flame-retardant resin having high bleed resistance and high flame retardance. CONSTITUTION:0.01-0.1mol based on 1mol phosphorus of oxide, hydroxide, carbonate, phosphate, polyphosphate, borate or silicate of one or more metals selected from the group consisting of alkaline earth metals such as magnesium, calcium and strontium and zinc and aluminum is contained to produce a slightly soluble ammonium polyphosphate compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel insoluble ammonium polyphosphate compound having no water-soluble component, a method for producing the same, and a flame-retardant resin containing the same.

[0002]

2. Description of the Related Art Ammonium polyphosphate has been a well-known substance, and has been produced by a method of dehydrating ammonium orthophosphate, a method of mixing polyphosphoric acid and ammonia or urea and heating. .

JP-B-43-19218 discloses that a small amount of water-insoluble ammonium polyphosphate is added to a composition consisting of a phosphate, an ammoniating agent, and a condensing agent.
A method for producing water-insoluble ammonium polyphosphate characterized by heating to 100 to 350 ° C. is disclosed. Further, Japanese Patent Publication No. 47-38319 discloses a mixture of ammonium orthophosphate and urea having a boiling point of 190 to 300.
After reacting in a hydrocarbon medium at 0 ° C, the reaction product is separated and heated at a temperature above the boiling point of the hydrocarbon to remove the hydrocarbon. Furthermore, Japanese Patent Publication 60-6
In 885, a small amount of melamine is added to a mixture of ammonium orthophosphate and phosphorus pentoxide, and the mixture is allowed to react at 50 to 150 ° C. in the presence of excess ammonia.
A method for producing a long-chain ammonium polyphosphate characterized by performing a tempering treatment at 0 to 300 ° C. is disclosed. JP-A-3-141109 discloses a mixture of ammonium orthophosphate and phosphorus pentoxide. Is reacted at 150 to 280 ° C. for 20 to 30 minutes in a pulverized state at a high mixing strength, and then heat treated in an ammonia atmosphere at 250 to 280 ° C. for 100 to 120 minutes. A method of making ammonium acid is disclosed.

On the other hand, various inventions have been made on flame-retardant resins. For example, JP-A-61-66736 is characterized in that a polyolefin-based polymer is blended with a hydroxide of alkaline earth metal, aluminum hydroxide, and a fibrous substance containing silica. A flame-retardant resin composition is disclosed. JP-A-61-213234 discloses that an olefin resin is blended with aluminum hydroxide and magnesium hydroxide to prepare red phosphorus, zinc borate, and titanium dioxide. Disclosed is a flame-retardant resin composition characterized by being added. Furthermore, JP-A-3-5654
Japanese Patent Publication No. 7 discloses a flame-retardant resin composition characterized by adding ammonium polyphosphate to polypropylene resin.

[0005]

The ammonium polyphosphate obtained by the above-mentioned method is an excellent flame retardant, but it is not always sufficient in terms of water insolubility and neutrality. . The problem to be solved by the present invention is to increase the insolubility in water and make it a neutral substance,
Kneading into resin, dispersibility when mixing with hydrate, etc.,
It is to improve workability when mixed in a high concentration in a resin, and further improve stability and storage stability after being dispersed in a resin to improve flame retardant properties and water resistance of the flame retardant resin.

[0006]

Means for Solving the Problems In order to solve the above problems, the present inventors have selected one or more selected from the group consisting of alkaline earth metals such as magnesium, calcium and strontium, zinc, and aluminum. Metal oxides, hydroxides, carbonates, phosphates, polyphosphates, borates,
Alternatively, silicate is added in an amount of 0.01 to 0.
Disclosed is a novel sparingly soluble ammonium polyphosphate compound containing 1 mol, and a method for producing the same is disclosed.
A resin composition containing wt% is provided.

One of the methods for producing the above-mentioned sparingly soluble ammonium polyphosphate compound according to the present invention is to use diphosphorus pentoxide, a condensing agent such as urea or melamine, and ammonium phosphate, ammonium carbonate, ammonium hydrogen carbonate or the like. An ammoniating agent is mixed in a ratio of 1.2 mol or more of nitrogen to 1 mol of phosphorus, and 0.01 to 1 mol of phosphorus is further added.
Oxide, hydroxide, carbonate, phosphate, boric acid of at least one metal selected from the group consisting of 0.1 mol of an alkaline earth metal such as magnesium, calcium and strontium, zinc and aluminum. It is characterized in that a solid-phase reaction product obtained by mixing a salt or a silicate and carrying out a solid-phase reaction is calcined at 150 to 350 ° C. in an ammonia atmosphere.

Another method for producing the above-mentioned sparingly soluble ammonium polyphosphate compound according to the present invention is diphosphorus pentoxide, a condensing agent such as urea or melamine, and ammonium phosphate, ammonium carbonate or ammonium hydrogen carbonate. The solid-phase reaction product obtained by mixing such an ammoniating agent with 1 mole of phosphorus at a ratio of 1.2 moles or more of nitrogen and solid-phase reaction is 0.01 ~ 0.1 mol of oxides, hydroxides, carbonates, phosphates of one or more metals selected from the group consisting of alkaline earth metals such as magnesium, calcium and strontium, zinc and aluminum; It is characterized by mixing borate or silicate and firing at 150 to 350 ° C. in an ammonia atmosphere.

In the method for producing a sparingly soluble ammonium polyphosphate compound according to the present invention, magnesium added in addition to diphosphorus pentoxide, a condensing agent and an ammoniating agent,
The compound of at least one metal selected from the group consisting of alkaline earth metals such as calcium and strontium, zinc, and aluminum is an oxide, hydroxide, carbonate, phosphate, borate, or It is preferably silicate,
Sulfates, nitrates and chlorides are not preferred. It is considered that during the reaction of forming ammonium polyphosphate, a part of these metal compounds is changed to phosphate or polyphosphate.

Further, these metal compounds are preferably mixed in a ratio of 0.01 to 0.1 mol per 1 mol of phosphorus. If it is less than 0.01 mol, almost no effect is exhibited, and if it exceeds 0.1 mol, ammonium polyphosphate is hard to be produced, and the flame retardancy is lowered, which is not preferable.

In the method for producing a slightly soluble ammonium polyphosphate compound according to the present invention, a kneader, It is preferable to use a ball mill, a raider, a vibration mill or the like. The obtained reaction product can be calcined batchwise using an electric furnace or the like, or continuously in a rotary kiln or the like.

As the resin used in the resin according to the present invention containing the above-mentioned sparingly soluble ammonium polyphosphate compound, a polyolefin resin such as polyethylene, polypropylene, ethylene-propylene copolymer, polyester resin, epoxy resin, Examples include phenol resin and urethane resin. The amount of the sparingly soluble ammonium polyphosphate compound added to these resins is in the range of 5 to 30% by weight, and if it is less than 5% by weight, the effects of flame retardancy and the like will be reduced. If it exceeds, problems may occur in terms of mechanical strength and the like. In addition to these resins, hydroxides such as aluminum hydroxide, halides,
Other flame retardants such as boron compounds, antimony oxide, and red phosphorus can be added and used in combination. Further, when a sparingly soluble ammonium polyphosphate compound or the like is added, it is effective if it is treated with a silane-based, titanium-based or aluminum-based coupling agent to further improve the dispersibility.

The resin thus produced is used not only as a block-shaped or plate-shaped product, but also as a fibrous or film-shaped product, and also as an adhesive or paint.
It is applied to clothes, housing materials, home appliances, etc. that take advantage of flame retardancy and solubility.

[0014]

The action of the sparingly soluble ammonium polyphosphate compound according to the present invention to show the sparingly soluble property while maintaining the structure of ammonium polyphosphate and the capability of maintaining the flame retardancy are unknown in detail. However, for the time being, the following actions are considered to be involved. That is, when synthesizing ammonium polyphosphate, or during firing, a metal such as an alkaline earth metal added accelerates the condensation of phosphoric acid, effectively insolubilizing phosphoric acid into a long chain,
Further, it is considered that it is bonded to the terminal of the condensed chain to improve the water resistance. Further, the sparingly soluble ammonium polyphosphate compound having such characteristics, even when kneaded into the resin, has high water resistance and hardly reacts with the resin or additives, so that it does not cause deterioration or deterioration of the resin, It is considered to exhibit excellent flame retardancy over a long period of time.

[0015]

【Example】

1 Production of flame-retardant ammonium polyphosphate compound [Example 1] 100 g of diphosphorus pentoxide, 44 g of urea, 67 g of ammonium bicarbonate, 12 ammonium dihydrogen phosphate
g, 9 g of aluminum hydroxide (0.
(082 mol) was put in a kneader and reacted at 25 ° C. for 0.5 hours. The obtained reaction product was placed in an externally heated rotary kiln and calcined at 280 ° C. for 8 hours. The obtained baked product was pulverized to 45 μm or less to obtain a powder (hereinafter referred to as “powder 1”).

Example 2 100 g of diphosphorus pentoxide, 32 g of urea, 67 g of ammonium bicarbonate, 12 g of diammonium hydrogen phosphate and 3 g of magnesium hydroxide (0.037 mol per mol of phosphorus) were placed in a kneader. The reaction was carried out at 25 ° C for 0.5 hours. The obtained reaction product was fired and pulverized in the same manner as in Example 1 to obtain a powder (hereinafter referred to as "powder 2").

Example 3 100 g of diphosphorus pentoxide, 30 g of urea, 49 g of ammonium bicarbonate, 12 g of diammonium hydrogen phosphate, 5 g of zinc oxide (0.044 mol per mol of phosphorus), 4 g of strontium carbonate (phosphorus) (0.019 mol per 1 mol) was put in a kneader and reacted at 25 ° C. for 0.5 hours. The obtained reaction product was fired and pulverized in the same manner as in Example 1 to obtain a powder (hereinafter referred to as "powder 3").

Example 4 100 g of diphosphorus pentoxide, 41 g of urea, 67 g of ammonium bicarbonate and 12 g of diammonium hydrogen phosphate were placed in a kneader and reacted at 25 ° C. for 0.5 hours. The obtained reaction product contained 9 g of calcium borate (CaB ₂ O ₄ ) (0.051 with respect to 1 mol of phosphorus).
Mol) was added and mixed well, then fired and pulverized in the same manner as in Example 1 to obtain a powder (hereinafter referred to as “powder 4”).

Example 5 100 g of diphosphorus pentoxide, 44 g of urea, 88 g of ammonium bicarbonate, 12 g of diammonium hydrogen phosphate, 4 g of magnesium hydrogen phosphate (phosphorus 1
0.024 mol with respect to mol), aluminum hydroxide 5
g (0.045 mol per 1 mol of phosphorus) was placed in a kneader and reacted at 25 ° C. for 0.5 hours. The obtained reaction product was fired and pulverized in the same manner as in Example 1 to obtain a powder (hereinafter referred to as "powder 5").

Example 6 100 g of diphosphorus pentoxide, 32 g of urea, 67 g of ammonium bicarbonate, 12 g of diammonium hydrogen phosphate, 5 g of magnesium hydrogen silicate (phosphorus 1
0.018 mol per mol), calcium carbonate 4 g
(0.028 mol per 1 mol of phosphorus) was placed in a kneader and reacted at 25 ° C. for 0.5 hours. The obtained reaction product was fired and pulverized in the same manner as in Example 1 to obtain a powder (hereinafter referred to as "powder 6").

Comparative Example 1 A mixed powder of 30 g of urea and 173 g of diammonium hydrogen phosphate was fired and pulverized in the same manner as in Example 1 to obtain a powder (hereinafter referred to as "powder 7").

Comparative Example 2 100 g of diphosphorus pentoxide, 30 g of urea, 37 g of ammonium bicarbonate and 12 g of diammonium hydrogen phosphate were placed in a kneader and reacted at 25 ° C. for 0.5 hours. The obtained reaction product was fired and crushed in the same manner as in Example 1 to obtain a powder (hereinafter referred to as "powder 8").

[Comparative Example 3] Powder 50 obtained in Comparative Example 1
2.5 g of aluminum hydroxide was mixed with g to obtain a mixed powder (hereinafter referred to as "powder 9").

2. Measurement of 1% PH and water insoluble matter From powders 1 to 9 obtained in Examples 1 to 6 and Comparative Examples 1 to 3, 1 g was precisely weighed as a sample, and pure water was added to make the total amount 100 g. After stirring for a minute, glass electrode P
It was measured with an H meter. The results obtained are shown in Table 1.

2 g of each of the powders 1 to 9 obtained in Examples 1 to 6 and Comparative Examples 1 to 3 was precisely weighed as a sample.
Was added to 100 g of precisely weighed pure water and stirred for 1 hour, then the solid-liquid was separated with a centrifuge (5000 rpm), and the soluble phosphoric acid content of the supernatant was measured. I asked for minutes. The results obtained are shown in Table 1.

[Table 1]

As can be seen in Table 1, the flame retardancy according to the invention compared to conventional ammonium polyphosphate compounds (powder 7, 8) or simple ammonium polyphosphate compositions (powder 9). Ammonium polyphosphate compound (powder 1 ~
It was found that 6) was almost neutral and almost insoluble in water.

3. Production and Testing of Flame Retardant Resin Powders 1-9 obtained in Examples 1-6 and Comparative Examples 1-3
Were adjusted with the formulations shown in Table 2, and extruded at a melt-kneading temperature of 170 ° C. to 220 ° C. using an extruder to obtain pellets.
Predetermined test pieces (hereinafter referred to as "test piece 1" to "test piece 9") were obtained. The flame retardancy test was performed by using a test piece having a wall thickness of 3.0 mm, and was evaluated based on a vertical combustion test defined in UL standard UL94. Burritability is 95 × 95 ×
The 2 mm test pieces were allowed to stand in a thermo-hygrostat controlled at 80 ° C and a humidity of 80%, and they were taken out every day and kept at 80 ° C.
After being dried for 2 hours in a constant temperature dryer of No. 1 and then allowed to stand overnight in a desiccator at room temperature, the bleeding state of the surface of the test piece was visually observed. The results obtained are shown in Table 3.

[Table 2]

[Table 3]

As can be seen in Table 3, the flame retardant ammonium polyphosphate compound according to the present invention was used as compared to the resins using conventional ammonium polyphosphate flame retardants (test pieces 7-9). It was found that the resins (test pieces 1 to 6) have excellent flame retardancy and bleed characteristics.

[0029]

Since the flame-retardant ammonium polyphosphate compound according to the present invention has the above-mentioned constitution and action, it improves the working characteristics such as mixing in the production of the flame-retardant resin, and In addition to enhancing chemical stability, the resin containing the flame-retardant ammonium polyphosphate compound according to the present invention has high bleeding resistance and high flame retardancy, and therefore is suitable for clothing, household electric appliances, and housing materials. It is considered to be useful for disaster prevention measures and contribute to social safety. Also,
The method for producing a flame-retardant ammonium polyphosphate compound according to the present invention is considered to be industrially significant in that it makes it possible for the first time to produce a compound having such excellent properties.

Claims (4)

[Claims] 1. An oxide, hydroxide, carbonate, phosphate or poly of one or more metals selected from the group consisting of alkaline earth metals such as magnesium, calcium and strontium, zinc and aluminum. Phosphate, borate or silicate is added in an amount of 0.01 to 0.1 per mol of phosphorus.
Slightly soluble ammonium polyphosphate compound containing mol 2. Diphosphorus pentoxide, a condensing agent such as urea or melamine, and an ammoniating agent such as ammonium phosphate, ammonium carbonate or ammonium hydrogencarbonate are contained in an amount of 1.2 mol or more of nitrogen per mol of phosphorus. 1) selected from the group consisting of 0.01 to 0.1 mol of phosphorus per mol of phosphorus, 0.01 to 0.1 mol of alkaline earth metal such as magnesium, calcium, strontium, zinc, and aluminum.
Oxides, hydroxides, carbonates, phosphates of more than one metal,
The borate or silicate is mixed and the solid-phase reaction product obtained by solid-phase reaction is used in an ammonia atmosphere for 15
A method for producing a sparingly soluble ammonium polyphosphate compound characterized by baking at 0-350 ° C 3. Diphosphorus pentoxide, a condensing agent such as urine, melamine, etc., and an ammoniating agent such as ammonium phosphate, ammonium carbonate, ammonium hydrogencarbonate, etc., are used in an amount of 1.2 mol or more of nitrogen per mol of phosphorus. The solid-phase reaction product obtained by mixing the solid-phase reaction products at a ratio of 0.01 to 0.1 mol with respect to 1 mol of phosphorus, alkaline earth metal such as magnesium, calcium and strontium, zinc, A mixture of oxides, hydroxides, carbonates, phosphates, borates, or silicates of at least one metal selected from the group consisting of aluminum is added in an amount of 150 to 35 in an ammonia atmosphere.
Method for producing poorly soluble ammonium polyphosphate compound characterized by baking at 0 ° C 4. An oxide, hydroxide, carbonate, phosphate or boric acid of at least one metal selected from the group consisting of alkaline earth metals such as magnesium, calcium and strontium, zinc and aluminum. Salt or silicate,
Resin composition containing 5 to 30% by weight of a poorly soluble ammonium polyphosphate compound in an amount of 0.01 to 0.1 mol per mol of phosphorus