JP2001262146A - Flame retardant auxiliary comprising polyalkylamine derivative, composite flame retardant using the same and flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant auxiliary that can be more readily produced than the conventional in an industrial scale and can effectively develop the flame-retardant properties of the conventional flame retardant even in the case that the formulation of the flame retardant, particularly the halogen atom- free flame retardant is decreased, as well as the underwater insulation resistance, and further provide a composite flame retardant prepared by combining this auxiliary with a flame retardant and a flame-retardant resin composition prepared by compounding the composite flame retardant. SOLUTION: The objective flame retardant auxiliary comprises the reaction product from a polyalkylamine bearing 3 or more primary and/or secondary amino groups and cyanuric chloride. The auxiliary is used to provide the objective composite flame retardant and a flame retardant resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to primary and / or secondary grades.
The present invention relates to a flame-retardant auxiliary, a composite flame-retardant comprising a reaction product of a polyalkylamine containing three or more graded amino groups and cyanuric chloride, and a flame-retardant resin composition comprising the same. The flame-retardant resin composition containing the composite flame retardant of the present invention is widely used as a material for various electric appliances, automobile parts, building materials, electric wires, cables and the like.

[0002]

2. Description of the Related Art Hitherto, halogen-based flame retardants have been widely used for flame retardancy of resins because of their excellent flame retardancy, resin properties, and price. Due to the problem of toxic gas generation during combustion, flame retardant formulations that do not use halogen compounds have been actively developed in recent years.

Phosphoric ester compounds (eg, triphenyl phosphate and tricresyl phosphate (both of which are disclosed, for example, in Japanese Patent Publication No. 53-418)) include flame retardants containing no halogen atoms for the purpose of flame retardation of resins. ,
Ammonium polyphosphate (for example, JP-A-7-33096)
No. 8), phosphorus-based flame retardants such as red phosphorus, amine phosphates (for example, ethylenediamine phosphate (for example, JP-A-5-156116)), and inorganic based flame retardants such as magnesium hydroxide, aluminum hydroxide, and zinc borate. Flame retardants and the like are known.

[0004] However, many phosphate ester compounds have high volatility and insufficient heat resistance, and further improvement has been demanded due to the problems of flame retardancy and mechanical properties of the compounded resin. Further, a resin composition containing a phosphorus compound represented by ammonium polyphosphate has a problem that water resistance is poor, and a resin composition containing red phosphorus is
There is a problem that the resin composition is colored, and furthermore, phosphine gas is generated during processing, and inorganic flame retardants represented by magnesium hydroxide and aluminum hydroxide are not always satisfied in terms of flame retardancy. There is no present.

Under these circumstances, in order to solve the above-mentioned problem, Japanese Patent No. 2567327 discloses that a reaction product obtained by reacting cyanuric chloride with diamines and having a reduced residual chlorine amount as much as possible is used as a flame retardant aid. It is disclosed that excellent flame retardancy can be exhibited with a low blending amount by combining with a specific phosphorus-based flame retardant. However,
In the case of reacting cyanuric chloride with diamines, scaling is likely to occur in the reactor during the production, and it is difficult to obtain a resin by incorporating a flame retardant using this reaction product and a phosphorus-based flame retardant into a resin. Flammable resin compositions have not yet been satisfactory in terms of flame retardancy and insulation resistance in water.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to make it easier to manufacture on an industrial scale than in the prior art, and to achieve the conventional method even if the compounding amount is low. A flame retardant, particularly a flame retardant that does not contain a halogen atom, which can effectively exhibit the flame retardancy and insulation resistance in water, and a flame retardant obtained by combining the flame retardant with the flame retardant An object of the present invention is to provide a composite flame retardant. It is a further object of the present invention to provide a flame-retardant resin composition obtained by blending a composite flame retardant with a resin.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a polyalkylamine containing three or more primary and / or secondary amino groups reacts with cyanuric chloride. By doing so, it can be easily manufactured with almost no scaling to the reactor during the manufacture, and is combined with a conventionally known flame retardant such as a phosphorus-based flame retardant, metal oxide, or expanded graphite to form a composite. As a result, they found that the function of these flame retardants was significantly improved, and completed the present invention.

That is, the present invention provides a flame retardant auxiliary, a composite flame retardant comprising a reaction product of a polyalkylamine containing three or more primary and / or secondary amino groups and cyanuric chloride.
And a flame retardant resin composition obtained by blending the composite flame retardant with a resin.

Hereinafter, the present invention will be described in detail.

The reaction product of the polyalkylamine and cyanuric chloride referred to in the present invention is a compound obtained by successively substituting three active chlorine atoms of cyanuric chloride with amino groups in the polyalkylamine. This compound is substantially insoluble in water and organic solvents. In addition, the polyalkylamine referred to in the present specification is a compound having three or more primary and / or secondary amino groups. For example, diaminetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aliphatic amines such as dipropanetriamine, high-boiling amines generated when producing these polyalkylamines, polyethyleneimine, polyvinylimidazoline, Compounds such as a polymer having a nitrogen atom such as polyallylamine are exemplified. The amino group in these compounds may have at least three primary and / or secondary amino groups capable of reacting with an active chlorine atom of cyanuric chloride, and some of the amino groups in the compound may be tertiary amino groups. It may be.

In the reaction of cyanuric chloride with a polyalkylamine, the activity of the remaining active chlorine atom in cyanuric chloride is greatly reduced each time one of the active chlorine atoms in the cyanuric chloride is replaced with an amino group. Therefore, the reaction between each active chlorine atom of cyanuric chloride and polyalkylamine is preferably performed in three stages.

First, in the first-stage reaction, the reaction between an active chlorine atom of cyanuric chloride dispersed in a reaction solvent and a polyalkylamine is carried out in the presence of a dehydrochlorinating agent at a reaction temperature of 10 ° C. or lower, preferably at a reaction temperature of 10 ° C. or lower. The reaction is performed at a reaction temperature of 5 ° C. or less.

The reaction solvent to be used is not particularly limited, but usually a solvent inert to cyanuric chloride is used, for example, an aromatic solvent such as benzene, toluene, xylene and the like, hexane, heptane and the like. And a halogen-based solvent such as methylene chloride and chloroform.

In the first stage reaction, the molar ratio of cyanuric chloride to polyalkylamine used is such that the molar ratio of amino groups in polyalkylamine to active chlorine atoms of cyanuric chloride is in the range of 0.1 to 2.0. It is preferably a molar ratio, and more preferably a molar ratio in the range of 0.2 to 1.0. The concentration of cyanuric chloride in the reaction solvent is not particularly limited, but is usually 1 to 50% by weight.

The dehydrochlorinating agent used in the present invention is not particularly limited, and is mainly used to react with hydrochloric acid generated by the reaction, and includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and carbonic acid. Inorganic metal bases such as sodium hydrogen and potassium hydrogen carbonate, and tertiary amines such as triethylamine, tripropylamine and tributylamine are used. The amount of the dehydrochlorinating agent used is usually a molar ratio in the range of 1.0 to 3.0 with respect to hydrochloric acid by-produced in the reaction. The method of adding the polyalkylamine and the dehydrochlorinating agent is not particularly limited, but usually, first, a solution in which the polyalkylamine is dissolved in the reaction solvent is dropped into a solution in which cyanuric chloride is dispersed in the reaction solvent,
Next, a method in which a solution in which a dehydrochlorinating agent is dissolved in water or the like is dropped, a method in which both are dropped simultaneously, or a method in which a mixed solution in which both are dissolved in water are dropped. Furthermore, in order to complete the reaction, 1 to 1 at a predetermined temperature after dropping.
It is desirable to perform ripening within the range of 0 hours.

In the second stage reaction, the reaction between the active chlorine atom in the product obtained in the first stage reaction and the polyalkylamine is carried out in the presence of a dehydrochlorinating agent as in the first stage. 40-8
The reaction is performed at a reaction temperature of 0 ° C. The reaction may be continued using the slurry reaction solution obtained in the first stage reaction as it is, and the product in the slurry reaction solution obtained in the first stage reaction may be filtered. There is no problem if used after drying.

In the second-stage reaction, the ratio of the product obtained in the first-stage reaction to the polyalkylamine is determined by the molar ratio of the amino group of the polyalkylamine to the active chlorine atom of the product. , 0.1 to 2.0, and more preferably 0.2 to 1.0.

As the dehydrochlorinating agent used in the reaction, the same dehydrochlorinating agent as that used in the first-stage reaction can be used, and the amount of hydrochloric acid used as a by-product in the reaction is the same as in the first-stage reaction. The molar ratio is preferably in the range of 1.0 to 3.0. In the second-stage reaction, the method of adding the polyalkylamine and the dehydrochlorinating agent is not particularly limited, but is usually performed in the same manner as in the first-stage reaction.
Furthermore, in order to complete the reaction, after dropping,
It is desirable to perform aging within a range of 20 hours.

In the third step, the reaction between the remaining active chlorine atom in the product obtained in the second step and the polyalkylamine is carried out in the presence of a dehydrochlorinating agent, as in the first step. And 1
The reaction is performed at a reaction temperature of 00 ° C or more.

The solvent used in the reaction is, for example, toluene or xylene having a boiling point of 100 ° C. or higher when the product is separated from the slurry reaction solution by filtration or the like after the completion of the second stage reaction. A polar solvent such as an aromatic solvent or N, N-dimethylformamide or dimethyl sulfoxide is used. When a high-boiling solvent such as toluene or xylene is used from the first stage, water is separated from the slurry reaction solution by an operation such as azeotropic distillation after the completion of the second stage reaction to carry out the reaction. No problem.

In the third reaction, the ratio of the product obtained in the second reaction to the polyalkylamine is as follows:
The molar ratio of the amino group of the polyalkylamine to the active chlorine atom of the product is preferably in the range of 0.1 to 2.0, and more preferably in the range of 0.2 to 1.0. preferable.

As the dehydrochlorinating agent used in the reaction, the same dehydrochlorinating agent as that used in the first-stage or second-stage reaction can be used, and the amount used is the same as in the first-stage reaction. The molar ratio is preferably in the range of 1.0 to 3.0 with respect to hydrochloric acid as a by-product.

In the third-stage reaction, the method of adding the polyalkylamine and the dehydrochlorinating agent is not particularly limited, but it is usually carried out by batch addition, and after the addition, it is necessary to complete the reaction. 5 to 50 hours at a predetermined temperature, preferably 1
It is desirable that the aging is performed in the range of 0 to 25 hours.

The product obtained by the third stage reaction is
Thereafter, the product is filtered, washed, and dried to obtain a product serving as the flame retardant aid of the present invention. This product is usually obtained as a white or slightly yellow powder.

Next, the composite flame retardant of the present invention will be described.

The composite flame retardant of the present invention comprises a product obtained by reacting the above-mentioned polyalkylamine with cyanuric chloride and a flame retardant. Although the detailed reason is not clear, the reaction product of this polyalkylamine and cyanuric chloride has low flame retardancy per se, but is used as a composite flame retardant blended with one or more flame retardants, It has a very excellent effect of synergistically improving its flame retardancy and exhibits useful performance as a flame retardant aid.

The flame retardant used in the composite flame retardant of the present invention is not particularly limited as long as it generally has an effect as a flame retardant. Examples thereof include phosphorus-based flame retardants, metal oxides, and expanded graphite. It is preferably used. These flame retardants may be used alone or in combination of two or more.

Further, when these flame retardants are specifically exemplified, as the phosphorus compound, ammonium polyphosphate, amide-modified ammonium polyphosphate, melamine phosphate, melamine polyphosphate, guanidine phosphate, ethylenediamine phosphate, Zinc ethylenediamine phosphate,
Preferable examples include phosphate amine salts such as 1,4-butanediamine phosphate, red phosphorus, and phosphate esters.

Examples of the metal compound include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, zinc hydroxystannate, zinc stannate, nickel oxide, cobalt oxide, iron oxide, copper oxide, molybdenum oxide, tin oxide,
Preferable examples include zinc oxide, silicon oxide, zeolite, zinc borate, zirconium oxide, antimony trioxide, and antimony pentoxide.

Further, as the expanded graphite, conventionally known substances can be used. For example, powders such as natural flaky graphite, pyrolytic graphite, and cache graphite are mixed with inorganic acids such as concentrated sulfuric acid and nitric acid, concentrated nitric acid, and perchloric acid. And a crystalline compound which maintains a layered structure of carbon which has been treated with a strong oxidizing agent such as perchlorate or permanganate to form a graphite intercalation compound.

The mixing ratio of these flame retardants and the flame retardant auxiliary of the present invention varies depending on the number of parts to be mixed with the resin to be compounded. However, if the weight ratio is in the range of 1/20 to 20/1, it is very low. Excellent flame retardant effect, and the effect can be further improved in the range of 1/10 to 10/1.

Next, the flame-retardant resin composition of the present invention will be described.

The flame-retardant resin composition of the present invention is obtained by mixing the composite flame retardant of the present invention with a resin.

The resins to which the composite flame retardant of the present invention can be compounded include phenol resins, urea resins, melamine resins, unsaturated polyester resins, polyurethanes, alkyd resins,
Thermosetting resins such as epoxy resins, low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, polystyrene, impact-resistant polystyrene, expanded polystyrene, acrylonitrile-styrene copolymer,
Acrylonitrile-styrene-butadiene copolymer, polypropylene, petroleum resin, polymethyl methacrylate,
Examples thereof include thermoplastic resins such as polyamide, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polyphenylene ether, and further include polymer alloys represented by polycarbonate-ABS, polyphenylene ether-polystyrene, etc. obtained by mixing two or more kinds of thermoplastic resins. it can. Among them, low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, and polyolefin-based thermoplastic resins such as polypropylene are exemplified as suitable resins.

The compounding amount of the composite flame retardant of the present invention to the resin is as follows:
It depends on the type of resin to be blended and the intended flame retardancy, and is not particularly limited.
It is preferable to add 5-200 parts by weight, more preferably 10-150 parts by weight, based on parts by weight. If the amount is less than 5 parts by weight, the flame retardant effect may be insufficient,
If it exceeds 200 parts by weight, the mechanical properties of the flame-retardant resin composition may be reduced. In addition, if necessary, a benzotriazole-based ultraviolet absorber,
A light stabilizer such as a 6,6-tetramethylpiperidine derivative, a hindered phenol-based antioxidant, and the like may be added.
It is usually preferable to add 0.05 to 5 parts by weight to 00 parts by weight. In addition to these, if necessary, an inorganic filler such as an antistatic agent, talc, or glass fiber may be added.

The method of compounding the composite flame retardant of the present invention into a resin is as follows. For example, when the compound flame retardant of the present invention is previously dispersed in a resin material and then cured, Well, when blended with thermoplastic resin,
For example, the composite flame retardant may be mixed using a conical blender or a tumbler mixer, and pelletized using a twin-screw extruder or the like. The method for processing the flame-retardant resin composition obtained by these methods is not particularly limited. For example, extrusion molding, injection molding, or the like can be performed to obtain a desired molded product.

[0037]

According to the present invention, the following effects can be obtained.

(1) The flame retardant auxiliary comprising the reaction product of the polyalkylamine and cyanuric chloride of the present invention more effectively expresses the properties of the conventional flame retardant, such as flame retardancy and underwater insulation resistance. be able to.

(2) By incorporating the composite flame retardant of the present invention into a resin, high flame retardancy and high water resistance can be exhibited.

(3) The flame-retardant resin composition obtained by blending the composite flame retardant of the present invention with a resin can be widely used as a material for various electric appliances, automobile parts, building materials, electric wires, cables and the like. Extremely useful.

[0041]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

Production Example 1 225 g of water and 75% by weight of phosphoric acid were charged into a 1-liter glass reactor having a stirring blade and a thermometer, and 323 g of zinc sulfate heptahydrate was added and dissolved while stirring and mixing. I let it. 41.0 g of ethylenediamine was added to this solution.
Was dissolved in 225 g of water, and the pH was adjusted to 7.0 with a 48% by weight aqueous sodium hydroxide solution.
The mixture was stirred for 22 hours while maintaining the temperature at 30 ° C. After the reaction, the product was filtered, washed with water, and dried under normal pressure at 120 ° C. to obtain 214.0 g of white zinc zinc ethylenediamine phosphate.
Hereinafter, the obtained ethylenediamine zinc phosphate is referred to as ED
Abbreviated as A-ZP.

Example 1 (First-stage reaction) 92.2 g of cyanuric chloride was placed in a 1-liter glass reactor having a stirring blade, a thermometer and a cooling pipe.
And 500 g of xylene, stirred while maintaining a temperature of 0 to 5 ° C., and a solution in which 17.2 g of diethylenetriamine and 20.0 g of sodium hydroxide were dissolved in 100 g of water was added dropwise over 1 hour. After completion of the dropping, 0-5
After stirring at a temperature of ° C. for 1 hour, the mixture was allowed to reach room temperature.

(Second Step Reaction) Subsequently, the reaction solution
At room temperature, a solution prepared by dissolving 17.2 g of diethylenetriamine and 20.0 g of sodium hydroxide in 100 g of water was added.
After dropping over time, the temperature was raised to 80 ° C.
Stir for 7 hours. After the completion of the reaction, the mixture was cooled and the reaction product was filtered.

(Third-stage reaction) Next, the above reaction product was charged into a glass reactor having a capacity of 1 liter having a stirring blade, a thermometer and a cooling tube, and 500 g of xylene was further charged and stirred under reflux. , And the attached water contained in the reaction product was azeotropically distilled off. After the distillation, 17.2 g of diethylenetriamine and 20.0 g of sodium hydroxide were charged into the solution, and the mixture was reacted at 140 ° C. with stirring for 24 hours. After the reaction, cool and filter the product,
After washing with water and drying under reduced pressure at 140 ° C., 89.0 g of a white powder was obtained.
I got

The obtained product was insoluble in organic solvents and water, had a melting point of> 300 ° C., and was subjected to elemental analysis. As a result, 5.1% of chlorine remained. The scaling of the reaction product in the reactor in each reaction step hardly occurred.

The obtained product and ammonium polyphosphate (manufactured by Hoechst Co., Ltd., trade name: Exolit46)
2) were mixed at a weight ratio of 1: 2, respectively.
Was prepared.

Example 2 (First-stage reaction) 92.2 g of cyanuric chloride was placed in a 1-liter glass reactor having a stirring blade, a thermometer and a cooling pipe.
And 500 g of xylene, stirred while maintaining a temperature of 0 to 5 ° C., and a solution in which 18.9 g of tetraethylenepentamine and 20.0 g of sodium hydroxide were dissolved in 120 g of water was added dropwise over 1.5 hours. . After the completion of the dropwise addition, the mixture was further stirred at the same temperature for 1 hour and allowed to stand at room temperature.

(Second Step Reaction) Subsequently,
At room temperature, a solution prepared by dissolving 18.9 g of tetraethylenepentamine and 20.0 g of sodium hydroxide in 120 g of water was added dropwise over 2 hours. After completion of the addition, the temperature was raised to 80 ° C., and the mixture was stirred for 18 hours. After the completion of the reaction, the mixture was cooled and the reaction product was filtered.

(Third-stage reaction) Next, the above reaction product was charged into a 1-liter glass reactor having a stirring blade, a thermometer and a cooling tube, and further, 500 g of xylene was charged and stirred under reflux. , And the attached water contained in the reaction product was azeotropically distilled off. After the distillation, 18.9 g of tetraethylenepentamine and 20.0 g of sodium hydroxide were charged into the solution, and the mixture was reacted at a temperature of 142 ° C. with stirring for 24 hours. After the reaction, the reaction mixture was cooled, and the product was filtered, washed with water, and dried at 140 ° C. under reduced pressure to give a slightly yellow powder 7.
3.0 g were obtained.

The obtained product was insoluble in organic solvents and water, had a melting point of> 300 ° C., and was subjected to elemental analysis. As a result, it was found that 2.0% of chlorine remained. The scaling of the reaction product in the reactor in each reaction step hardly occurred.

The obtained product was mixed with ammonium polyphosphate (Exolit 4 manufactured by Hoechst Co., Ltd.).
62), EDA-ZP prepared in Production Example 1 was mixed at a weight ratio of 1: 1: 1 to prepare a composite flame retardant 2.

Example 3 (First reaction) 92.2 g of cyanuric chloride was placed in a 1-liter glass reactor having a stirring blade, a thermometer and a cooling tube.
And 500 g of xylene, stirred while maintaining the temperature of 0 to 5 ° C., and a solution of 16.5 g of pentaethylenehexamine dissolved in 49.5 g of xylene and a solution of 20.0 g of sodium hydroxide dissolved in 80 g of water At the same time 2.
It was added dropwise over 2 hours. After dropping, add
Stirred for hours and allowed to reach room temperature.

(Second Stage Reaction) Subsequently, the reaction solution
At room temperature, a solution of 16.5 g of pentaethylenehexamine dissolved in 49.5 g of xylene was added dropwise over 0.3 hours, followed by sodium hydroxide 2 dissolved in 80 g of water.
0.0 g of the solution was added dropwise over 0.4 hours. After completion of the dropwise addition, the temperature was raised to 80 ° C., and the mixture was stirred for 20 hours. After the completion of the reaction, the mixture was cooled and the reaction product was filtered.

(Third-stage reaction) Next, the above reaction product was charged into a glass reactor having a capacity of 1 L having a stirring blade, a thermometer and a cooling tube, and 500 g of xylene was further charged and stirred to be refluxed. The mixture was heated until the temperature reached, and the attached water contained in the reaction product was azeotropically distilled off. After the distillation, 16.5 g of pentaethylenehexamine and 20.0 g of sodium hydroxide were charged into the solution, and reacted while stirring at a temperature of 135 ° C. for 48 hours. After the reaction, the mixture was cooled, the product was filtered, washed with water, and dried under reduced pressure at 140 ° C. to obtain 42.7 g of a slightly yellow powder.

The obtained product was insoluble in organic solvents and water, had a melting point of> 300 ° C., and was subjected to elemental analysis. As a result, 1.8% of chlorine remained. The scaling of the reaction product in the reactor in each reaction step hardly occurred.

The obtained product was mixed with ammonium polyphosphate (Exolit 46, manufactured by Hoechst Co., Ltd.).
2) were mixed in a weight ratio of 1: 2, respectively, and a composite flame retardant 3
Was prepared.

Examples 4 to 6 Ethylene-vinyl acetate copolymers (trade name: Ultracene UE635, manufactured by Tosoh Corp., hereinafter referred to as "EVA") were obtained in Examples 1 to 3 based on 100 parts by weight. Compound flame retardants 1 to 3 were mixed in parts by weight as shown in Table 1 to obtain 13
Roll kneading at a temperature of 0 ° C, press molding at 150 ° C,
A flame-retardant resin composition was prepared. Next, the flame retardancy and water resistance of the prepared flame retardant resin composition were evaluated by the following methods.

That is, the evaluation of flame retardancy is based on JIS K7
201, a combustion test method for polymer materials by the oxygen index method, Underwriters Lab, USA
The test was performed according to UL94V (1/8 inch thickness of test piece) which is a standard of Oratories. The evaluation of water resistance was performed on test pieces (100 × 100 ×
0.2 mm) in water at 20 ° C. for 6 hours, and the volume resistivity of the test piece was measured by ULTRA HIGH RESIS.
TANCE METER (R manufactured by Advantest Corporation)
8340). Table 1 shows the types of the composite flame retardants used, EVA in the flame retardant resin composition,
The evaluation results of the amounts of ammonium polyphosphate, EDA-ZP and the flame retardant aid, and the flammability and water resistance of the flame retardant resin composition are shown.

[0060]

[Table 1]

Examples 7 to 9 The composite flame retardants obtained in Examples 1 to 3 based on 100 parts by weight of low density polyethylene (manufactured by Tosoh Corporation, trade name: Petrocene 202, hereinafter referred to as "LDPE") 1 to 3 were mixed in parts by weight as shown in Table 2, roll-kneaded at a temperature of 130 ° C, and press-formed at 150 ° C to prepare a flame-retardant resin composition. Next, the flame retardancy and water resistance of the prepared flame retardant resin composition were evaluated in the same manner as in Examples 4 to 6. Table 2 shows the types of composite flame retardants used, LDPE in the flame retardant resin composition, ammonium polyphosphate, E
The amounts of DA-ZP and the flame retardant aid, and the results of evaluation of the flammability and water resistance of the flame retardant resin composition are shown.

[0062]

[Table 2]

Comparative Example 1 (First-stage reaction) 92.2 g of cyanuric chloride was placed in a 1-liter glass reactor having a stirring blade, a thermometer and a cooling pipe.
And 294 g of acetone, stirred while maintaining a temperature of 0 to 5 ° C., and a solution of 14.7 g of ethylenediamine dissolved in 49.0 g of acetone and a solution of 19.7 g of sodium hydroxide dissolved in 58.8 g of water Was simultaneously added dropwise over 2.5 hours. After the completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours and allowed to reach room temperature.

(Second-Step Reaction) Subsequently,
At room temperature, a solution of 14.7 g of ethylenediamine dissolved in 49.0 g of acetone was added dropwise over 0.5 hours, and then 19.7 g of sodium hydroxide dissolved in 58.8 g of water.
g of solution was added dropwise over 0.3 hours. After dropping, 6
The temperature was raised to 0 ° C., and the mixture was stirred for 17 hours. After completion of the reaction, the reaction mixture was cooled, the reaction product was filtered, and dried under reduced pressure.

(Third-stage reaction) Next, the above reaction product was charged into a 1-liter glass reactor having a stirring blade, a thermometer, and a cooling pipe.
3 g and 20.4 g of sodium hydroxide were charged.
The reaction was carried out with stirring at a temperature of ° C for 17 hours. After the reaction, the mixture was cooled, and the product was filtered, washed with water, and dried under reduced pressure at 140 ° C. to obtain 74.2 g of a slightly yellow powder.

The obtained product was insoluble in organic solvents and water, had a melting point of> 300 ° C., and was subjected to elemental analysis. As a result, 8.6% of chlorine remained. In each of the reaction steps, scaling of the reaction product to the reactor occurred.

When Examples 1 to 3 and Comparative Example 1 are compared,
It can be seen that scaling occurs when ethylenediamine is reacted with cyanuric chloride, whereas no scaling occurs with the amine used in Examples 1-3.

Comparative Example 2 The product obtained in Comparative Example 1 and ammonium polyphosphate (Exolit 462, manufactured by Hoechst Co., Ltd.)
Were mixed in a weight ratio of 1: 2 to prepare a composite flame retardant 4.

Comparative Example 3 The product obtained in Comparative Example 1, ammonium polyphosphate (Exolit 462, manufactured by Hoechst KK)
And EDA-ZP prepared in Production Example 1 respectively:
The mixture was mixed at a weight ratio of 1: 1 to prepare a composite flame retardant 5.

Comparative Examples 4 to 5 The composite flame retardant 4 obtained in Comparative Example 2 or the composite flame retardant 5 obtained in Comparative Example 3 was mixed with 100 parts by weight of EVA in parts by weight as shown in Table 1. Roll kneading was performed at a temperature of 130 ° C., and press molding was performed at 150 ° C. to prepare a flame-retardant resin composition. Next, the flame retardancy and water resistance of the prepared flame retardant resin composition were evaluated in the same manner as in Examples 4 to 6. Table 1 shows the types of the composite flame retardants used, the amounts of EVA, ammonium polyphosphate, and the flame retardant aid in the flame retardant resin composition, and the evaluation of the flammability and water resistance of the flame retardant resin composition. The results are shown.

Comparative Examples 6 and 7 The compound flame retardant 4 obtained in Comparative Example 2 or the compound flame retardant 5 obtained in Comparative Example 3 was mixed with 100 parts by weight of LDPE in parts by weight as shown in Table 2. Roll kneading was performed at a temperature of 130 ° C., and press molding was performed at 150 ° C. to prepare a flame-retardant resin composition. Next, the flame retardancy and water resistance of the prepared flame retardant resin composition were evaluated in the same manner as in Examples 4 to 6. Table 2 shows the types of composite flame retardants used, LDPE in the flame retardant resin composition, ammonium polyphosphate, EDA-
The amounts of ZP and the flame retardant aid, and the evaluation results of the flammability and water resistance of the flame retardant resin composition are shown.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/45 C08K 5/45 C08L 39/00 C08L 39/00 79/02 79/02 101/00 101 / 00 C09K 21/02 C09K 21/02 21/04 21/04 F term (reference) 4H028 AA03 AA07 AA08 AA30 AA42 AB03 BA06 4J002 AA001 BB031 BB061 BJ002 CM012 DA027 DA057 DE077 DE087 DE097 DE107 DE117 DE127 DE147 DJ187 017 DK0 EW047 EW157 FB077 FD010 FD040 FD050 FD070 FD100 FD132 FD136 FD137 GL00 GN00 GQ00

Claims (6)

[Claims] 1. A flame retardant auxiliary comprising a reaction product of a polyalkylamine having three or more primary and / or secondary amino groups and cyanuric chloride. 2. A composite flame retardant comprising a flame retardant and the flame retardant auxiliary according to claim 1. 3. The composite flame retardant according to claim 2, wherein the compounding ratio of the flame retardant and the flame retardant auxiliary is 1/20 to 20/1 by weight. 4. The composite flame retardant according to claim 2, wherein the flame retardant is a phosphorus-based flame retardant, metal oxide or expandable graphite. 5. The composite according to claim 2, wherein the flame retardant is two or three selected from the group consisting of phosphorus-based flame retardants, metal oxides and expandable graphite. Flame retardants. 6. A flame-retardant resin composition comprising the resin and the composite flame retardant according to claim 2 blended in an amount of 5 to 200 parts by weight per 100 parts by weight of the resin.