JP2020109150A - Flame retardant composition, flame retardant resin composition using the same, molded article, and method for producing molded article - Google Patents

Abstract

To provide a flame retardant composition that has an excellent heat resistance.SOLUTION: The flame retardant composition of the present invention contains a triphosphate salt and at least one of an orthophosphate salt and a pyrophosphate salt from the group consisting of predetermined orthophosphate salts, pyrophosphate salts and triphosphate salts, and in which, when measuring the flame retardant composition by an ion chromatography method and setting the peak area of orthophosphoric acid derived from orthophosphate as O, the peak area of pyrophosphoric acid derived from pyrophosphate as P, and the peak area of triphosphoric acid derived from triphosphate as T, T, O satisfy 4.0×10-2% ≤ T/(T+O) ≤ 95.0%, or T, P satisfy 1.3×10-2% ≤ T/(T+P) ≤ 25.0%.SELECTED DRAWING: None

Description

The present invention relates to a flame retardant composition, a flame retardant resin composition using the same, a molded article, and a manufacturing method for producing a molded article.

Until now, various developments have been made on techniques for modifying the flame retardancy of resin materials. As this type of technology, for example, the technologies described in Patent Documents 1 and 2 are known. Patent Document 1 describes a technique in which a polyphosphate of a triazine compound having an average degree of condensation of more than 20 is added to a resin material as a flame retardant component (claim 1 of Patent Document 1).
On the other hand, Patent Document 2 describes melamine orthophosphate as a flame retardant component of a resin material (claim 16 of Patent Document 2 and the like).

JP, 2011-174095, A JP, 2014-122329, A

However, as a result of examination by the present inventors, in the flame retardant described in Patent Documents 1 and 2, when a low molecular weight phosphate such as orthophosphate or pyrophosphate is included, there is room for improvement in heat resistance. Turned out to be.

In the technical field of phosphate-based flame retardants, among polyphosphates, highly condensed polyphosphate is generally used as a flame retardant component. For this reason, studies on phosphate-based flame retardants using low-molecular-weight phosphates such as orthophosphates and pyrophosphates have not been sufficiently studied so far.

The present inventor has made investigations in view of such circumstances and found that the heat resistance of a phosphate flame retardant containing a low molecular weight phosphate can be controlled by using triphosphate as a flame retardant component. .. Further intensive research based on such findings has revealed that the content of triphosphate in the phosphate-based flame retardant containing orthophosphate or pyrophosphate is set within a predetermined range to obtain a phosphate-based flame retardant. The inventors have found that the heat resistance of can be improved and have completed the present invention.

（上記一般式（１）中、ｎは１〜３の数、Ｘ^１は下記一般式（２）で表されるトリアジン誘導体を表し、ｐは、０＜ｐ≦ｎ＋２の関係式を満たす数である。）

（上記一般式（２）中、Ｚ^１及びＺ^２は、同一でも異なっていてもよく、−ＮＲ^５Ｒ^６基、水酸基、メルカプト基、炭素原子数１〜１０の直鎖または分岐のアルキル基、炭素原子数１〜１０の直鎖または分岐のアルコキシ基、フェニル基及びビニル基からなる群より選ばれる基を表し、Ｒ^５およびＲ^６は各々独立して、水素原子、直鎖または分岐を有する炭素原子数１〜６のアルキル基、または、メチロール基を表す。）

（上記一般式（３）中、ｒは１〜３の数、Ｙ^１はピペラジンまたはピペラジン環を含むジアミンであり、ｑは、関係式０＜ｑ≦ｒ＋２を満たす数である。） According to the invention,
Of the group consisting of orthophosphate, pyrophosphate, and triphosphate represented by the following general formula (1) or the following general formula (3),
With the triphosphate,
At least one of the orthophosphate and the pyrophosphate,
A flame retardant composition comprising:
The flame retardant composition is measured by an ion chromatography method,
The peak area of orthophosphate derived from the orthophosphate is O,
The peak area of pyrophosphate derived from the pyrophosphate is P,
When the peak area of triphosphate derived from the triphosphate is T,
T and O satisfy the following formula (I), or
T and P satisfy the following formula (II),
A flame retardant composition is provided.
4.0×10 ⁻² %≦T/(T+O)≦95.0% Formula (I)
1.3×10 ⁻² %≦T/(T+P)≦25.0% Formula (II)

(In the general formula (1), n is a number of 1 to 3, X ¹ is a triazine derivative represented by the following general formula (2), and p is a number satisfying the relational expression 0<p≦n+2. is there.)

(In the general formula (2), Z ¹ and Z ² may be the same or different, and are a —NR ⁵ R ⁶ group, a hydroxyl group, a mercapto group, a linear or branched alkyl group having 1 to 10 carbon atoms. Represents a group selected from the group consisting of a linear or branched alkoxy group having 1 to 10 carbon atoms, a phenyl group and a vinyl group, and R ⁵ and R ⁶ are each independently a hydrogen atom, a linear or branched group. It represents an alkyl group having 1 to 6 carbon atoms or a methylol group.)

(In the general formula (3), r is a number of 1 to 3, Y ¹ is piperazine or a diamine containing a piperazine ring, and q is a number satisfying the relational expression 0<q≦r+2.)

According to the invention,
With the above flame retardant composition,
A thermoplastic resin,
A flame-retardant resin composition containing is provided.

Further, according to the present invention, there is provided a molded product using the flame-retardant resin composition.

Further, according to the present invention, there is provided a manufacturing method for manufacturing a molded article using the flame-retardant resin composition.

ADVANTAGE OF THE INVENTION According to this invention, the flame retardant composition excellent in heat resistance, the flame retardant resin composition using the same, the molded product, and the manufacturing method for manufacturing the molded product are provided.

The flame retardant composition of this embodiment will be described.
The flame retardant composition is a phosphate flame retardant containing a (poly)phosphate, and is represented by the following general formula (1) or the following general formula (3), orthophosphate, pyrophosphate, And triphosphate, and at least one of orthophosphate and pyrophosphate in the group consisting of and.

In the general formula (1), n is a number from ^{1 to} 3, X ¹ is a triazine derivative represented by the following general formula (2), and p is a number satisfying the relational expression 0<p≦n+2. .. )

In the general formula (2), Z ¹ and Z ² may be the same or different, and are —NR ⁵ R ⁶ group, hydroxyl group, mercapto group, linear or branched alkyl group having 1 to 10 carbon atoms, It represents a group selected from the group consisting of a linear or branched alkoxy group having 1 to 10 carbon atoms, a phenyl group and a vinyl group, and R ⁵ and R ⁶ each independently have a hydrogen atom, a linear or branched group. It represents an alkyl group having 1 to 6 carbon atoms or a methylol group.

In the general formula (3), r is a number from ^{1 to} 3, Y ¹ is piperazine or a diamine containing a piperazine ring, and q is a number satisfying the relational expression 0<q≦r+2.

In the present specification, the (poly)phosphate represented by the general formula (1) is referred to as a triazine (poly)phosphate (a salt of (poly)phosphoric acid and a triazine derivative), and The (poly)phosphate represented by (3) may be referred to as piperazine (poly)phosphate (a salt of (poly)phosphoric acid and piperazine or a diamine containing a piperazine ring).

Among the above triazine (poly)phosphates, in the general formula (1), when n is 1, an orthophosphate, when n is 2 is a pyrophosphate, and when n is 3, it is a triphosphate. .. Of the above piperazine (poly)phosphates, in the general formula (3), when r is 1, orthophosphate, when r is 2, pyrophosphate, and when r is 3, triphosphate. ..

In addition, in the present specification, (poly)phosphoric acid refers to either one of phosphoric acid and polyphosphoric acid, or a mixture of phosphoric acid and polyphosphoric acid. The low molecular weight polyphosphoric acid is a condensate of phosphoric acid, and means either pyrophosphoric acid having a condensation degree of 2, or triphosphoric acid having a condensation degree of 3, or a mixture thereof.
Note that the (poly)phosphate may include two or more having different degrees of polymerization or different kinds of salts.

Examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by Z ¹ and Z ² in the general formula (2) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and tert-butyl. , Isobutyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, decyl, etc. Examples of the linear or branched alkoxy group of 10 include groups derived from these alkyl groups. Moreover, as the linear or branched alkyl group having 1 to 6 carbon atoms represented by R ⁵ and R ⁶ in the —NR ⁵ R ⁶ group which Z ¹ and Z ² can take, the alkyl groups listed above can be used. Among them, those having 1 to 6 carbon atoms can be mentioned.

In the general formula (2), specific examples of the triazine derivative represented by X ¹ include melamine, acetoguanamine, benzoguanamine, acrylguanamine, 2,4-diamino-6-nonyl-1,3,5-. Triazine, 2,4-diamino-6-hydroxy-1,3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1 ,3,5-Triazine, 2,4-diamino-6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6 -Isopropoxy-1,3,5-triazine, 2,4-diamino-6-mercapto-1,3,5-triazine, 2-amino-4,6-dimercapto-1,3,5-triazine and the like. To be

The flame retardant composition preferably contains the pyrophosphate salt (triazine pyrophosphate) represented by the general formula (1). Further, the flame retardant composition preferably contains a pyrophosphate salt (triazine pyrophosphate) in which X ¹ in the general formula (1) is melamine. Thereby, heat resistance can be improved stably.

In the general formula (3), examples of the diamine represented by Y ¹ include R ¹ R ² N(CH ₂ ) _m NR ³ R ⁴ , piperazine, and diamines containing a piperazine ring. R ^{1 to} R ⁴ may be the same or different and each represents a linear or branched alkyl group having 1 to 5 carbon atoms.

Examples of the straight-chain or branched alkyl group having 1 to 5 carbon atoms represented by R ^{1 to} R ⁴ above include those listed as specific examples of the alkyl group represented by Z ¹ and Z ² . Those having 1 to 5 carbon atoms can be mentioned.
Examples of the diamine containing a piperazine ring include compounds obtained by substituting one or more positions of the 2, 3, 5, and 6-positions of piperazine with an alkyl group (preferably having 1 to 5 carbon atoms); Alternatively, a compound in which the amino group at the 4-position is substituted with an alkyl group (preferably having a carbon number of 1 to 5) is exemplified.

Specific examples of the diamine represented by Y ¹ in the general formula (3) include N,N,N′,N′-tetramethyldiaminomethane, ethylenediamine, N,N′-dimethylethylenediamine, N,N. '-Diethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-diethylethylenediamine, tetramethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10- Diaminodecane, piperazine, trans-2,5-dimethylpiperazine, 1,4-bis(2-aminoethyl)piperazine, 1,4-bis(3-aminopropyl)piperazine and the like can be mentioned.

Further, the flame retardant composition preferably contains a pyrophosphate salt (piperazine pyrophosphate) in which Y ¹ in the general formula (3) is piperazine. Thereby, heat resistance can be improved stably.

Here, the manufacturing process of the said (poly)phosphate is demonstrated.
The triazine (poly)phosphate is obtained by reacting (poly)phosphoric acid or (poly)phosphate with the triazine derivative. For example, by reacting (poly)phosphoric acid and melamine in an arbitrary reaction ratio, or by adding sodium (poly)phosphate and melamine and then neutralizing with hydrochloric acid, a triazine (poly)phosphate is obtained. be able to.

The piperazine (poly)phosphate is obtained by reacting (poly)phosphoric acid or (poly)phosphate with the piperazine or diamine containing a piperazine ring. For example, (poly)phosphoric acid or sodium (poly)phosphate is reacted with piperazine or a diamine containing the above piperazine ring in water or an aqueous methanol solution to give piperazine (poly)phosphate as a sparingly water-soluble precipitate. Obtainable.

In the manufacturing process of the (poly)phosphate, the (poly)phosphoric acid or the (poly)phosphate may include at least a part containing triphosphoric acid or the triphosphate.
Further, after the reaction step, heat treatment may be further performed. By carrying out the heat treatment at an appropriate temperature, the condensation reaction of orthophosphoric acid or triphosphoric acid can be promoted. The temperature of the heat treatment is, for example, 150°C to 280°C, preferably 200°C to 250°C. The heating time may be, for example, about 1 h to 30 h. Mild conditions are preferable for the heat treatment such as heating temperature and heating time. If the heating temperature is too high or the heating time is too long, the dehydration condensation reaction may proceed, and the triphosphate may become a tetraphosphate or a polyphosphate condensed further.
Moreover, you may wash and refine|purify after a reaction process. By washing with a small amount of water, the orthophosphate or pyrophosphate having a relatively high solubility can be washed and the ratio of triphosphate can be increased.
Further, water can be sufficiently removed by a drying treatment such as reduced pressure or vacuum. This can suppress hydrolysis of triphosphate.
Further, two or more compounds having different salts or condensation degrees, or two or more compounds having different peak area ratios of (poly)phosphoric acid derived from (poly)phosphate are combined and blended at an appropriate ratio. Alternatively, the above flame retardant composition may be obtained.

As described above, the triazine (poly)phosphate and the piperazine (poly)phosphate are obtained. These may be used alone or in combination of two or more. The flame retardant composition containing such a (poly)phosphate can improve the flame retardancy of the resin material.

According to the knowledge of the present inventor, it has been found that the heat resistance of a flame retardant composition containing a low molecular weight phosphate can be controlled by using triphosphate as a flame retardant component. As a result of further intensive research based on such findings, the content ratio of triphosphate in the flame retardant composition containing an orthophosphate or a pyrophosphate is set to be a predetermined value or more and a predetermined value or less, and thus the flame retardant composition. It was found that the heat resistance of the product can be improved.

By using such a flame retardant composition, it is possible to suppress decomposition and volatilization of a part of the flame retardant composition at the time of heat processing, so that it is possible to reduce contamination of the inside of the processing machine caused by volatile matter. The heat processing refers to a general processing method of heating and mixing when the flame retardant composition is mixed with a resin (thermoplastic resin).
Further, by using the flame retardant composition of the present embodiment, it is possible to suppress molding defects such as foaming due to volatile substances, or to suppress deterioration of the work environment due to decomposed substances and volatile substances. become.

Normally, it is thought that the higher the molecular weight of the (poly)phosphate, the lower the volatility due to heating, but as a result of the study by the present inventors, it was found that the opposite result is shown. That is, although the detailed mechanism is not clear, if the content of triphosphate is excessive, which has a larger molecular weight than orthophosphate or pyrophosphate, the volatilization amount of these mixtures may increase. Do you get it.

Therefore, in the flame retardant composition containing an orthophosphate or a pyrophosphate, not only the lower limit value of the content ratio of triphosphate, but as described above, by appropriately setting the upper limit value, the volatilization amount by heating It has been found that a flame retardant composition that can be reduced and has good heat resistance can be realized.

In the present embodiment, the content of (poly)phosphate such as orthophosphate, pyrophosphate, and triphosphate in the flame retardant composition is measured by using an ion chromatography method, It can be calculated from the peak area ratio of (poly)phosphoric acid.

The ion chromatography method will be described.
First, using the ion chromatography method of the following measurement conditions, in the flame retardant composition, orthophosphate derived from orthophosphate, pyrophosphate derived from pyrophosphate, and the peak area of triphosphate derived from triphosphate taking measurement.
Then, the peak area of orthophosphoric acid is O, the peak area of pyrophosphoric acid is P, the peak area of triphosphoric acid is T, and the peak area ratio of O, P, T (% ) Is calculated.

(Measurement condition)
・Measuring device: Ion Chromatograph ICS-2100 (Thermo Fisher Scientific Co., Ltd.)
・Column: Dionex IonPac AS-19 (Thermo Fisher Scientific Co., Ltd.)
-Detector: electric conductivity detector-Elution condition: 1.0 mmol/L potassium hydroxide aqueous solution (0 minutes) -> 60.0 mmol/L potassium hydroxide aqueous solution (42 minutes). The concentration of the potassium hydroxide aqueous solution (eluent) was changed as follows.
From 0 min to 1 min: Gradient from 1.0 mmol/L to 10.0 mmol/L.
More than 1 minute to 10 minutes: constant at 10.0 mmol/L.
Greater than 10 minutes to 15 minutes: Gradient from 10.0 mmol/L to 60.0 mmol/L.
Greater than 15 minutes to 42 minutes: constant at 60.0 mmol/L.
・Flow rate: 1.0 mL/min
・Sample injection volume: 25 μL
・Column temperature: 35℃

Moreover, orthophosphoric acid, pyrophosphoric acid, and triphosphoric acid, or salts thereof are used as standard substances. The retention time (elution time) at the three peaks of orthophosphoric acid, pyrophosphoric acid, and triphosphoric acid of the standard substance is measured using the same measurement conditions as the ion chromatography method for the flame retardant composition. Based on the measured retention time, three peaks of orthophosphoric acid, pyrophosphoric acid, and triphosphoric acid in the flame retardant composition can be identified.

In the case where the flame retardant composition contains at least a triphosphate and an orthophosphate represented by the general formula (1) or the general formula (3), T and O satisfy the following formula (I). Is.
4.0×10 ⁻² %≦T/(T+O)≦95.0% Formula (I)

In the above formula (I), the lower limit of T/(T+O) is 4.0×10 ⁻² % or more, preferably 2.0×10 ⁻¹ % or more, more preferably 1.0% or more. This can improve the heat resistance of the flame retardant composition. On the other hand, the upper limit of T/(T+O) is 95.0% or less, preferably 94.0% or less, and more preferably 91.0% or less. This can improve the heat resistance of the flame retardant composition.

When the flame retardant composition contains at least a triphosphate and a pyrophosphate represented by the general formula (1) or the general formula (3), T and P satisfy the following formula (II). Is.
1.3×10 ⁻² %≦T/(T+P)≦25.0% Formula (II)

In the above formula (II), the lower limit value of T/(T+P) is 1.3×10 ⁻² % or more, preferably 3.0×10 ⁻² % or more, more preferably 6.0×10 ⁻² %. That is all. This can improve the heat resistance of the flame retardant composition. On the other hand, the upper limit of T/(T+O) is 25.0% or less, preferably 20.0% or less, more preferably 15.0% or less. This can improve the heat resistance of the flame retardant composition.

The flame retardant composition may include an orthophosphate, a pyrophosphate, and a triphosphate represented by the general formula (1) or the general formula (3). In this case, it is preferable that O, P, and T of the flame retardant composition satisfy the following formula (III).
1.0×10 ⁻² %≦T/(O+P+T)≦25.0% Formula (III)

In the above formula (III), the lower limit of T/(O+P+T) is, for example, 1.0×10 ⁻² % or more, preferably 3.0×10 ⁻² % or more, and more preferably 6.0×10 ^{−. It is 2} % or more. This can improve the heat resistance of the flame retardant composition. On the other hand, the upper limit of T/(O+P+T) is, for example, 25.0% or less, preferably 20.0% or less, and more preferably 15.0% or less. This can improve the heat resistance of the flame retardant composition.

Further, in the flame retardant composition, O and T may satisfy the following formula (IV).
4.0×10 ⁻⁴ ≦T/O≦20.0... Formula (IV)

In the above formula (IV), the lower limit of T/O is, for example, 4.0×10 ⁻⁴ or more, preferably 5.0×10 ⁻³ or more, more preferably 1.0×10 ⁻² or more. .. This can improve the heat resistance of the flame retardant composition. On the other hand, the upper limit of T/O is, for example, 20.0 or less, preferably 18.0 or less, and more preferably 15.0 or less. This can improve the heat resistance of the flame retardant composition.

Moreover, O, P, and T of the flame retardant composition may satisfy the following general formula (V).
75.0%≦P/(O+P+T)≦99.0%... General formula (V)

In the general formula (V), the lower limit of P/(O+P+T) is, for example, 75.0% or more, preferably 76.0% or more, more preferably 77.0% or more. On the other hand, the upper limit of P/(O+P+T) is, for example, 99.0% or less, preferably 98.5% or less. Within such a numerical range, the heat resistance of the flame retardant composition can be stably improved.

In the present embodiment, for example, the ratio represented by O, P, and T can be set by appropriately selecting the type and amount of each component contained in the flame retardant composition, the method for preparing the flame retardant composition, and the like. It is possible to control. Among these, for example, the heating temperature, the heating time, the washing method or the drying method is appropriately adjusted, the raw material containing triphosphoric acid or triphosphate is used, and the blending conditions of two or more compounds are appropriately selected. The above is mentioned as an element for making the ratios represented by O, P and T within the desired numerical range.

The flame retardant composition is a pyrophosphate in which X ¹ in the general formula (1) is melamine (melamine pyrophosphate) and a pyrophosphate in which Y ¹ in the general formula (3) is piperazine. (Piperazine pyrophosphate) is preferable. Thereby, it is possible to further improve the flame retardancy. The content ratio of both may be appropriately selected.

Further, the lower limit of the total content of the orthophosphate, the pyrophosphate, and the triphosphate represented by the general formula (1) or the general formula (3) is 100% by weight of the flame retardant composition. On the other hand, it is, for example, 20% by weight or more, preferably 50% by weight or more, more preferably 80% by weight or more. This can enhance the flame retardancy of the resin material. In addition, the heat resistance of the flame retardant composition can be improved. On the other hand, the upper limit of the total content of the orthophosphate, pyrophosphate, and triphosphate is not particularly limited, but may be, for example, 100% by weight or less with respect to 100% by weight of the flame retardant composition, It may be 99% by weight or less, or 95% by weight or less. This makes it possible to achieve a balance with the characteristics according to various uses.

The flame retardant composition may contain other (poly)phosphate in addition to the (poly)phosphate represented by the general formula (1) or the general formula (3). As the other (poly)phosphate, a high-molecular-weight polyphosphate having a high degree of condensation of 4 or more and a known ammonium (poly)phosphate may be used. These may be used alone or in combination of two or more.

In addition, the flame retardant composition may contain additives such as an auxiliary agent, a surface treatment agent, and a dust suppressor, if necessary, as long as the effects of the invention are not impaired.
The flame retardant composition can be obtained by mixing the (poly)phosphate and the additive. As a method for mixing, known methods generally used can be applied as they are.

The content of the additive in the flame retardant composition is, for example, 0.001 to 15 parts by weight, preferably 0.005 to 10 parts by weight, and more preferably 100 parts by weight of the (poly)phosphate. Is preferably 0.01 to 5 parts by weight. The effect of the additive can be improved by setting the value in such a range.

The flame retardant composition may include an auxiliary agent.
Examples of the auxiliary include a flame retardant auxiliary, a drip prevention auxiliary, a processability auxiliary, and the like.

The flame retardant aid may include a metal oxide or a polyhydric alcohol compound. This can improve the flame retardancy of the resin.

Examples of the metal oxide include titanium oxide, zinc oxide, calcium oxide, magnesium oxide, calcium oxide, zirconium oxide, barium oxide, tin dioxide, lead dioxide, antimony oxide, molybdenum oxide and cadmium oxide. Among these, zinc oxide, titanium oxide, magnesium oxide and silicon oxide can be used. These may be used alone or in combination of two or more. This can improve the flame retardancy of the resin. Further, it is possible to suppress the occurrence of agglomeration in the powdery granular flame retardant composition. From the viewpoint of flame retardancy, zinc oxide is preferable.

The zinc oxide may be surface-treated or may not be surface-treated.
Examples of the zinc oxide include zinc oxide type 1 (manufactured by Mitsui Metal Industry Co., Ltd.), partially coated zinc oxide (manufactured by Mitsui Metal Industry Co., Ltd.), Nanofine 50 (ultrafine particles having an average particle size of 0.02 μm). Commercially available products such as zinc oxide: manufactured by Sakai Chemical Industry Co., Ltd., nanofine K (Zinc silicate-coated ultrafine zinc oxide having an average particle size of 0.02 μm: manufactured by Sakai Chemical Industry Co., Ltd.), etc. may be used. ..

The polyhydric alcohol is a compound in which a plurality of hydroxyl groups are bonded, and for example, pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, 1, 3,5-Tris(2-hydroxyethyl)isocyanurate (THEIC), polyethylene glycol, glycerin, diglycerin, mannitol, maltitol, lactitol, sorbitol, erythritol, xylitol, xylose, sucrose (sucrose), trehalose, inositol, Examples include fructose, maltose and lactose. Among these polyhydric alcohol compounds, one or more selected from the group of pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, and the like, pentaerythritol, and a condensate of pentaerythritol are preferable. Condensates are particularly preferred, and dipentaerythritol is most preferred. Moreover, THEIC and sorbitol can also be used conveniently. These may be used alone or in combination of two or more.

Examples of the anti-drip agent include layered silicates, fluorine-based anti-drip agents, and silicone rubbers. As a result, it is possible to suppress drip when the resin burns.

The layered silicate may be natural or synthetic and is not particularly limited.
Examples of the layered silicate include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite and nontronite, and vermiculite, halloysite, swelling mica, talc and the like. These may be used alone or in combination of two or more.
Among these, saponite or talc is preferable from the viewpoint of drip prevention, and talc is particularly preferable from the viewpoint of economical efficiency such as price.

The layered silicate is a layered silicate mineral and may have cations between layers.
The cation may be a metal ion, or part or all of it may be a cation other than a metal ion, such as an organic cation, a (quaternary) ammonium cation, or a phosphonium cation.
Examples of the metal ion include sodium ion, potassium ion, calcium ion, magnesium ion, lithium ion, nickel ion, copper ion, zinc ion and the like.
Examples of the organic cation or quaternary ammonium cation include lauryl trimethyl ammonium cation, stearyl trimethyl ammonium cation, trioctyl methyl ammonium cation, distearyl dimethyl ammonium cation, di-cured tallow dimethyl ammonium cation, and distearyl dibenzyl ammonium cation. Can be mentioned. These may be used alone or in combination of two or more.

Specific examples of the above-mentioned fluorine-based drip prevention auxiliary agent include, for example, fluorine-based resins such as polytetrafluoroethylene, polyvinylidene fluoride, and polyhexafluoropropylene, sodium perfluoromethanesulfonate, potassium perfluoro-n-butanesulfonate. Perfluoroalkanesulfonic acid alkali metal salt compounds such as salts, perfluoro-t-butanesulfonic acid potassium salt, perfluorooctanesulfonic acid sodium salt, perfluoro-2-ethylhexanesulfonic acid calcium salt, or perfluoroalkanesulfonic acid alkali Examples thereof include earth metal salts. Among them, polytetrafluoroethylene may be used from the viewpoint of drip prevention property. These may be used alone or in combination of two or more.

The above-mentioned processing aid can be appropriately selected from known processing aids, but may include an acrylic acid-based processing aid.

Examples of the acrylic acid-based processing aid include homopolymers or copolymers of alkyl methacrylate such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; the alkyl methacrylate and alkyl acrylate such as methyl acrylate, ethyl acrylate and butyl acrylate. A copolymer of the alkyl methacrylate with an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene; a copolymer of the alkyl methacrylate with a vinyl cyan compound such as acrylonitrile or methacrylonitrile. Examples thereof include polymers. These may be used alone or in combination of two or more.

The flame retardant composition may include a surface treatment agent.
Examples of the surface treatment agent include silicone oil and silane coupling agents.
By using the silicone oil, the dispersibility of the flame retardant composition in the resin can be enhanced. In addition, water resistance can be improved.

Any known silicone oil having a polysiloxane skeleton can be used as the silicone oil without particular limitation. The silicone oil may be a polymer having a linear polysiloxane skeleton, all side chains of the polysiloxane may be methyl groups, some side chains may have phenyl groups, and some side chains may have phenyl groups. It may have hydrogen. A part of these silicone oils may be modified by epoxy modification, amino modification, carboxy modification, or the like. These may be used alone or in combination of two or more.

Examples of the method of adding the surface treatment agent include a method of mixing the powdery granular flame-retardant composition and the surface treatment agent, a method of spray-drying the surface treatment agent, and the addition and mixing. Moreover, you may add the said surface treatment agent to a flame retardant composition by surface-treating a part of the component which comprises a flame retardant composition.

Examples of the silane coupling agent include, as silane coupling agents having an alkenyl group, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris(2-methoxyethoxy)silane, vinylmethyldimethoxysilane, and octane. Examples thereof include tenyltrimethoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane, and the like. Examples of the silane coupling agent having an acrylic group include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane. As a silane coupling agent having a methacryl group, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, Methacryloxyoctyltrimethoxysilane and the like can be mentioned, and as a silane coupling agent having an epoxy group, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid Examples include xypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and glycidoxyoctyltrimethoxysilane. As a silane coupling agent having an amino group, N -2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N Examples thereof include hydrochloride of -(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, and examples of the silane coupling agent having an isocyanurate group include tris-(trimethoxysilylpropyl)isocyanurate. Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane. Examples of the silane coupling agent having: 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane and the like, and examples of the silane coupling agent having a sulfide group include bis(triethoxysilylpropyl) tetrasulfide. Examples of the silane coupling agent having a thioester group include 3-octanoylthio-1-propyltriethoxysilane, and examples of the silane coupling agent having an isocyanate group include 3-isocyanatepropyltriethoxysilane and 3-isocyanatepropyltrimethoxysilane. Etc. These may be used alone or in combination of two or more.
Among these silane coupling agents, a silane coupling agent having an epoxy group is preferable from the viewpoint of flame retardancy, handling property, and further prevention of aggregation of the flame retardant powder and improvement of storage stability, 2-(3 4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane , Glycidoxyoctyltrimethoxysilane is more preferred

The flame retardant composition may include a dust suppressor.
Examples of the dust suppressant include an aliphatic dicarboxylic acid ether ester compound, the above-mentioned silane coupling agent, and the like.

The aliphatic dicarboxylic acid ether ester compound may include a compound represented by the following general formula (4). This can suppress the dustiness of the powdery granular flame retardant composition. These may be used alone or in combination of two or more.

In the general formula (4), n represents an integer of 2 to 6, m represents an integer of 1 to 3, and R ¹ represents an alkyl group having 1 to 6 carbon atoms.
In the general formula (4), the alkyl group having 1 to 6 carbon atoms may be a linear alkyl group or a branched alkyl group, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl and sec-butyl. , Tert-butyl, amyl, isoamyl, tert-amyl, hexyl groups and the like. R ¹ is preferably a butyl group from the viewpoint of flame retardancy, particularly handling properties and storage stability.
In the above general formula (4), n is preferably 4 from the viewpoint of flame retardancy, particularly handling property and storage stability. Further, in the general formula (4), m is preferably 2 from the viewpoint of flame retardancy, particularly handling property and storage stability.

The flame retardant composition may contain other components as long as the effects of the present invention are not impaired. As the other component, an additive usually used for modifying a thermoplastic resin can be used, and examples thereof include an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, and other flame retardants/flame retardants. Auxiliary agent, reinforcing material, nucleating agent (clarifying agent), cross-linking agent, antistatic agent, metal soap, filling agent, antifogging agent, antiplateout agent, fluorescent agent, antifungal agent, bactericidal agent, foaming agent , Metal deactivators, release agents, pigments and the like. These may be used alone or in combination of two or more.

It should be noted that one or more of the above-mentioned auxiliary agent, surface treatment agent, dust suppressor and other components may be blended in the above flame retardant composition, but it is difficult to include the flame retardant composition and thermoplastic resin. You may mix|blend with a flammable resin composition.

Next, the flame-retardant resin composition of this embodiment will be described.
The flame-retardant resin composition contains the flame-retardant composition described above and a thermoplastic resin.

The content of the flame retardant composition is usually 10 to 400 parts by weight, preferably 15 to 200 parts by weight, and more preferably 20 to 70 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Can be within. Thereby, the effect of modifying the thermoplastic resin can be sufficiently obtained.

Examples of the thermoplastic resin include synthetic resins such as polyolefin resins, styrene resins, polyester resins, polyether resins, polycarbonate resins, polyamide resins, and halogen-containing resins. These may be used alone or in combination of two or more.

Further examples of the thermoplastic resin, for example, petroleum resin, coumarone resin, polyvinyl acetate, acrylic resin, polymethylmethacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyphenylene sulfide, polyurethane, fibrin resin, polyimide Thermoplastic resins such as resins, polysulfones, liquid crystal polymers, and blends thereof can be used.

The thermoplastic resin is isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, polyester elastomer, nitrile elastomer, nylon elastomer, vinyl chloride elastomer, polyamide elastomer, polyurethane. It may be a thermoplastic elastomer such as a system elastomer, or may be used in combination.

Specific examples of the thermoplastic resin include, but are not limited to, polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, ethylene/ Polyolefin-based polymer such as α-olefin polymer such as propylene block or random copolymer; thermoplastic linear polyester-based polymer such as polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate; polysulfide-based polymer such as polyphenylene sulfide Molecules; polylactic acid polymers such as polycaprolactone; linear polyamide polymers such as polyhexamethylene adipamide; crystalline polystyrene polymers such as syndiotactic polystyrene.

The flame-retardant resin composition is, in addition to the flame-retardant composition, one or two or more selected from the above-mentioned auxiliaries, surface-treating agents, dust suppressors and additives consisting of other components, if necessary. May be included. These may be used alone or in combination of two or more.

The content of the additive in the flame-retardant resin composition is, for example, 0.001 to 15 parts by weight, preferably 0.005 to 10 parts by weight, and more preferably 100 parts by weight of the thermoplastic resin. 0.01 to 5 parts by weight is preferable. The effect of the additive can be improved by setting the value in such a range.

Next, a method for producing the flame-retardant resin composition will be described.
The flame-retardant resin composition can be obtained by mixing the flame-retardant composition with the thermoplastic resin. If necessary, the above additives may be mixed. The additive may be mixed in the flame retardant composition or in the mixture of the flame retardant composition and the thermoplastic resin.

As a method for mixing, known methods generally used can be applied as they are. For example, a kneading machine is used to mix the flame retardant composition, the thermoplastic resin and, if necessary, additives. Examples of the mixer include a tumbler mixer, a Henschel mixer, a ribbon blender, a V-type mixer, a W-type mixer, a super mixer, and a Nauta mixer.

The flame-retardant resin composition can be used in various forms, and may be in the form of pellets, granules or powder, for example. From the viewpoint of handleability, pellet form is preferable.

Next, a molded product can be manufactured by molding using the flame-retardant resin composition.

The molding method is not particularly limited, and includes injection molding method, extrusion molding method, blow molding method, rotational molding, vacuum molding method, inflation molding method, calender molding method, slush molding method, dip molding method, foaming. A molding method and the like can be mentioned. Among these, the injection molding method, the extrusion molding method, and the blow molding method are preferable.
As a result, molded products of various shapes such as resin plates, sheets, films, and odd-shaped products can be manufactured.

Molded articles using the flame-retardant resin composition can be used in various applications, for example, various applications such as electric/electronic parts, mechanical parts, optical devices, building members, automobile parts and daily necessities. Can be used for. Among these, from the viewpoint of flame retardancy, it can be suitably used for electric/electronic parts.

The flame-retardant resin composition and the molded article thereof are, for example, electric/electronic/communication, agriculture, forestry and fisheries, mining, construction, food, textiles, clothing, medical care, coal, petroleum, rubber, leather, automobiles, precision instruments, wood. It can be used in a wide range of industrial fields such as building materials, civil engineering, furniture, printing, musical instruments, etc. Specifically, the flame-retardant synthetic resin composition of the present invention and the molded article thereof are used in printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copying machines, facsimiles, ECR (electronic monetary registration). Machines), calculators, electronic organizers, cards, holders, stationery and other office work, OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, kotatsu and other home electric appliances, TVs, VTRs, videos AV equipment such as cameras, radio cassette recorders, tape recorders, mini discs, CD players, speakers, liquid crystal displays, connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulation materials, LED encapsulation materials, electric wires, cables, transformers. It can be used for electric/electronic parts such as a deflection yoke, a distribution board, a timepiece, and a communication device.

The flame-retardant resin composition and the molded article thereof include, for example, seats (filling, outer material, etc.), belts, ceiling coverings, compatible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, wheel covers, mattresses. Covers, airbags, insulation materials, hoists, hoist belts, wire covering materials, electric insulation materials, paints, coating materials, upholstery materials, floor materials, corner walls, carpets, wallpaper, wall covering materials, exterior materials, interior materials Materials, roofing materials, deck materials, wall materials, pillar materials, floor boards, fence materials, frames and moldings, window and door profiles, shingles, siding, terraces, balconies, soundproof boards, heat insulation boards, window materials, etc. , Automobiles, vehicles, ships, aircraft, buildings, housing materials, construction materials and civil engineering materials, clothing, curtains, sheets, plywood, plywood, carpets, entrance mats, sheets, buckets, hoses, containers, glasses, It can be used in various fields such as bags, cases, goggles, skis, rackets, tents, musical instruments, and other daily necessities, sports equipment and the like.

The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the scope of achieving the object of the present invention are included in the present invention.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the description of these examples.

<Synthesis of (poly)phosphate A>
100.0 g (1.16 mol) of anhydrous piperazine and 2.5 L of water were put into a 5 L five-necked flask equipped with a Dimroth condenser and heated to 100°C. 304.0 g (2.33 mol) of 75% phosphoric acid aqueous solution was added dropwise thereto over 4 hours, and then stirred at 100° C. for 5 hours. Then, the Dimroth cooler was replaced with a Liebig cooler, and about 2 L of water was distilled off. The mixture was cooled to 3° C. in an ice bath, and the precipitated crystals were collected by filtration and dried under vacuum at 110° C. for 4 hours to obtain 247.2 g of (poly)phosphate A.

<Synthesis of (poly)phosphate B>
A test tube containing 1.2 g of (poly)phosphate A was placed in an aluminum block bath heated to 250° C. and held for 120 minutes to obtain 1.1 g of (poly)phosphate B.

<Synthesis of (poly)phosphate C>
300 mL of ultrapure water and 150 mL of cation exchange resin (SK1BH, Mitsubishi Kagaku, 2.0 meq/mL) were placed in a 2 L beaker, and cooled to 1°C or lower in an ice bath. 19.0 g of pentasodium triphosphate was added thereto, and the mixture was stirred for 1.5 hours, and then the cation exchange resin was removed by filtration. In order to complete the ion exchange, the solution was passed through a column tube filled with 100 mL of the cation exchange resin, and the solution in the column was flown out with 800 mL of ultrapure water. 6.60 g of piperazine was added to the passed solution, and the mixture was stirred at room temperature for 3 hours. Then, using a rotary evaporator, water was completely distilled off at 30° C. or lower under reduced pressure to obtain a white solid. The obtained white solid was washed with 25 mL of water and subsequently with 100 mL of acetone, and dried under vacuum at room temperature to obtain 8.2 g of (poly)phosphate C.

<Synthesis of (poly)phosphate D>
Melamine 60.0 g (0.47 mol) and water 2.5 L were put into a 5 L five-necked flask equipped with a Dimroth condenser and heated to 100°C. After adding 68.3 g (0.52 mol) of 75% phosphoric acid aqueous solution thereto over 3 hours, the mixture was stirred at 100° C. for 5 hours. Then, the Dimroth cooler was replaced with a Liebig cooler, and about 2 L of water was distilled off. After cooling to room temperature, the precipitated crystals were collected by filtration and dried under vacuum at 110° C. for 4 hours to obtain (poly)phosphate D 95.0 g.

<Synthesis of (poly)phosphate E>
169.4 g of sodium pyrophosphate decahydrate (purity 99%<), 95.8 g of melamine (0.76 mol) and 600 mL of water were placed in a 1 L flask, and 158.3 g (1.52 mol) of 35% hydrochloric acid was used for 3 hours. The mixture was added dropwise and stirred for 3 hours. The solid was collected by filtration and washed with about 1 L of water. The obtained solid was dried under vacuum at 70° C. for 10 hours to obtain (poly)phosphate E 146.8 g.

<Synthesis of (poly)phosphate F>
A test tube containing 1.2 g of (poly)phosphate E was placed in an aluminum block bath heated to 230° C. and held for 1500 minutes to obtain 1.1 g of (poly)phosphate F.

With respect to the obtained (poly)phosphates A to F, the peak areas of orthophosphoric acid, pyrophosphoric acid, and triphosphoric acid were measured using the ion chromatography method under the following measurement conditions.
The peak area of orthophosphate derived from orthophosphate was designated as O, the peak area of pyrophosphate derived from pyrophosphate was designated as P, and the peak area of triphosphate derived from triphosphate was designated as T.
Table 1 shows the peak area ratios (%) of O, P, and T when the total area of O+P+T is 100%.

The retention times (elution times) at the three peaks of orthophosphoric acid, pyrophosphoric acid, and triphosphoric acid were measured by using the following standard substances and using the ion chromatography method under the same measurement conditions as above. Based on the measured retention times, three peaks of orthophosphoric acid, pyrophosphoric acid and triphosphoric acid were identified when using (poly)phosphates AF.

<Ion chromatography method>
(Measurement condition)
・Measuring device: Ion Chromatograph ICS-2100 (Thermo Fisher Scientific Co., Ltd.)
・Column: Dionex IonPac AS-19 (Thermo Fisher Scientific Co., Ltd.)
-Detector: electric conductivity detector-Elution condition: 1.0 mmol/L potassium hydroxide aqueous solution (0 minutes) -> 60.0 mmol/L potassium hydroxide aqueous solution (42 minutes). The concentration of the potassium hydroxide aqueous solution (eluent) was changed as follows.
From 0 min to 1 min: Gradient from 1.0 mmol/L to 10.0 mmol/L.
More than 1 minute to 10 minutes: constant at 10.0 mmol/L.
Greater than 10 minutes to 15 minutes: Gradient from 10.0 mmol/L to 60.0 mmol/L.
Greater than 15 minutes to 42 minutes: constant at 60.0 mmol/L.
・Flow rate: 1.0 mL/min
・Sample injection volume: 25 μL
・Column temperature: 35℃

(Reference material)
・Phosphorus standard solution (P: 1000 mg/l, KH ₂ PO ₄ in H ₂ O), Wako Pure Chemical Industries, Ltd.・Sodium pyrophosphate decahydrate (purity 99%<), Wako Pure Chemical Industries, Ltd.・Triphosphoric acid Pentasodium, manufactured by Wako Pure Chemical Industries

<Preparation of flame retardant composition>
The obtained (poly)phosphates A to F were mixed at the compounding ratio (% by weight) shown in Table 2 below to obtain 14 g of a flame retardant composition (Samples 1 to 19).

Regarding the flame retardant compositions of Samples 1 to 19 thus obtained, O, P and T were measured using the above <ion chromatography method>, and the respective peaks when the total area of O+P+T was set to 100% The area ratio (%) was calculated. The results are shown in Table 3.

Based on the obtained O, P, and T measurement results, for the flame retardant compositions of Samples 1 to 19, Samples 4 to 16 are Examples 1 to 13, Samples 1 to 3 and 17 to 19 are Comparative Examples 1 to 6. Used as.

The flame retardant compositions of Examples and Comparative Examples were evaluated based on the following evaluation items.

<Heat resistance>
5 mg of the obtained flame retardant composition of each of Examples and Comparative Examples was weighed and used as a measurement sample.
Using Rigaku Thermoplus 2/(TG-DTA series), under nitrogen atmosphere (flow rate: 200 ml/min), measurement sample: 5 mg, heating rate: 10° C./min, 25° C. to 250° C. After reaching 0° C., it was kept at 250° C. for 30 minutes (heat treatment). The weight of the measurement sample at this time (the weight of the measurement sample after the heat treatment) was measured. Using the weight of the obtained measurement sample before and after the heat treatment, the volatilization amount (%) based on thermogravimetric analysis (TGA) was calculated by the following formula. The results are shown in Table 3.
Volatilization amount (%)=[1-(weight of measurement sample after heat treatment/(weight of measurement sample before heat treatment)]×100

The obtained volatilization amount was evaluated based on the following evaluation criteria.
◯: Volatile amount is 3.0% or less Δ: Volatile amount is more than 3.0% and 4.0% or less x: Volatile amount is more than 4.0%

<Flame resistance>
0.1 part by weight of calcium stearate (lubricant), 100 parts by weight of polypropylene (Mitsui Chemicals, injection molding grade), tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate ] Polypropylene resin obtained by blending 0.1 part by weight of methane (phenolic antioxidant) and 0.1 part by weight of tris(2,4-ditert-butylphenyl)phosphite (phosphorus antioxidant) 43 parts by weight of the obtained flame retardant compositions of Examples 1 to 13 were blended with the composition and press-molded at 200 to 230°C to obtain a test piece having a thickness of 1.6 mm.
The UL-94V test based on the following was measured using the obtained test piece.

(Flame retardancy UL-94V test)
UL-94 standard: A test piece having a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm was held vertically, the lower end of the burner was indirectly fired for 10 seconds, and then the flame was removed to ignite the test piece. The time for the fire to go out was measured. Next, when the fire was extinguished, the second flame contact was started for 10 seconds, and the time for extinguishing the ignited fire was measured in the same manner as in the first flame. In addition, whether or not the cotton under the test piece ignites depending on the type of fire falling was also evaluated at the same time.

Combustion rank was set according to the above-mentioned UL-94 standard based on the first and second combustion times, the presence or absence of cotton ignition. The combustion rank is V-0, which is the highest, and the flame retardancy decreases as V-1 and V-2 become below. However, those that do not correspond to any of the ranks V-0 to V-2 are NR.

As a result of the flame retardancy UL-94V test, Example 5 shows better flame retardancy than Examples 1 and 2, and Examples 3, 4, 6 to 13 show better flame retardancy than Example 5. It showed flammability (V-0). From these results, among the (poly)phosphates, melamine (poly)phosphoric acid alone, piperazine (poly)phosphoric acid alone, piperazine (poly)phosphoric acid and a mixture of melamine (poly)phosphoric acid were difficult in order. It was found that the flammability was improved.

The flame retardant compositions of Examples 1 to 13 showed excellent heat resistance as compared with Comparative Examples 1 to 6.
It has been found that such a flame retardant composition can be suitably used as a flame retardant because it can improve the flame retardancy of the thermoplastic resin.

Claims (16)

Of the group consisting of orthophosphate, pyrophosphate, and triphosphate represented by the following general formula (1) or the following general formula (3),
With the triphosphate,
At least one of the orthophosphate and the pyrophosphate,
A flame retardant composition comprising:
The flame retardant composition is measured by an ion chromatography method,
The peak area of orthophosphate derived from the orthophosphate is O,
The peak area of pyrophosphate derived from the pyrophosphate is P,
When the peak area of triphosphate derived from the triphosphate is T,
T and O satisfy the following formula (I), or
T and P satisfy the following formula (II),
Flame retardant composition.
4.0×10 ⁻² %≦T/(T+O)≦95.0% Formula (I)
1.3×10 ⁻² %≦T/(T+P)≦25.0% Formula (II)

(In the general formula (1), n is a number of 1 to 3, X ¹ represents a triazine derivative represented by the following general formula (2), and p is a number satisfying a relational expression of 0<p≦n+2. is there.)

(In the general formula (2), Z ¹ and Z ² may be the same or different, and are a —NR ⁵ R ⁶ group, a hydroxyl group, a mercapto group, a linear or branched alkyl group having 1 to 10 carbon atoms. Represents a group selected from the group consisting of a linear or branched alkoxy group having 1 to 10 carbon atoms, a phenyl group and a vinyl group, and R ⁵ and R ⁶ each independently represent a hydrogen atom, a linear or branched group. It represents an alkyl group having 1 to 6 carbon atoms or a methylol group.)

(In the general formula (3), r is a number of 1 to 3, Y ¹ is piperazine or a diamine containing a piperazine ring, and q is a number satisfying the relational expression 0<q≦r+2.) The flame retardant composition according to claim 1, wherein
The flame retardant composition contains the orthophosphate, the pyrophosphate, and the triphosphate,
A flame retardant composition in which O, P and T satisfy the following formula (III).
1.0×10 ⁻² %≦T/(O+P+T)≦25.0% Formula (III) The flame retardant composition according to claim 2, wherein
A flame retardant composition in which O and T satisfy the following formula (IV).
4.0×10 ⁻⁴ ≦T/O≦20.0... Formula (IV) The flame retardant composition according to claim 2 or 3, wherein
A flame retardant composition in which O, P and T satisfy the following general formula (V).
75.0%≦P/(O+P+T)≦99.0%... General formula (V) The flame retardant composition according to any one of claims 1 to 4,
A flame retardant composition comprising the pyrophosphate represented by the general formula (1). A flame retardant composition according to any one of claims 1 to 5, wherein
A flame retardant composition containing the pyrophosphate salt wherein X ¹ in the general formula (1) is melamine. The flame retardant composition according to any one of claims 1 to 6,
A flame retardant composition comprising the pyrophosphate salt wherein Y ¹ in the general formula (3) is piperazine. A flame retardant composition according to any one of claims 1 to 7, wherein
The pyrophosphate in which X ¹ in the general formula (1) is melamine;
The above pyrophosphate in which Y ¹ in the general formula (3) is piperazine;
A flame retardant composition comprising: A flame retardant composition according to any one of claims 1 to 8, wherein
The flame retardant composition, wherein the total content of the orthophosphate, the pyrophosphate, and the triphosphate is 20% by weight or more based on 100% by weight of the flame retardant composition. The flame retardant composition according to any one of claims 1 to 9,
A flame retardant composition containing an auxiliary agent. A flame retardant composition according to any one of claims 1 to 10, wherein
A flame retardant composition comprising a surface treatment agent. The flame retardant composition according to any one of claims 1 to 11,
A flame retardant composition comprising a dust suppressor. A flame retardant composition according to any one of claims 1 to 12,
A thermoplastic resin,
A flame-retardant resin composition containing: The flame-retardant resin composition according to claim 13,
A flame-retardant resin composition in which the thermoplastic resin contains a polyolefin resin. A molded article comprising the flame-retardant resin composition according to claim 13 or 14. A manufacturing method for manufacturing a molded article using the flame-retardant resin composition according to claim 13.