JP3800660B2 - Metal-containing ethylenediamine phosphate, method for producing the same, and flame-retardant resin composition containing the same - Google Patents

Description

【００４３】
実施例７〜実施例１２
実施例２〜実施例５の方法により得られた金属含有エチレンジアミンリン酸塩を、ポリプロピレン１００重量部に対して表１に示すような配合量で混練した以外は実施例６と同様の方法により各種評価用試験片を得、測定評価した。その結果を表１にあわせて示す。
【００４４】
実施例１３
実施例１の方法により得られたマグネシウム含有エチレンジアミンリン酸塩を、アクリル酸エチル含有率が１５重量％のエチレン−アクリル酸エチル共重合体（日石化学製レクストロンＡ１１５０）１００重量部に対して５０重量部配合し、１５０℃にてロール混練を行った。ロール混練により得られた樹脂組成物を１８０℃、１２０ｋｇ／ｃｍ２で４分間プレス成形し、これより各種評価用試験片を得、測定評価した。その結果を表２に示す。
【００４５】
【表２】

【００４６】
実施例１４〜実施例１６
実施例３〜実施例５の方法により得られた金属含有エチレンジアミンリン酸塩を用いた以外は実施例１３と同様の方法により各種評価用試験片を得、測定評価した。その結果をあわせて表２に示す。
【００４７】
比較例１〜比較例５
参考例１〜参考例３の方法により得られた金属含有エチレンジアミンリン酸塩、及び金属塩と反応させていない平均粒径１１μのエチレンジアミンリン酸塩を用いた以外は実施例６と同様の方法により各種評価用試験片を得、測定評価した。その結果を表１にあわせて示す。
【００４８】
比較例６〜比較例８
参考例１〜参考例３の方法により得られた金属含有エチレンジアミンリン酸塩及び金属塩と反応させていない平均粒径１１μのエチレンジアミンリン酸塩を用いた以外は実施例１３と同様の方法により各種評価用試験片を得、測定評価した。その結果を表２にあわせて示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a metal-containing ethylenediamine phosphate comprising ethylenediamine, phosphoric acid, and a Group IIA alkaline earth metal or Group IIB metal useful as a flame retardant, a method for producing the same, and a flame retardant resin composition containing the same.
[0002]
[Prior art]
Conventionally, halogen-based flame retardants have been widely used for flame retardancy of resins because they are excellent in terms of flame retardancy, resin physical properties, and price. Occurrence has been regarded as a problem, and in recent years there has been a shift to a method for making flame retardant without using halogen compounds. Non-halogen flame retardants include metal hydroxides such as magnesium hydroxide and aluminum hydroxide, nitrogen compounds such as isocyanuric acid and melamine, phosphorus compounds such as red phosphorus, triphenyl phosphate and phosphate ester oligomers, and Compounds containing nitrogen and phosphorus, such as ammonium polyphosphate, melamine phosphate, and ethylenediamine phosphate are known. Nitrogen and phosphorus-containing flame retardants generally have high flame retardancy, and ethylenediamine phosphate exhibits excellent flame retardancy, and its use is disclosed in JP-T-5-508187 and JP-A-7-156116. Is described.
[0003]
[Problems to be solved by the invention]
However, the water resistance of the flame retardant resin composition containing ethylenediamine phosphate is not sufficient, and the electrical properties are not sufficient, and the practical level for each application such as wire / cable, metal tube coating material, home appliance parts, various sheets, etc. There is a problem of not reaching. In addition, although the flame retardant performance of ethylenedimine phosphate is higher than that of other non-halogen flame retardants, it requires a higher blending amount than halogen-based flame retardants, so there is a problem that deterioration in mechanical properties is inevitable. is there.
[0004]
This invention is made | formed in view of said subject, It aims at providing the metal containing ethylenediamine phosphate useful as a flame retardant, and a flame retardant resin composition containing the same.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors obtain a flame retardant resin composition having good flame retardancy and resin physical properties by treating ethylenediamine phosphate with an aqueous metal salt solution. It has been found that this is possible, and the present invention has been completed.
[0006]
That is, the present invention relates to a metal-containing ethylenediamine phosphate comprising ethylenediamine, phosphoric acid, and a Group IIA alkaline earth metal or Group IIB metal, a method for producing the same, and a flame-retardant resin composition containing the same.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0008]
The metal-containing ethylenediamine phosphate of the present invention is characterized by comprising ethylenediamine, phosphoric acid, and a Group IIA alkaline earth metal or Group IIB metal.
[0009]
The amount of Group IIA or Group IIB metal contained in the metal-containing ethylenediamine phosphate of the present invention is not particularly limited, but is preferably 0.2 to 4% by weight in the following points. That is, when the metal content exceeds 4% by weight, (1) flame retardant performance is significantly lower than that of ethylenediamine phosphate before treatment, and (2) the crystal structure of ethylenediamine phosphate is destroyed and the product is destroyed. The composition of ethylenediamine and phosphoric acid in (3) changes. (3) The ethylenediamine phosphate and metal salt do not react completely, and the counter anion of the metal salt remains in the metal-containing ethylenediamine phosphate. (4) Metal salt In some cases, the ethylenediamine phosphate dissolves and the yield decreases due to the high concentration. On the other hand, if it is 0.2% by weight or less, flame retardancy and resin physical properties may not be sufficient when blended with a resin.
[0010]
The metal contained in the metal-containing ethylenediamine phosphate of the present invention is a Group IIA alkaline earth metal or Group IIB metal, and among these, magnesium, calcium, zinc, and barium are preferred, and among these, magnesium is preferred. Particularly preferred.
[0011]
The metal-containing ethylenediamine phosphate of the present invention can be obtained by reacting a group IIA or group IIB metal salt with a phosphoric acid portion of ethylenediamine phosphate dispersed in an aqueous solution.
[0012]
The metal salt used in the method of the present invention is not particularly limited, and examples thereof include halide salts or hydrates thereof, and specific examples include magnesium chloride, calcium chloride, zinc chloride, bromide. Examples thereof include magnesium and zinc bromide.
[0013]
Although the quantity of the metal salt added to the aqueous solution at the time of making ethylenediamine phosphate and a metal salt react is not specifically limited, the metal part of a metal salt is 0.3-3. If it adds so that it may become 5 weight%, the ethylenediamine phosphate containing the metal of 0.2-4 weight% of this invention is obtained.
[0014]
The amount of water used for ethylenediamine phosphate is preferably within a range where good dispersion and stirring conditions are obtained and the slurry concentration is not too low. Specifically, the amount of water is 100 per 100 g of ethylenediaminephosphate. It is preferred to use ~ 500 ml of water. If the slurry concentration is too high, the particles tend to aggregate, and the metal may not be uniformly bonded to the ethylenediamine phosphate particles. Moreover, when the slurry concentration is too low, dissolution of ethylenediamine phosphate in water becomes remarkable and the yield decreases, and the reaction rate of the charged metal salt to ethylenediamine phosphate may decrease.
[0015]
The method for adding the metal salt is not particularly limited, and the metal salt aqueous solution may be added to the ethylenediamine phosphate powder, or the metal salt aqueous solution may be dropped into the ethylenediamine phosphate aqueous dispersion slurry.
[0016]
The particle diameter of ethylenediamine phosphate used in the method of the present invention is not particularly specified, but those having an average particle diameter in the range of 1 to 100 μm are suitable. If it is less than 1 μm, the dissolution rate in water may increase and the yield may decrease. On the other hand, when it exceeds 100 μm, the reaction rate of the charged metal salt to ethylenediamine phosphate may be lowered, and when it is blended with a resin, the physical properties may be lowered.
[0017]
About reaction temperature, in order to avoid melt | dissolution of ethylenediamine phosphate in water, it is preferable to make it as low temperature as possible, and the range of 0-30 degreeC is preferable.
[0018]
After the reaction operation, the metal-containing ethylenediamine phosphate is obtained by drying the powder obtained by filtering the reaction mixture at 70 to 150 ° C.
[0019]
The metal-containing ethylenediamine phosphate obtained by the present invention is useful as a flame retardant and can be blended into various resins.
[0020]
Usable resins include, for example, thermosetting resins such as phenol resin, urea resin, melamine resin, unsaturated polyester, alkyd resin, epoxy resin, low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, Polypropylene, polystyrene, high-impact polystyrene, expanded polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer (ABS), petroleum resin, polymethyl methacrylate, polyamide, polycarbonate, polyacetal, polyethylene terephthalate, polybutylene terephthalate , Polyphenylene ether, and thermoplastic resin such as polycarbonate / ABS mixed resin. The metal-containing ethylenediamine phosphate of the present invention is particularly suitable for low-density polyethylene. Rene, high density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-α olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, etc. Suitable for flame retarding of polyolefin.
[0021]
The compounding amount of the metal-containing ethylenediamine phosphate of the present invention in the resin varies depending on the type of resin to be blended and the intended flame retardancy, but it is blended in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the resin Is preferred.
[0022]
In the resin composition containing the metal-containing ethylenediamine phosphate of the present invention, another flame retardant may be used in combination with 1 to 100 parts by weight, if necessary. Also, 0.05 to 5% by weight of a benzotriazole-based ultraviolet absorber, a light stabilizer such as a 2,2,6,6-tetramethylpiperidine derivative, a hindered phenol-based antioxidant, etc. Also good. In addition, if necessary, an inorganic filler such as an antistatic agent or talc may be added.
[0023]
As a method for blending the metal-containing ethylenediamine phosphate of the present invention into a resin, when it is blended in a thermosetting resin, it is preliminarily dispersed in a resin raw material and then cured. When blended with a thermoplastic resin, for example, a necessary blending reagent may be mixed using a conical blender, a tumbler mixer, or the like, and pelletized using a twin screw extruder or the like. The processing method of the resin composition thus obtained is not particularly limited, and for example, the target molded product can be obtained by performing extrusion molding, injection molding or the like.
[0024]
【The invention's effect】
The metal-containing ethylenediamine phosphate of the present invention is useful as a flame retardant, and by using this, a flame retardant resin composition excellent in flame retardancy and resin physical properties can be obtained.
[0025]
【Example】
EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to an Example.
[0026]
(Preparation of metal-containing ethylenediamine phosphate)
Example 1
A 2 l flask equipped with a stirrer, a dropping funnel, a thermometer, and a condenser is charged with 300 g of ethylenediamine phosphate having an average particle diameter of 11 μm and 600 ml of (distilled) water, and stirred at a liquid temperature of 15 ° C. A solution prepared by dissolving 76.2 g of magnesium chloride hexahydrate (9.0 g of magnesium, 3.0% by weight with respect to ethylenediamine phosphate) in 200 ml of water from a dropping funnel for 15 minutes. The mixture was added dropwise and stirred for 2 hours after completion of the addition. The reaction mixture was then filtered and dried at 90 ° C. to obtain ethylenediamine phosphate containing 2.7% magnesium in a yield of 253 g.
[0027]
Example 2
The same procedure as in Example 1 was carried out except that 25.4 g of magnesium chloride hexahydrate (3.0 g of magnesium, 1.0 wt% based on ethylenediamine phosphate) was used. An ethylenediamine phosphate containing 0.9% magnesium was obtained in a yield of 255 g.
[0028]
Example 3
The same procedure as in Example 1 was performed, except that 19.2 g of zinc chloride (9.0 g of zinc content, 3.0 wt% with respect to ethylenediamine phosphate) was used. An ethylenediamine phosphate containing 3.2% zinc was obtained in a yield of 237 g.
[0029]
Example 4
The same procedure as in Example 1 was carried out except that 6.4 g of zinc chloride (3.0 g of zinc content, 1.0 wt% with respect to ethylenediamine phosphate) was used. An ethylenediamine phosphate containing 1.0% zinc was obtained in a yield of 257 g.
[0030]
Example 5
The same procedure as in Example 1 was performed except that 25.0 g of calcium chloride (9.0 g of calcium content, 3.0 wt% with respect to ethylenediamine phosphate) was used. An ethylenediamine phosphate containing 2.9% calcium was obtained in a yield of 277 g.
[0031]
(Preparation of comparative reference compounds)
Reference example 1
The same procedure as in Example 1 was conducted, except that 127.0 g of magnesium chloride hexahydrate (magnesium content: 15.0 g, 5.0 wt% based on ethylenediamine phosphate) was used. An ethylenediamine phosphate containing 4.9% magnesium was obtained in a yield of 239 g.
[0032]
Reference example 2
The same procedure as in Example 1 was performed, except that 2.5 g of magnesium chloride hexahydrate (0.3 g of magnesium content, 0.1 wt% with respect to ethylenediamine phosphate) was used. An ethylenediamine phosphate containing 0.1% magnesium was obtained in a yield of 274 g.
[0033]
Reference example 3
The same procedure as in Example 1 was carried out except that 50.0 g of calcium chloride (calcium content: 18.0 g, 6.0 wt% based on ethylenediamine phosphate) was used. An ethylenediamine phosphate containing 5.8% calcium was obtained in a yield of 271 g.
[0034]
Evaluation as a flame retardant resin composition was performed by the following method.
[0035]
(Combustion test)
The measurement of the oxygen index based on JIS-K-7201 and the UL combustion test based on the UL94V vertical flammability test were performed.
[0036]
(Fluidity during processing)
Based on JIS-K-7210, the melt flow rate when a load of 2.16 kg was applied at 230 ° C. was measured.
[0037]
(Measurement of resin density)
Measurement was performed by an underwater substitution method in accordance with JIS-K-7112.
[0038]
(Tensile test) In accordance with JIS-K-7113, a No. 2 test piece described in JIS-K-7113 was used.
[0039]
(water resistant)
Evaluation was performed by measuring the dissolution rate of a flame retardant when a 0.5 × 1.5 × 0.125 inch (about 1.7 g) test piece was immersed in 100 ml of hot water at 70 ° C. for 2 days.
[0040]
(Volume resistivity)
The resistance (Ω · cm) when a voltage of DC 500 V was applied to a test piece having a thickness of about 2 mm was measured.
[0041]
(Evaluation of flame retardant resin composition containing metal-containing ethylenediamine phosphate)
Example 6
45 parts by weight of magnesium-containing ethylenediamine phosphate obtained by the method of Example 1 was blended with respect to 100 parts by weight of polypropylene (7030B manufactured by Tosoh Corporation), and roll kneading was performed at 180 ° C. The resin composition obtained by roll kneading was press-molded at 190 ° C. and 120 kg / cm 2 for 4 minutes to obtain various test pieces for evaluation and measurement and evaluation. The results are shown in Table 1.
[0042]
[Table 1]

[0043]
Example 7 to Example 12
Various methods were used in the same manner as in Example 6 except that the metal-containing ethylenediamine phosphate obtained by the methods of Examples 2 to 5 was kneaded in an amount as shown in Table 1 with respect to 100 parts by weight of polypropylene. Test specimens for evaluation were obtained and measured and evaluated. The results are also shown in Table 1.
[0044]
Example 13
50 mg of the magnesium-containing ethylenediamine phosphate obtained by the method of Example 1 with respect to 100 parts by weight of an ethylene-ethyl acrylate copolymer (Lextron A1150 manufactured by Nisseki Chemical Co., Ltd.) having an ethyl acrylate content of 15% by weight. Part by weight was blended and roll kneading was performed at 150 ° C. The resin composition obtained by roll kneading was press-molded at 180 ° C. and 120 kg / cm 2 for 4 minutes to obtain various test pieces for evaluation and measurement and evaluation. The results are shown in Table 2.
[0045]
[Table 2]

[0046]
Example 14 to Example 16
Various test pieces for evaluation were obtained and evaluated by the same method as in Example 13 except that the metal-containing ethylenediamine phosphate obtained by the methods of Examples 3 to 5 was used. The results are also shown in Table 2.
[0047]
Comparative Examples 1 to 5
By the method similar to Example 6 except having used the metal-containing ethylenediamine phosphate obtained by the method of Reference Example 1 to Reference Example 3 and the ethylenediamine phosphate having an average particle diameter of 11 μm that was not reacted with the metal salt. Various test pieces for evaluation were obtained and measured and evaluated. The results are also shown in Table 1.
[0048]
Comparative Example 6 to Comparative Example 8
Various methods were used in the same manner as in Example 13 except that the metal-containing ethylenediamine phosphate obtained by the method of Reference Examples 1 to 3 and the ethylenediamine phosphate having an average particle size of 11 μm not reacted with the metal salt were used. Test specimens for evaluation were obtained and measured and evaluated. The results are also shown in Table 2.

Claims (6)

Ethylenediamine, phosphoric acid, and Ri Do from Group IIA or Group IIB metal, ethylenediamine phosphate, characterized in that the Group IIA or Group IIB metal containing 0.2 to 4% by weight. The metal-containing ethylenediamine phosphate according to claim 1, wherein the Group IIA or Group IIB metal is magnesium. The method for producing a metal-containing ethylenediamine phosphate according to claim 1 or 2, wherein ethylenediaminephosphate dispersed in an aqueous solution is reacted with a metal salt. A flame retardant resin composition comprising a resin and the metal-containing ethylenediamine phosphate according to any one of claims 1 to 3 . The flame-retardant resin composition according to claim 4 , wherein the metal-containing ethylenediamine phosphate is blended in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the resin. The flame retardant resin composition according to claim 4 or 5 , wherein the resin is a polyolefin.