JP2000129263A - Low-smoke-generation flame retardant composition and low-smoke-generation flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant composition which effectively forms char and is excellent in resistances to moisture and heat by combining red phosphorus with a condensed melamine phosphate which is obtained by baking a composition of melamine and phosphoric acid in a specified molar ratio at a specified temperature by solid phase reaction. SOLUTION: At least one composition which is selected from among one consisting of melamine and ammonium primary phosphate and/or melamine phosphate; one consisting of ammonium primary phosphate and melamine phosphate; and one consisting of melamine phosphate and which has a molar ratio of melamine/phosphoric acid of 1.05-1.50 is baked at 300-350 deg.C by solid phase reaction to give a condensed melamine phosphate which has a P content of 13.0-14.7 wt.%, a water solubility of 0.05 g/100 mL water or lower at room temperature, weak X-ray diffraction patterns at 10.95±0.5 Å, 7.94±0.3 Å, 5.49±0.1 Å, 4.21±0.1 Å, 3.98±0.1 Å, and 2.56±0.05 Å, a medium X-ray diffraction pattern at 2.99±0.05 Å, and strong X-ray diffraction patterns at 5.97±0.1 Åand 3.37±0.08 Å, The condensed melamine phosphate is combined with red phosphorus.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention has a high flame retardant effect,
The present invention relates to a low-smoke-resistant flame retardant composition and a low-smoke-resistant flame-retardant resin composition for a synthetic resin having low smoke emission, high char generation effect, and excellent moisture resistance and heat resistance.

[0002]

2. Description of the Related Art Conventionally, many polymer materials have been subjected to flame retarding treatment from the viewpoint of fire prevention. Representative flame retardants include halogen-based flame retardants such as decabromodiphenyl ether and tetrabromobisphenol A, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and triphenyl phosphate, tricresyl phosphate, ammonium polyphosphate, and red There are phosphorus-based flame retardants such as phosphorus and have played a central role as flame retardants for synthetic resins.

However, the above-mentioned halogen-based flame retardants generate a large amount of harmful gases such as hydrogen halide and smoke at the time of combustion, and thus do not meet the requirements of recent ecological flame-retarding technology. Antimony trioxide used in combination with a halogen-based flame retardant is also a deleterious substance, and there is a concern about carcinogenic substances. Therefore, in recent years, the demand for halogen-free and antimony-free flame retardants has increased. In addition, the above-mentioned metal hydroxides have a relatively small flame-retarding action, so that they need to be added in large amounts by themselves, and have the disadvantage of deteriorating the physical properties of the resin.

[0004] On the other hand, synthetic resins requiring flame retardancy are widely used from general-purpose resins to engineering plastics.
Further, it extends to extremely advanced fields such as electronic parts and semiconductor element encapsulants which have high quality requirements. Along with this, the quality requirements for flame retardants for synthetic resins are not limited to simple halogenation, but also have low smoke emission, low harmful gas generation, good moisture and heat resistance, and affinity with resin. Although various proposals have been made according to application fields, they have not been solved yet.

[0005] Under such circumstances, it is known that a resin composition containing phosphorus and nitrogen generates a relatively large amount of char during combustion, and is attracting attention from an ecological point of view. Char stands for "char" in English and refers to a graphite-like carbonized residue generated by the burning of resin. It is nonflammable in itself, and is flame-retardant by coating and fixing the burning components and insulating it. It contributes to the conversion. Phosphorus-nitrogen flame retardants are thought to promote char formation, and are expected to be effective in reducing smoke emission and harmful gas generation.
The above requirements have not yet been sufficiently evaluated. A typical phosphorus-nitrogen flame retardant is ammonium polyphosphate, but its use is limited due to poor moisture resistance.

In addition, melamine phosphate, melamine pyrophosphate, melamine-modified ammonium polyphosphate and the like have been proposed. For example, Japanese Patent Publication No. 40-28594 discloses that melamine orthophosphate having a phosphoric acid content of 27 to 54% is temperature-controlled.
A method of heating and sintering at 180 to 250 ° C. to partially convert to melamine pyrophosphate has been disclosed.
No. 6091 discloses a method of obtaining a condensed phosphoric acid melamine by subjecting a condensed phosphoric acid and melamine to a solid phase reaction in a substantially absence of an aqueous medium under a temperature condition of a spontaneous generation temperature to 170 ° C. Further, JP-A-49-61099 discloses a method of obtaining a modified ammonium polyphosphate by firing ammonium phosphate and urea or crystalline urea phosphate in the presence of melamine or melamine phosphate.

These are developed for the purpose of reducing the solubility, but have a solubility in water of 0.1 (g / 100 g of water) or more. If the flame resistance of the flame retardant is poor, a decrease in the affinity with the matrix resin, the occurrence of bleeding, and a decrease in the physical properties such as electrical insulation occur, and the above-mentioned solubility level cannot satisfy the current requirement for the moisture resistance.

Further, the above-mentioned conventional phosphorus-nitrogen flame retardants have not shown any interest in heat resistance. These are all fired at a relatively low temperature of 270 ° C. or lower, and the differential thermal analysis curve is described in JP-A-61-260991. It shows an endothermic peak around ° C. If the flame retardant is thermally decomposed below the processing temperature of the resin, the effective flame retardant amount will be reduced and the flame retardant effect will be reduced, and the gas generated by the thermal decomposition will result in poor flame retardant compound production and poor product molding. And develop into troubles. Therefore, when synthetic resin processing temperature is high, heat resistance is also required for flame retardants,
Although a flame retardant exhibiting heat resistance even at about 0 ° C. is desired, a conventional phosphorus-nitrogen flame retardant has not been satisfactory in this regard.

Further, JP-A-7-330995 and JP-A-8-30995
No. 217935 discloses a styrene-based flame-retardant resin composition using melamine pyrophosphate and condensed melamine phosphate and red phosphorus as a flame retardant, and the purpose thereof is non-halogenation and improvement of water resistance. But no interest in smoke emission. The condensed melamine phosphate has a composition and characteristic values that fluctuate significantly depending on the production conditions.Here, only known techniques for the condensed melamine phosphate to be used are described, and specific production methods and physical property values are described. It cannot be specified what kind of substance melamine phosphate refers to.

[0010] As described above, the phosphorus-nitrogen flame retardants found in the prior art not only have drawbacks such as low moisture resistance and insufficient flame retardancy by themselves, but also have increased in recent years. Almost no evaluation has been made on the low smoke emission effect and heat resistance. That is, a flame retardant which satisfies all of the flame retardant effect, the smoke-lowering effect, the moisture resistance and the heat resistance has not yet been developed.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to provide a high flame-retardant effect, a low smoke emission, a high char generation effect, and An object of the present invention is to provide a non-halogen flame retardant excellent in moisture resistance and heat resistance and a resin composition using the same.

[0012]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted research with a focus on phosphorus-nitrogen-based flame retardants, and found that condensed melamine phosphate obtained under specific conditions can be used. It has been found that a composition comprising red phosphorus has a high flame-retardant effect, a low fuming property, a high char-forming effect, and a non-halogen flame retardant excellent in moisture resistance and heat resistance.
The present invention has been completed. In other words, condensed melamine phosphate and red phosphorus obtained under specific conditions do not achieve satisfactory levels of low smoke emission and char generation during combustion even when used alone. As a result, a synergistic effect is developed, and the object of the present invention has been solved.

[0013] The low smoke generating flame retardant composition according to the present invention comprises:
Any of the following (A) to (C) containing a melamine condensed phosphate and red phosphorus as a flame retardant component, and wherein the condensed melamine phosphate is adjusted to have a melamine / phosphoric acid molar ratio of 1.05 to 1.50. Raw material composition consisting of one kind
It is obtained by calcining at 300 to 350 ° C., has an X-ray diffraction pattern shown below, has a phosphorus content of 13.0 to 14.7% by weight, and has a solubility in water of 0.05 g in 100 ml of water at room temperature.
A low smoke emission flame retardant composition comprising the following condensed melamine phosphate. (A) melamine and ammonium monophosphate and / or melamine phosphate, (B) ammonium monophosphate and melamine phosphate, (C) melamine phosphate [X-ray diffraction pattern] d (］) Intensity 10.95 ± 0.5 W 7.94 ± 0.3 W 5.97 ± 0.1 S to VS 5.49 ± 0.1 W 4.88 ± 0.1 S 4.21 ± 0.1 W 3.98 ± 0.1 W 3.37 ± 0.08 S to VS 2.99 ± 0.05 M 2.56 ± 0.05 W (The sign in the above “strength” "W, M, S, VS" represent "weak, medium, strong, very strong" respectively.) "(Claim 1) as the gist (items specifying the invention); And red phosphorus in a weight ratio of 1: 1
It is characterized by being blended at a ratio of up to 5: 1 (claim 2).

The low-smoke, flame-retardant resin composition according to the present invention is characterized in that "a low-smoke flame-retardant resin composition is obtained by blending 10 to 400 parts by weight of condensed melamine phosphate and red phosphorus with 100 parts by weight of synthetic resin. A smoke-containing flame-retardant resin composition, wherein the condensed melamine phosphate has a melamine / phosphoric acid molar ratio of 1.05 to 1.50.
A raw material composition comprising any one of the following (A) to (C) adjusted at a temperature of 300 to 350 ° C. by a solid-phase reaction and having an X-ray diffraction pattern shown below, Content
A low-smoke-resistant flame-retardant resin composition comprising 13.0 to 14.7% by weight and having a solubility in water of not more than 0.05 g of condensed melamine phosphate in 100 ml of water at room temperature. (A) melamine and ammonium monophosphate and / or melamine phosphate; (B) ammonium monophosphate and melamine phosphate; (C) melamine phosphate. [X-ray diffraction pattern] d (Å) Intensity 10.95 ± 0.5 W 7.94 ± 0.3 W 5.97 ± 0.1 S to VS 5.49 ± 0.1 W 4.88 ± 0.1 S 4.21 ± 0.1 W 3.98 ± 0.1 W 3.37 ± 0.08 S to VS 2.99 ± 0.05 M 2.56 ± 0.05 W (The symbols “W, M, S, VS” in the above “strength” represent “weak, medium, strong, and very strong,” respectively). Matters that specify the invention).

Further, a low self-extinguishing, low-smoke, flame-retardant composition according to the present invention comprises: A condensed melamine phosphate is a raw material composition comprising any one of the following (A) to (C) in which the molar ratio of melamine / phosphoric acid is adjusted to 1.05 to 1.50 by a solid-phase reaction at 300 to 350 ° C. Having the following X-ray diffraction pattern, a phosphorus content of 13.0 to 14.7% by weight, and a solubility in water of not more than 0.05 g of condensed melamine phosphate in 100 ml of water at room temperature. (A) melamine and ammonium monophosphate and / or melamine phosphate, (B) ammonium monophosphate and melamine phosphate, (C) Melamine phosphate [X Diffraction pattern] d (Å) Intensity 10.95 ± 0.5 W 7.94 ± 0.3 W 5.97 ± 0.1 S to VS 5.49 ± 0.1 W 4.88 ± 0.1 S 4.21 ± 0.1 W 3.98 ± 0.1 W 3.37 ± 0.08 S to VS 2.99 ± 0.05 M 2.56 ± 0.05 W (The signs “W, M, S, VS” in the above “strength” represent “weak, medium, strong, and very strong,” respectively). (Claim 4) Matters).

[0016]

Embodiments of the present invention will be described below. The present invention is characterized in that a composition comprising a condensed melamine phosphate obtained under specific conditions and red phosphorus is used as a flame retardant component.

The fused melamine phosphate in the present invention is disclosed in Japanese Patent Application No. 9-30118 filed by the same applicant as the present invention.
No. 5 is a fused melamine phosphate, wherein the melamine / phosphate molar ratio is adjusted to 1.05 to 1.50, (A) melamine and ammonium phosphate monobasic and / or melamine phosphate, (B) melamine phosphate A raw material composition of ammonium phosphate and melamine phosphate, or (C) melamine phosphate,
It is obtained by firing at 300 to 350 ° C. by a solid phase reaction (hereinafter, referred to as “the present condensed melamine phosphate”).

The melamine phosphate used as a starting material for obtaining the condensed melamine phosphate is a general term for salts obtained by reacting orthophosphoric acid with melamine. Can also be used. In particular, “C ₃ H ₆ N ₆・ H ₃ PO ₄ ”, “6
(C ₃ H ₆ N ₆ ) / 5 (H ₃ PO ₄ ) / 4 (H ₂ O) ”or“ 4 (C ₃ H
_{6 N 6) · 3 (H} 3 PO 4) · 3 (H 2 O) "is preferable since it is easily obtained by adding phosphoric acid to melamine dispersing water.

When the phosphorus content of the condensed melamine phosphate obtained by calcining the raw material composition of (A), (B) or (C) is in the range of 13.0 to 14.7% by weight, the solubility in water is low, For example, in 100 ml of room temperature water 0.0
It becomes 5g or less, and it rises rapidly outside the range. This phosphorus content can be achieved by adjusting the melamine / phosphoric acid molar ratio of the starting material and the calcination temperature. That is, the melamine / phosphoric acid molar ratio is set to 1.05 to 1.50, and the firing temperature is set to 300 to 350 ° C.
It is an essential requirement of the present invention to adjust to. The condensation reaction is completed in a firing time of about one hour. If the calcination time is too long, the amount of free phosphate groups increases due to volatilization of melamine, so that the solubility of the product increases and the moisture resistance decreases, which is not preferable. As the reaction vessel, it is convenient to use a closed external heat type reaction apparatus which can be stirred and mixed and has a gas outlet, and a kneader, a ribbon mixer and the like can be used.

The condensed melamine phosphate of the present invention has higher heat resistance than the above-mentioned conventional melamine phosphate because of the high calcination temperature. When the decomposition temperature was measured by differential thermal analysis, the condensed melamine phosphate was about 370 ° C., whereas the conventional melamine pyrophosphate showed a remarkable difference of about 290 ° C. Further, the fused melamine phosphate of the present invention shows a specific X-ray diffraction pattern I shown below, which is clearly different from the X-ray diffraction pattern of melamine pyrophosphate, and has a highly condensed structure due to a high firing temperature. it is conceivable that.

[X-ray diffraction pattern I] d (Å) Intensity 10.95 ± 0.5 W 7.94 ± 0.3 W 5.97 ± 0.1 S ~ VS 5.49 ± 0.1 W 4.88 ± 0.1 S 4.21 ± 0.1 W 3.98 ± 0.1 W 3.37 ± 0.08 S ~ VS 2.99 ± 0.05 M 2.56 ± 0.05 W (The symbols “W, M, S, VS” in the above “strength” represent “weak, medium, strong, and very strong,” respectively.)

The term "red phosphorus" in the present invention is not particularly limited, and includes not only those obtained by the following production method but also those subjected to a surface treatment thereafter. ing. The solubility of red phosphorus in water is about 3
The substance is ranked as insoluble in terms of ppm, and has a high sublimation temperature of 416 ° C., so it has high thermal stability and can be said to be a substance excellent in moisture resistance and heat resistance as a flame retardant. However, red phosphorus
It is very slow, but it reacts slowly with water under high temperature and high humidity to produce a small amount of hygroscopic phosphorus oxo acid. Is desirable.

Red phosphorus is produced by pulverizing a lump obtained by heat-treating yellow phosphorus for several days in a reaction vessel usually referred to as an inversion kettle. It is preferable in terms of properties and ease of handling. In addition, yellow phosphorus is heated to 250 to 600 ° C. to convert a part of yellow phosphorus to red phosphorus, and to obtain unconverted yellow phosphorus from a fluid mixture having a content of red phosphorus of 70% by weight or less. Red phosphorus is composed of spherical red phosphorus and / or an aggregate thereof without a crushed surface, and has lower adsorption and reaction of water than the above-mentioned ground red phosphorus (Japanese Patent No. 189967).
No. 3 and Japanese Patent No. 1907576), and in the field where moisture resistance is required, it is preferable to use such red phosphorus. Further, when stability and moisture resistance are required, it is preferable to use stabilized red phosphorus subjected to a surface treatment.

Red phosphorus composed of fine powdery sphere-like particles is obtained by performing a conversion reaction of yellow phosphorus in the presence of a dispersant, and has a very fine and uniform particle size distribution. It is a fine powdery sphere-like red phosphorus composed of sphere-like single particles or a low-order conjugate thereof. This sphere-like red phosphorus is composed of fine particles having an average particle size of 10 μm or less, and has high moisture resistance and high heat stability despite its fineness (see Japanese Patent No. 2601743 and Japanese Patent Application Laid-Open No. 7-53779). In particular, in the fields of molded articles, films, coating materials, and the like in which complicated shaped structures and good appearance are required, a fine flame retardant is required. Therefore, it is preferable to use such red phosphorus or a surface-treated product thereof. .

As the surface treatment means for red phosphorus, any conventional coating method using various inorganic compounds or synthetic resins can be applied. As the coating inorganic compound, aluminum hydroxide, magnesium hydroxide, zinc hydroxide,
Metal hydroxides such as titanium hydrate and the like, and as the coating synthetic resin, phenol resin, furan resin, xylene resin, ketone resin, urea resin, melamine resin, aniline resin, alkyd resin, unsaturated polyester resin, Epoxy resins, urethane resins and the like can be mentioned.

It is essential that the flame retardant composition of the present invention contains the two components of the present condensed melamine phosphate and red phosphorus, but the blending ratio in the flame retardant depends on the characteristics of the applied resin. It can be changed as appropriate. From the measurement results of the flame retardancy, the amount of combustion residue, and the amount of smoke, the optimum blending ratio (weight ratio) of the present condensed melamine phosphate and red phosphorus is preferably from 1: 1 to 5: 1, and especially around 2: 1. Particularly preferred.

In the present invention, a third component may be further added. Particularly, zirconium dioxide or molybdenum trioxide is preferably added from the viewpoint of flame retardancy. Since such a three-component-containing resin composition has a short burning time and an increased combustion residue, zirconium dioxide and molybdenum trioxide work together with the condensed melamine phosphate and red phosphorus to provide self-extinguishing properties. It is supposed to increase. Also,
Since red phosphorus originally has an impact ignition property, a powder may be mixed with a metal hydroxide such as aluminum hydroxide or magnesium hydroxide as a flame retardant for the purpose of improving the impact ignition property.

In addition to the two components of the present melamine phosphate and red phosphorus, fillers and other additives which are usually added to flame retardants for resins may be blended. In the flame retardant composition of the present invention, the method of mixing the present condensed melamine phosphate and red phosphorus is not particularly limited, and may be performed by any method. For example, there are a method of simply mixing the condensed melamine phosphate powder and red phosphorus powder and a method of tablet molding.

When the present condensed melamine phosphate alone is used as the flame retardant component, the smoke generating property during combustion is improved, but the flame retardant effect and char formation effect are low, while the red phosphorus flame retardant alone has a relatively high flame retardant effect. However, it is unsatisfactory in terms of smoke generation during combustion and char generation effect. However, by using the condensed melamine phosphate and red phosphorus together, not only the flame retardant effect is improved, but also the smoke-reducing effect and the char generation effect are dramatically improved. For example, the two-component resin composition of the present condensed melamine phosphate and red phosphorus has a fuming property equal to or less than that of the base resin, and the combustion residue is considerably larger than that of the base resin, In some cases, it is about 50% of the weight before combustion, and the char generation effect is high.

Comparison of ammonium polyphosphate, which is well-known as a phosphorus-nitrogen flame retardant, with the present melamine phosphate in combination with red phosphorus, surprisingly shows that the present melamine phosphate having a low phosphorus content per unit weight can be obtained. The higher the flame retardant effect, the lower the smoke emission and the char generation effect. Despite the fact that the phosphorus content of the condensed melamine phosphate is in a range equal to or lower than the calculated value of melamine pyrophosphate, the poor solubility and high heat stability are due to the fact that the condensed melamine phosphate is a highly condensed chain. It is presumed that the highly condensed polyphosphoric acid structure and the network structure developed from melamine act on red phosphorus and combustion products of the resin to promote char formation.

The effect of reducing the smoke emission of the flame retardant component and the effect of producing char were determined by measuring the combustion behavior of various resin compositions containing the flame retardant with a corn calorimeter and comparing the amount of smoke emitted and the amount of residual combustion. Strictly speaking, the combustion residue includes a portion that has not reached combustion or a portion where combustion has not completed, that is, an incompletely combusted substance, but is generally used as a material for determining the char generation effect. Although the amount of char generation cannot be directly derived from the amount of combustion residue, the fact that the amount of combustion residue is large means that even if the amount of char generation is large or the amount of char generation is small, the flame retardant action of the char (char quality) ) Indicates that fire extinguishing occurs before all of the material burns.

The flame retardant composition of the present invention comprises polyethylene,
Polyolefin resin such as polypropylene, PET, P
Polyester resin such as BT, nylon 6, nylon 66
It can be applied to flame retardancy of various synthetic resins such as polyamide resins such as PS, AS, AS, ABS, etc., polystyrene resins such as PPE, polyvinyl chloride resin. In particular, cellulose acetate, urethane rubber, phenolic resin, PET,
Low smoke emission can be achieved in flame retardancy of polyamide, styrene butadiene rubber, polycarbonate, epoxy resin, ABS resin, polypropylene, polystyrene and the like.

The conventional melamine phosphate compound has a low decomposition temperature and its application is limited by the processing temperature during molding. However, each component of the flame retardant composition of the present invention is 370 ° C.
It is stable up to the vicinity and can be used in a wide range up to higher processing temperatures. For example, nylon 66, polycarbonate, heat-resistant ABS resin, PET, modified PPE, and the like are molded in a relatively high temperature range of 250 to 350 ° C. Flammability and low smoke emission can be imparted.

The amount of the flame retardant composition of the present invention to be added to the synthetic resin depends on the type of the resin. However, usually 10 to 40 parts by weight per 100 parts by weight of the synthetic resin provides sufficient flame retardancy and low smoke generation. Property is obtained. If it is 10 parts by weight or less, for example, 5 parts by weight, a sufficient combustion effect cannot be obtained, and if it exceeds 40 parts by weight, the physical properties of the resin product are adversely affected. Further, a masterbatch with an increased concentration of a flame retardant can be produced. As a method for producing a master batch, there are a method of mixing the present condensed melamine phosphate, red phosphorus and a synthetic resin in powder, and a method of kneading and molding into a pellet. Pellets are easier to handle, and have additional advantages such as less dust and more uniform kneading with the resin. In this case, the compounding amount of the flame retardant component with respect to 100 parts by weight of the synthetic resin is preferably within 400 parts by weight, and if it exceeds 400 parts by weight, the viscosity at the time of kneading increases and the workability deteriorates, and the flame retardant component is not uniformly dispersed. It is not preferable. As the synthetic resin used for the masterbatch, there are various types as described above, and it is preferable to select the type according to the type of the resin to be made flame-retardant.

Since the flame retardant composition of the present invention does not contain halogen, no harmful gas derived from halogen is generated during processing or burning. Furthermore, in the case of a flame retardant for synthetic resins, high moisture resistance and high heat resistance are also important prerequisites. However, in the present invention, the condensed melamine phosphate and red phosphorus obtained under the above specific conditions are used as flame retardant components. The flame retardant composition of the present invention exhibits a satisfactory effect in this respect as well. When the melamine / phosphoric acid molar ratio and the sintering temperature during the production of the condensed melamine phosphate do not satisfy the above-mentioned specific conditions, those having insufficient moisture resistance and heat resistance can be obtained. It can be used for applications with low requirements. Melamine pyrophosphate is one example.

[0036]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the present invention. (About the flame retardant component) Condensed Melamine Phosphate Condensed melamine phosphates A to D produced as follows were used.

(Production Example A of Melamine Condensed Phosphate) 115 g of ammonium monophosphate (manufactured by Wako Pure Chemical Industries) and 139 g of melamine (manufactured by Wako Pure Chemical Industries) are kneaded with [FM- NW-1 type (capacity: 1 liter) "] and heated while introducing nitrogen at a rate of 0.03 liter / min. 300
It took 2 hours to raise the temperature to <RTIgt; C </ RTI> and kept at 300-330 <0> C for 1 hour. Thereafter, the heating was stopped, and the mixture was allowed to cool for 5 hours while continuing the rotation of the kneader and the supply of nitrogen. During this time, the off-gas from the kneader was brought into contact with water to collect ammonia.
After allowing to cool, the upper lid of the kneader was removed, and the product was taken out by turning the container upside down to obtain 193 g of the product. The calcined product was pulverized with a pulverizer [“Bantham Mill AP-B” manufactured by Hosokawa Micron Corporation) to obtain condensed melamine phosphate A.

(Production Examples B to D of Melamine Condensed Phosphate) The reaction conditions were changed to the conditions shown in Table 1, respectively.
D was obtained. However, the melamine phosphates A and B as raw materials were produced by the inventor in a laboratory, and were determined to be “6 (C ₃ H ₆ N ₆ ) · 5 (H ₃ PO ₄ ) · 4 by X-ray diffraction, respectively. (H ₂ O) "," C ₃ H
₆ N ₆ · H ₃ PO ₄ '. Condensed melamine phosphate AD
Table 1 shows the starting materials, the melamine / phosphoric acid molar ratio of the starting materials, the calcination conditions, the product yield, the phosphorus content of the obtained condensed melamine phosphate, the solubility in water, and the decomposition temperature.

[0039]

[Table 1]

Each of the condensed melamine phosphates A to C was obtained by calcining the raw material at 300 to 330 ° C., and showed a unique X-ray diffraction pattern I. The molar ratios of melamine / phosphoric acid as starting materials are 1.10, 1.20, 1.60, respectively. In the flame retardant composition of the present invention, this molar ratio is limited to 1.05 to 1.50, and the condensed melamine phosphates A and B are condensed melamine phosphates that can be used in the flame retardant composition of the present invention. Melamine acid C is not included in the scope of the present invention. The molar ratio of the starting materials affects the phosphorus content and the solubility in water of the condensed melamine phosphate, and the solubility in water of the condensed melamine phosphates A and B whose molar ratio is within a limited range is 0.02 and 0.006 g / 100 ml. Condensed melamine phosphate C having a small molar ratio but outside the limited range was as high as 0.10 g / 100 ml.
Condensed melamine phosphates A and B having low water solubility are less likely to cause a decrease in affinity with a matrix resin due to moisture absorption, bleeding, and a decrease in physical properties such as electrical insulation, as compared to the condensed melamine phosphate C. It is useful as a flame retardant for synthetic resins that have high requirements for these properties. The condensed melamine phosphate D was prepared by setting the melamine / phosphoric acid molar ratio of the starting material to 1.03 and the calcination temperature to 240 to 270 ° C. Out of range.

The calcination temperature affects the heat resistance of the condensed melamine phosphate, and the decomposition temperature of condensed melamine phosphates A to C whose calcination temperature is within a limited range is as high as about 370 ° C. Melamine phosphate D was as low as 292 ° C.
Condensed melamine phosphates A to C having high heat resistance have a decomposition temperature increased by about 80 ° C. as compared with condensed melamine phosphate D, and can be used for synthetic resins having a high processing temperature.

The method for measuring the phosphorus content, solubility in water, and decomposition temperature of the product is as follows. (A) Phosphorus content measurement method Condensed melamine phosphate was precisely weighed, decomposed with a mixed solution of concentrated nitric acid and perchloric acid, and then measured by a spectrophotometric method of phosphorus vanadomolybdic acid. ", Maruzen,
(1958), p. 371-372). (B) Method for measuring solubility in water 1. Og of condensed melamine phosphate is dispersed in 100 ml of pure water,
After stirring at room temperature (25 ° C.) for 1 hour, the mixture was filtered through a membrane filter having a pore size of 0.45 μm. The filtrate was received in a weighing bottle at least 50 ml, evaporated in a thermostat at 105 ° C., and the solid residue was precisely weighed to 100 ml. It was converted to per hit. (C) Decomposition temperature measuring method Simultaneous differential thermogravimetric analyzer TG / DT for condensed melamine phosphate
It was measured using A200 (manufactured by Seiko Instruments Inc.), and the first endothermic peak was taken as the decomposition temperature. (Nitrogen flow rate 200ml / mi
n, heating rate 5 ° C / min, sample amount 10mg)

2. Akarin Rinka Chemical Industry Co., Ltd. product name "NOVA Excel 140" was used.

3. Other additives and synthetic resins-Decabromodiphenyl ether (trade name "Frame Cut 110R" manufactured by Tosoh Corporation)-Antimony trioxide (trade name "Frame Cut 610R" manufactured by Tosoh Corporation)-Zirconium dioxide (Wako Pure Chemical Industries, Ltd.) Molybdenum trioxide (reagent manufactured by Wako Pure Chemical Industries, Ltd.) Melamine (reagent manufactured by Wako Pure Chemical Industries, Ltd.) Ammonium polyphosphate (trade name manufactured by Rin Kagaku Kogyo Co., Ltd.) NOVA WHITE PA-2, phosphorus content 31-32% by weight)-High impact polystyrene (trade name "Stylon H8117" manufactured by Asahi Kasei Kogyo Co., Ltd .; hereinafter referred to as HIPS)-Polyphenylene ether (trade name manufactured by Asahi Kasei Kogyo Co., Ltd.)・ Nylon 66 (trade name "Amilan CM30" manufactured by Toray Industries, Inc.)
01-N ")

[Examples 1 to 10 and Comparative Examples 1 to 10] Flame retardant components were mixed at the compounding ratios shown in Tables 2 to 6 to prepare flame retardant compositions. This flame retardant composition was mixed with the resin at the compounding ratios shown in Tables 2 to 6, and the number of revolutions was 55 rp using a Labo Plastomill (manufactured by Toyo Seiki Seisakusho) at the melting temperature shown in Tables 2 to 6.
The mixture was melted at m for 5 minutes to obtain a resin composition.

The evaluation in Examples and Comparative Examples was performed using the following measuring methods or measuring instruments. Test pieces were prepared from the resin compositions obtained in Examples and Comparative Examples for various tests by a hot press, and the flame retardancy, the amount of residual combustion, the burning time, the amount of smoke, and the moisture resistance of the resin composition were evaluated. . -Measurement of flame retardancy Evaluated by the UL-94 test. (1/8 "test piece) ・ Measurement of combustion residue, burning time, and smoke generation Measurement was performed using CONE2 manufactured by Atlas, USA, according to ISO 5660. The test piece (100mmxlOOmmxlOmm) was placed horizontally, The heat flux of the cone type heater was fixed at 40 kW / m ² , the displacement was fixed at 24 l / s, and the ignition was performed using an electric spark.From the measurement results, the combustion residue (g) per 100 g of the sample, The burning time (sec) and the amount of smoke (m ² / kg) per 100 g of the sample were determined, and the burning time per 100 g of the sample was calculated from the burning time from ignition to the end of flaming combustion. Indicates the amount of smoke (m ² / kg) generated from 1 kg of material, and is a measured value.
It is represented as a tinction area.・ Measurement of moisture resistance Test piece (100mmxlOOmmx2mm) at temperature 65 ℃, relative humidity 95%
After a 28-day treatment in a thermo-hygrostat adjusted to, the change in the appearance of the test piece surface was visually observed.
Those with precipitates or blisters were evaluated as x. The results are shown in Tables 2 to 6.

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

[Table 6]

From the measurement results shown in Table 2, the following became clear. In Examples 1 to 3, the present condensed melamine phosphate and red phosphorus were blended. Compared with Comparative Example 1 in which only a synthetic resin containing no flame retardant was used, flame retardancy was improved and the amount of smoke was low. The amount of combustion residue was also large.

Further, when Examples 1 to 3 are compared with Comparative Example 2 in which a flame retardant is used with a halogen-based flame retardant, the flame retardancy is the same. It is less than 1/2, and the combustion residue is large. This shows that the flame retardant composition comprising the present condensed melamine phosphate and red phosphorus is remarkably superior to the halogen-based flame retardant in terms of low smoke emission and char generation effect. . This is because the halogen-based flame retardant acts in the gas phase, resulting in an increase in the amount of smoke generated. On the other hand, the flame retardant composition of the present invention promotes the formation of char, and the char forms It is assumed that the amount of smoke emitted was suppressed as a result of the suppression of the emission of the combustion material into the phase. Since the flame retardant composition of the present invention does not contain a halogen compound, it goes without saying that no harmful gas derived from the halogen-based flame retardant is generated.

Further, when Example 1 is compared with Comparative Example 3 in which condensed melamine phosphate C outside the range defined in the present invention is blended, the resin composition has the same flame retardancy and the same amount of residual combustion. There was a difference in the moisture resistance of the resin composition. That is, in Example 1 using condensed melamine phosphate A, there was no abnormality in the moisture resistance test, but Comparative Example 3 using condensed melamine phosphate C was used.
Produced blisters and poor moisture resistance. This is due to the difference in water solubility of the condensed melamine phosphate, and it is believed that the difference in water solubility was caused by the difference in the melamine / phosphoric acid molar ratio during production.

Furthermore, comparing Example 1 with Comparative Example 4 in which ammonium polyphosphate was blended in place of the present fused melamine phosphate, Example 1 showed that the amount of smoke was reduced to about 60% and the amount of residual combustion was reduced. Increased nearly 1.5 times. The content of phosphorus, which is a flame retardant element, was determined according to the condensed melamine phosphate A of Example 1.
It is a remarkable effect that Example 1 is superior since (phosphorus content 14.7% by weight) is lower than ammonium polyphosphate (phosphorus content 31-32% by weight). The moisture resistance of Example 1 was not abnormal (O),
In Comparative Example 4, blistering occurred (x). This is considered to be due to the difference in moisture resistance between the present fused melamine phosphate and ammonium polyphosphate.

Further, when Examples 1 to 3, which are a two-component combination system of the present condensed melamine phosphate and red phosphorus, are compared with Comparative Example 5, which is a single system of red phosphorus, Examples 1 to 3 show that the residual amount of combustion is low. Many, low smoke. It can be seen that red phosphorus alone is not preferable from the viewpoint of the amount of combustion residue and smoke emission. Similarly,
When Examples 1 to 3 which are a two-component combined system are compared with Comparative Example 6 which is a condensed melamine phosphate alone system, Examples 1 to 3
Is excellent in terms of flame retardancy, while the present condensed melamine phosphate alone system has a low smoke emission amount, but lacks flame retardancy and a small amount of combustion residue. From these facts, it is not possible to simultaneously satisfy the flame retardant effect, the char generation effect and the low smoke emission by using the present condensed melamine phosphate and red phosphorus alone, and a synergistic effect is exhibited only when these two components are used in combination. It is clear that.

Table 3 is an example in which 20 parts by weight of the flame retardant composition of the present invention was blended with 100 parts by weight of the synthetic resin.
The compounding ratio of the condensed melamine phosphate and red phosphorus is flame retardant,
The effect on the combustion residue and the amount of smoke is understood. The compounding ratio of the condensed melamine phosphate in Comparative Example 7 was the smallest, followed by Example 4, Example 5, Example 6, and Comparative Example 8 in increasing order. Decreased. Further, the red phosphorus compounding ratio was low in the above order, and in Comparative Example 7 having the largest red phosphorus compounding ratio, although there was flame retardancy, a large amount of smoke was generated, and the effect of the condensed melamine phosphate was not sufficiently exhibited. In Comparative Example 8 having the smallest red phosphorus compounding ratio, the flame retardancy was V1, and the amount of residual combustion was small. That is, the compounding ratio of condensed melamine phosphate and red phosphorus is 1: 1 to 1
In the range of 5: 1, favorable results were obtained for the flame retardancy, the amount of residual combustion, and the amount of smoke.

Table 4 shows an example in which the addition amount of the flame retardant composition having a blending ratio of the condensed melamine phosphate and red phosphorus of 2: 1 to the synthetic resin was changed. Example 1 has the largest amount of addition, followed by Example 5, Example 7, and Comparative Example 9 in which the addition amount is small, and Comparative Example 9 in which 5 parts by weight of the flame retardant composition is added has difficulty. Flammability was insufficient. That is, the flame retardant composition needs to be added in an amount of 10 parts by weight or more based on 100 parts by weight of the synthetic resin.

Examples 8 and Comparative Example 10 in Table 5 are examples using the flame retardant composition at a relatively high melting temperature of 290 ° C. Since the heat resistance of the flame retardant composition of the present invention is good, it is recognized that high flame retardancy is obtained even in Example 8 where the processing temperature is high. On the other hand, in Comparative Example 10 using the condensed melamine phosphate D having low heat resistance, the flame retardancy was reduced, possibly due to partial decomposition during processing. In Example 8, no abnormality was recognized in the moisture resistance test, but Comparative Example 10
It was recognized that precipitates formed and the moisture resistance was inferior. These differences are thought to be due to differences in water solubility and thermal stability of the fused melamine phosphate.

Examples 9 and 10 in Table 6 are examples of the three-component combination of the present condensed melamine phosphate, red phosphorus and zirconium dioxide or molybdenum trioxide. Also described. In each case, the flame retardant composition was added in total of 40 parts by weight to 100 parts by weight of the synthetic resin.
Examples 9 and 10 are examples in which 10 parts by weight of the condensed melamine phosphate of Example 2 were replaced with zirconium dioxide and molybdenum trioxide, respectively. It can be seen that Examples 9 and 10 which are a three-component combined system have a shorter burning time and superior self-extinguishing properties than Example 2 which is a two-component combined system. This indicates that the addition of zirconium dioxide or molybdenum trioxide enhances the self-extinguishing property of the flame-retardant resin composition.

[0061]

As described in detail above, the present invention provides a high flame retardant effect, a low smoke emission and a char generation effect by using the above-mentioned condensed melamine phosphate and red phosphorus together with a flame retardant composition. It is possible to provide a flame retardant composition for a synthetic resin that is high and has excellent moisture resistance and heat resistance. In addition, since the flame retardant composition of the present invention does not contain halogen, the flame retardant resin composition containing the same generates harmful gas derived from halogen at the time of processing or burning in addition to the above-mentioned characteristics. It has excellent effects such as not being performed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 21/04 C09K 21/04 21/10 21/10 (72) Inventor Sachiko Numa 34 Shinbori, Shinminato City, Toyama Prefecture Address R-Chemical Co., Ltd. F-term (Reference) 4H028 AA07 AA08 AA40 4J002 AB021 AC081 BB031 BB121 BC031 BC061 BD041 BN151 CC031 CD001 CF061 CF071 CG001 CH071 CK021 CL011 CL031 DA057 DE098 DH0186 FD0130 DH0186 FD

Claims (4)

[Claims] Claims 1. A melamine condensed phosphate and red phosphorus are contained as flame retardant components, and the condensed melamine phosphate is adjusted to a melamine / phosphoric acid molar ratio of 1.05 to 1.50 by the following (A) to (C). A) a raw material composition consisting of any one of the above, which is obtained by baking at 300 to 350 ° C. by a solid-phase reaction, has an X-ray diffraction pattern shown below, and has a phosphorus content of 13.0 to 14.7% by weight; A low-smoking flame-retardant composition having a solubility in water of not more than 0.05 g of condensed melamine phosphate in 100 ml of water at room temperature. (A) melamine and ammonium monophosphate and / or melamine phosphate, (B) ammonium monophosphate and melamine phosphate, (C) melamine phosphate [X-ray diffraction pattern] d (］) Intensity 10.95 ± 0.5 W 7.94 ± 0.3 W 5.97 ± 0.1 S to VS 5.49 ± 0.1 W 4.88 ± 0.1 S 4.21 ± 0.1 W 3.98 ± 0.1 W 3.37 ± 0.08 S to VS 2.99 ± 0.05 M 2.56 ± 0.05 W (The sign in the above “strength” "W, M, S, VS" represent "weak, medium, strong, very strong" respectively.) 2. The low-smoking flame-retardant composition according to claim 1, wherein the melamine condensed phosphate and red phosphorus are blended in a weight ratio of 1: 1 to 5: 1. 3. A low smoke-generating flame-retardant resin composition obtained by blending 10 to 400 parts by weight of a melamine condensed phosphate and red phosphorus based on 100 parts by weight of a synthetic resin. Melamine acid has a melamine / phosphoric acid molar ratio of 1.05 to
A raw material composition comprising any one of the following (A) to (C) adjusted to 1.50 is obtained by firing at 300 to 350 ° C. by a solid phase reaction, and has an X-ray diffraction pattern shown below, A low smoke-generating flame-retardant resin composition having a phosphorus content of 13.0 to 14.7% by weight and a solubility in water of not more than 0.05 g of condensed melamine phosphate in 100 ml of water at room temperature. (A) melamine and ammonium monophosphate and / or melamine phosphate; (B) ammonium monophosphate and melamine phosphate; (C) melamine phosphate. [X-ray diffraction pattern] d (Å) Intensity 10.95 ± 0.5 W 7.94 ± 0.3 W 5.97 ± 0.1 S to VS 5.49 ± 0.1 W 4.88 ± 0.1 S 4.21 ± 0.1 W 3.98 ± 0.1 W 3.37 ± 0.08 S to VS 2.99 ± 0.05 M 2.56 ± 0.05 W (The symbols “W, M, S, VS” in the above “strength” represent “weak, medium, strong, and very strong,” respectively.) 4. A fused melamine phosphate as a flame retardant component,
Containing red phosphorus and zirconium dioxide or molybdenum trioxide, and wherein the fused melamine phosphate is melamine /
The following (A) to which the molar ratio of phosphoric acid was adjusted to 1.05 to 1.50
A raw material composition comprising any one of (C) is obtained by baking at 300 to 350 ° C. by a solid-phase reaction, has an X-ray diffraction pattern shown below, and has a phosphorus content of 13.0 to 14.7% by weight. A low self-extinguishing, low-smoke, flame-retardant composition having a solubility in water of 0.05 g or less of condensed melamine phosphate in 100 ml of water at room temperature. (A) melamine and ammonium monophosphate and / or melamine phosphate, (B) ammonium monophosphate and melamine phosphate, (C) melamine phosphate [X-ray diffraction pattern] d (］) Intensity 10.95 ± 0.5 W 7.94 ± 0.3 W 5.97 ± 0.1 S to VS 5.49 ± 0.1 W 4.88 ± 0.1 S 4.21 ± 0.1 W 3.98 ± 0.1 W 3.37 ± 0.08 S to VS 2.99 ± 0.05 M 2.56 ± 0.05 W (The sign in the above “strength” "W, M, S, VS" represent "weak, medium, strong, very strong" respectively.)