JPH0940686A - Ethylenediaminephosphatozinc, its production and flame retardant resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound for a flame retardant, etc., having a X-ray diffraction pattern with a specific lattice distance and capable of giving a resin composition having a little smoke generation by mixing a zinc-containing aqueous solution with ethylenediamine and subsequently reacting the mixture with phosphoric acid. SOLUTION: Ethylenediaminephosphatozinc having the following X-ray diffraction pattern [lattice distance (d) (angstrom); 2θ(determined with CuKα-ray of 1.5405 angstrom); relative strength (VS; very strong, S; strong, M; medium, W; weak)]: (6.89±0.30; 12.8; VS), (6.86±0.30; 13.3; S), (4.20±0.10; 21.1; W), (4.09±0.10; 21.7; S-W), (3.79±0.08; 23.4; S), (3.38±0.07; 26.3; S), (3.32±0.05; 26.8; W), (3.14±0.05; 28.4; M), (28.2±0.04; 31.7; M), (27.4±0.04; 32.6; S-M), (27.0±0.04; 33.1; M) and (26.0±0.04; 34.4; W). The compound is obtained by reacting a zinc-containing aqueous solution with ethylenediamine to produce a complex and reacting the complex with phosphoric acid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to zinc ethylenediamine phosphate, a method for producing the same, and uses thereof. The flame-retardant resin composition containing ethylenediamine zinc phosphate is widely used as a material for various electric parts, automobile parts, building materials, cables and the like.

[0002]

2. Description of the Related Art Plastic materials (resins) typified by polyethylene, polypropylene, polystyrene, vinyl chloride, etc. are used for electric parts, automobile parts, building materials, cables,
It is often used for structural materials such as ships. Generally, when a flammable plastic material is used as a structural material, it is used by adding a flame retardant to the material to impart flame retardancy. Conventionally used flame retardants include phosphoric acid esters, ammonium polyphosphate, red phosphorus, phosphorus-based flame retardants such as amine phosphate, tetrabromobisphenol A,
There are halogen-based flame retardants such as decabromodiphenyl oxide and chlorinated paraffin, and inorganic flame retardants such as magnesium hydroxide, aluminum hydroxide and zinc borate. Of these, halogen-based flame retardants have excellent flame retardancy and are widely used.

[0003]

However, a resin containing a halogen-based flame retardant releases a harmful halogen-containing gas during combustion. In addition, there is a problem that a lot of smoke is generated.

Generation of harmful gas and smoke increases personal injury at the time of fire, and the safety of materials including low harmful gas and low smoke is an important technique together with flame retardant technology. There is.

Inorganic flame retardants typified by magnesium hydroxide are materials capable of reducing harmful gas and smoke, but are not always satisfactory in terms of flame retardancy and decomposition temperature. The current situation.

The present invention has been made in view of the above problems, and an object thereof is to propose a new flame-retardant resin composition that does not generate harmful gas and emits a small amount of smoke.

[0007]

Means for Solving the Problems In order to develop a flame-retardant resin composition which is excellent in flame retardancy, does not generate harmful gas, and emits a small amount of smoke, the present inventors have paid particular attention to the flame retardant compounded in the resin. As a result of earnestly studying, the flame-retardant resin composition containing ethylenediamine zinc phosphate in the resin is a flame-retardant resin composition having excellent flame-retardant effect, harmful gas generation suppressing effect, and low smoke-producing effect. The present invention has been completed and the present invention has been completed.

That is, the present invention relates to zinc ethylenediamine phosphate, a method for producing the same, and uses thereof. Specifically, zinc ethylenediamine phosphate characterized by an X-ray diffraction pattern including a specific plane spacing, and a zinc-containing aqueous solution and ethylenediamine are mixed to generate a trisethylenediamine zinc complex, and then reacted with phosphoric acid. The present invention relates to a method for producing zinc ethylenediamine phosphate characterized by synthesizing, and a flame-retardant resin composition obtained by mixing 5 to 200 parts by weight of zinc ethylenediamine phosphate with 100 parts by weight of resin.

The present invention will be described in detail below.

The zinc ethylenediamine phosphate of the present invention is
At least the table below

[0011]

[Table 2]

It is a compound characterized by an X-ray diffraction pattern including the interplanar spacing shown in, and the X-ray diffraction pattern measured by CuKα ray is as shown in FIG. Although the composition formula is unknown, from the result of the composition analysis, the Zn / P molar ratio is 1/1,
It is a compound having an N / P molar ratio of 1/1.

H ₂ NC _{2 in} zinc ethylenediamine phosphate
H ₄ NH ₂ is released at about 360 ° C, and Z at about 700 ° C.
The structure changes to n ₂ P ₂ O ₇ . The decomposition temperature of a typical inorganic flame retardant is about 340 ° C. for magnesium hydroxide and about 200 ° C. for aluminum hydroxide. The zinc ethylenediamine phosphate of the present invention has a higher decomposition temperature than conventional inorganic flame retardants, and can be used as a flame retardant for resins that cannot be applied due to high processing temperatures. It is a highly versatile material.

The powdery physical properties of ethylenediamine zinc phosphate are not particularly limited, but the secondary particle size is 1 to 20 μm, BET
The specific surface area is about 0.1 to ²⁰ m ² / g. When the secondary particle size exceeds 20 μm, it may not be preferable in terms of dispersibility when blended with a resin.

Next, the method for producing the zinc ethylenediamine phosphate of the present invention will be described.

The ethylenediamine zinc phosphate of the present invention is
Synthesis of trisethylenediamine zinc complex by mixing zinc-containing aqueous solution and ethylenediamine, crystallization by reaction of trisethylenediamine zinc complex with phosphoric acid, filtration, washing,
It is manufactured through the steps of drying and crushing. Although the detailed crystallization mechanism is unknown, it is an essential technique to obtain the zinc ethylenediaminephosphate of the present invention by reacting the trisethylenediaminezinc complex with phosphoric acid for production.

The trisethylenediamine zinc complex is [Z
n (H ₂ NC ₂ H ₄ NH ₂ ) ₃ ] ²⁺ , a complex in which ethylenediamine is coordinated with Zn ^{2+ in} a octahedral 6-coordination. The method for producing the trisethylenediamine zinc complex is not particularly limited, and for example, it is obtained by mixing the zinc-containing aqueous solution and ethylenediamine at a zinc / ethylenediamine molar ratio of 1/4 to 1/3 while stirring at a temperature of 5 to 90 ° C. . The concentration of the zinc-containing aqueous solution is several mol / l, and the zinc-containing aqueous solution dissolves water-soluble salts such as zinc nitrate, zinc chloride and zinc sulfate in water, and zinc compounds such as zinc oxide and zinc hydroxide are nitric acid. It may be prepared by dissolving it in an aqueous solution of hydrochloric acid, sulfuric acid or the like.

The reaction between the trisethylenediamine zinc complex and phosphoric acid is carried out by mixing an aqueous solution of trisethylenediamine zinc complex and an aqueous solution of phosphoric acid. The mixing ratio of the trisethylenediamine zinc complex and phosphoric acid is about 2/1 to 1/2 (molar ratio), and it is preferable to mix them while stirring in order to make the inside of the reaction tank uniform. The temperature at this time is 5 to 90
It is sufficient that the temperature and the homogenization time are about 5 minutes to 3 days.

The crystallized zinc ethylenediamine phosphate is washed after solid-liquid separation. The solid-liquid separation method is not particularly limited, and includes Nutsche, drum filter, filter press,
Examples include belt filters. The amount of washing water is not particularly limited, and washing may be performed until the unreacted substances are removed.

Next, drying is carried out, but the temperature at the time of drying is not particularly limited and may be 60 to 250 ° C.

It is crushed more lightly, but it may be crushed by a method such as an automatic mortar or a hammer mill.

The ethylenediamine zinc phosphate of the present invention can be produced by the above method.

The flame-retardant resin composition of the present invention contains zinc ethylenediamine phosphate in an amount of 5 to 2 with respect to 100 parts by weight of the resin.
00 parts by weight, particularly preferably 50 to 150 parts by weight, is the composition. Zinc ethylenediamine phosphate 5 to 2
The flame-retardant resin composition blended with 00 parts by weight is preferable because it has an excellent flame-retardant effect and can significantly prevent deterioration of the mechanical properties of the resin.

The resin can be used without particular limitation depending on the application.

For example, polyethylene, polypropylene,
It is a homopolymer or copolymer of an olefin-based monomer such as an ethylene-propylene copolymer, an ethylene-propylene-diene monomer terpolymer, an ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer. Polyolefin, styrene homopolymer, rubber modified polystyrene, rubber and acrylonitrile or (meth)
Polyesters such as polystyrene, poly (meth) acrylic resins, polyethylene terephthalate, polybutylene terephthalate, polyarylate which are homopolymers or copolymers mainly composed of vinyl aromatic monomers such as graft polymers of acrylate and styrene. , 6-nylon,
6,6-nylon, 12-nylon, 46-nylon,
Polyamide such as aromatic polyamide, polyphenylene ether, modified polyphenylene ether, polyether such as polyoxymethylene, polycarbonate, styrene-conjugated diene copolymer, polybutadiene, polyisoprene,
Examples thereof include acrylonitrile-butadiene copolymer, rubber such as polychloroprene, polyvinyl chloride and the like. Also,
Phenolic resin, epoxy resin, unsaturated polyester,
Thermosetting resins such as polyurethane may also be used. These resins may be used alone or in combination of two or more.

Examples of the method of blending the flame retardant with the resin include roll kneading, kneader kneading, extrusion kneading, Banbury kneading, etc., but the method is not particularly limited and may be a method suitable for the resin used. .

The flame-retardant resin composition of the present invention can be prepared by the above method.

Zinc ethylenediamine phosphate of the present invention,
The combined use of a 1,3,5-triazine derivative is preferable because the flame retardancy is further improved.

The 1,3,5-triazine derivative of the present invention is not particularly limited as long as it has a 1,3,5-triazine skeleton, but 1,3,5-triazine, melamine, methylolated melamine, Examples thereof include (iso) cyanuric acid and its salts and esters with melamine and the like.

When the 1,3,5-triazine derivative is used in combination, the composition of the flame-retardant resin is such that zinc ethylenediamine phosphate is 5 to 200 parts by weight, particularly preferably 50 to 150 parts by weight, based on 100 parts by weight of the resin. 2 to 100 parts by weight of 1,3,5-triazine derivative, particularly preferably 15 to 4
5 parts by weight. A flame-retardant resin composition containing 5 to 200 parts by weight of ethylenediamine zinc phosphate and 2 to 100 parts by weight of a 1,3,5-triazine derivative with respect to 100 parts by weight of a resin is excellent in flame retardant effect, and is a resin. It is preferable because it is possible to prevent the deterioration of mechanical properties.

If desired, other additives may be added to the flame-retardant resin composition of the present invention. Examples of the additive include other flame retardants, flame retardant aids, plasticizers, lubricants, fillers, antioxidants, and UV inhibitors. Also,
A cross-linking agent, a cross-linking aid and the like can also be used.

[0032]

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

Example 1 A trisethylenediamine zinc complex was synthesized by adding ethylenediamine in an amount of a zinc / ethylenediamine molar ratio of 1/3 to a 2 mol / l zinc nitrate aqueous solution. To this aqueous solution was added phosphoric acid in an amount such that the zinc / phosphoric acid molar ratio was 1/1, and the mixture was reacted at 25 ° C. for 1 hour, followed by solid-liquid separation,
Zinc ethylenediamine phosphate was prepared by washing and drying (hereinafter, this powder is abbreviated as "flame retardant 1"). The X-ray diffraction diagram of the flame retardant 1 is shown in FIG. The values of the interplanar spacings obtained from FIG. 1 are also shown in the table below together with the peak intensities of the diffraction lines.

[0034]

[Table 3]

50 parts by weight of flame retardant 1 was mixed with 100 parts by weight of low-density polyethylene (trade name "PETROSEN 202" manufactured by Tosoh Corporation), and after roll kneading at a temperature of 105 ° C, press molding was performed at a temperature of 150 ° C. Then, a flame-retardant resin composition was prepared.

The flame retardancy was evaluated according to the combustion test method for polymer materials by the oxygen index method standardized in JIS K 7201, and the oxygen index was 21.

Example 2 Low density polyethylene (manufactured by Tosoh Corporation, trade name "Petrosene 2"
02 ") 100 parts by weight of flame retardant 1 was mixed with 100 parts by weight to prepare a flame retardant resin composition in the same manner as in Example 1.

The flame retardancy was evaluated in the same manner as in Example 1, and the oxygen index was 24.

Example 3 Low density polyethylene (manufactured by Tosoh Corporation, trade name "Petrosene 2"
02 "), 150 parts by weight of flame retardant 1 was added to 100 parts by weight of the mixture, and a flame-retardant resin composition was prepared in the same manner as in Example 1.

The flame retardancy was evaluated by the same method as in Example 1, and the oxygen index was 28.

Example 4 Low-density polyethylene (manufactured by Tosoh Corporation, trade name "Petrosene 2"
02 ") 100 parts by weight of flame retardant 1 and 28 parts by weight of melamine were mixed to prepare a flame retardant resin composition in the same manner as in Example 1.

The flame retardancy was evaluated by the same method as in Example 1, and the oxygen index was 29.

Comparative Example 1 Low-density polyethylene (manufactured by Tosoh Corporation, trade name "Petrosene 2"
02 ") and 100 parts by weight of zinc phosphate (manufactured by Kishida Chemical Co., Ltd.) were mixed, and a flame-retardant resin composition was prepared in the same manner as in Example 1.

The flame retardancy was evaluated by the same method as in Example 1, and the oxygen index was 19.

Comparative Example 2 Low density polyethylene (manufactured by Tosoh Corporation, trade name "Petrosene 2"
02 ″), 100 parts by weight of zinc phosphate (manufactured by Kishida Chemical Co., Ltd.) and 28 parts by weight of melamine were mixed, and a flame-retardant resin composition was prepared in the same manner as in Example 1.

The oxygen index measured by the same method as in Example 1 was 19.

Comparative Example 3 Low density polyethylene (manufactured by Tosoh Corporation, trade name "Petrosene 2"
02 ") and 100 parts by weight of magnesium hydroxide (trade name" Kismar 5A-1 ", manufactured by Kyowa Chemical Co., Ltd.), and a flame-retardant resin composition was prepared in the same manner as in Example 1. did.

The flame retardancy was evaluated by the same method as in Example 1, and the oxygen index was 24.

Comparative Example 4 Low density polyethylene (manufactured by Tosoh Corporation, trade name "Petrosene 2"
02 ") 100 parts by weight, and 100 parts by weight of magnesium hydroxide (Kyowa Chemical Co., Ltd., trade name" Kismer 5A-1 ") and 28 parts by weight of melamine are mixed, and flame retardancy is obtained by the same method as in Example 1. A resin composition was prepared.

The oxygen index measured by the same method as in Example 1 was 24, and no synergistic effect with melamine was observed.

[0051]

EFFECTS OF THE INVENTION The flame-retardant resin composition of the present invention has excellent flame retardancy, does not generate a harmful gas, and has a small amount of smoke and high performance. Also, the ethylenediamine zinc phosphate of the present invention has a higher decomposition temperature than conventional inorganic flame retardants,
It is a versatile material that can be used as a flame retardant even for resins that cannot be applied due to its high processing temperature.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction diagram showing a crystal structure of a flame retardant 1 in Example 1.

Claims (5)

[Claims] 1. At least the following table Zinc ethylenediamine phosphate characterized by an X-ray diffraction pattern including the interplanar spacing shown in. 2. The method for producing zinc ethylenediamine phosphate according to claim 1, wherein the zinc-containing aqueous solution is mixed with ethylenediamine to form a trisethylenediamine zinc complex, and then the trisethylenediamine zinc complex is reacted with phosphoric acid for synthesis. . 3. A flame-retardant resin composition obtained by blending 5 to 200 parts by weight of the ethylenediamine zinc phosphate according to claim 1 with respect to 100 parts by weight of the resin. 4. A flame-retardant resin composition comprising the flame-retardant resin composition according to claim 3 and 2 to 100 parts by weight of a 1,3,5-triazine derivative. 5. The 1,3,5-triazine derivative is one or more selected from the group consisting of melamine, cyanuric acid, cyanuric acid derivative, isocyanuric acid, isocyanuric acid derivative, melamine cyanurate and melamine isocyanurate. The flame-retardant resin composition according to claim 4, wherein the flame-retardant resin composition is present.