JPH10259275A - Flame retardant and flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant, capable of manifesting excellent flame retardance and water resistance, suppressing the deterioration in mechanical properties and generation of toxic gases and imparting good flame restadance and low smoking properties to a resin and useful as the resin, etc., for building materials by using a halogen-based flame retardant with a specific phosphate in combination. SOLUTION: This flame retardant is that composed of (A) a halogen-based flame retardant such as a compound represented by the formula A is an alkylene, carbonyl or an ether group; X is bromine or chlorine; (a) and (b) are each a number so as to provide [(a)+(b)] with 1-10} and (B) ethylenediamine-zinc phophosphate and is obtained by compounding the components A with B so as to afford usually 1-15, preferably 4-13 weight ratio of the halogen to zinc. The flame retardant is preferably compounded in an amount of preferably 5-100 pts.wt. based on 100 pts.wt. resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame retardant comprising a halogen-based flame retardant and zinc ethylenediamine phosphate, and a flame-retardant resin composition comprising the same. The flame-retardant resin composition containing the flame retardant of the present invention has excellent flame retardancy and 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 Various plastic materials (resins) are used for insulation materials and sheath materials for electric wires and cables, electric / electronic / OA.
It is widely used for packaging materials and internal parts of equipment, vehicle interior materials, building materials, and the like. However, when plastic materials that are flammable materials are used in the above-mentioned applications,
It is used by adding a flame retardant to a plastic material to impart flame retardancy.

Conventionally used flame retardants include:
Phosphorus flame retardants such as phosphate esters, ammonium polyphosphate, and red phosphorus; halogen flame retardants such as tetrabromobisphenol A, decabromodiphenyl ether, and chlorinated paraffin; inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide Etc.

[0004]

However, phosphorus-based flame retardants are not satisfactory materials. For example, ammonium polyphosphate has a problem of poor flame retardancy and water resistance. There was a problem that it occurred.

[0005] In addition, although inorganic flame retardants are excellent in suppressing smoke emission, they have a small flame retarding effect, so that a high content of inorganic flame retardants is required to impart sufficient flame retardancy to resins. As a result, there has been a problem that the mechanical properties of the resin composition are greatly deteriorated.

[0006] Halogen-based flame retardants are materials having excellent flame-retardant effects and are widely used. However, development of flame-retardants having further excellent flame-retardant effects is eagerly desired.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a new high-performance flame retardant excellent in flame-retardant effect and a new flame-retardant resin composition using the same. To provide.

[0008]

Means for Solving the Problems In order to develop a flame-retardant resin composition having excellent flame retardancy, the present inventors have concentrated on the development of a high-performance flame retardant having excellent flame retardancy and made intensive studies. As a result,
The present invention has been completed.

That is, the present invention provides a flame retardant comprising a halogen-based flame retardant and zinc ethylenediamine phosphate;
The flame retardant resin composition is obtained by blending 5 to 100 parts by weight of the flame retardant with respect to 00 parts by weight.

Hereinafter, the present invention will be described in detail.

The flame retardant of the present invention is a flame retardant comprising a halogen-based flame retardant and zinc ethylenediamine phosphate. Although the detailed reason is unknown, the flame retardant effect of the halogen-based flame retardant and ethylenediamine zinc phosphate has a synergistic effect,
The flame retardant of the present invention is a material having an excellent flame retardant effect.

In the present invention, zinc ethylenediamine phosphate is a compound of ethylenediamine and zinc phosphate, and is not particularly limited.
n ₂ P ₂ O ₈ C ₂ N ₂ H ₁₀ , and an X-ray diffraction pattern at least

[0013]

[Table 1]

[0014] Zinc ethylenediamine phosphate (hereinafter abbreviated as EDA-ZP1) containing the plane spacing shown in
X-ray diffraction pattern at least as shown in Table 2

[0015]

[Table 2]

And zinc ethylenediamine phosphate (hereinafter abbreviated as EDA-ZP2) containing the plane spacing shown in (1).

[0017] EDA-ZP1 is tetrahedral ZnO ₄ and tetrahedral PO ₄ 3-dimensional open framework formed by ZnPO ₄ ^- and the _{H 3 NC 2 H 4 NH 3} 2+ is occluded (R. H. Jon
es et al., Studies in Surface Se
ence and Catalysis, Zeoli
tes and Related Microporo
us Materials, Vol. 84, p. 222
9 (1994), Elsevier Science
B. V. FIG. 1 shows an X-ray diffraction pattern measured using CuKα rays.

Although the detailed crystal structure of EDA-ZP2 is unknown, the X-ray diffraction pattern measured using CuKα radiation is as shown in FIG.

The decomposition temperature of the ethylenediamine zinc phosphate used in the present invention is about 400 ° C., which is a material having excellent heat resistance. The powder physical properties of the ethylenediamine zinc phosphate are not particularly limited, but the BET specific surface area is 0.1 to
20 m ² / g, secondary particle size is about 20 μm or less.

The method for producing the zinc ethylenediamine phosphate of the present invention is not particularly limited, but EDA-ZP1, EDA
A preferred embodiment will be described with reference to -ZP2 as an example.

The zinc ethylenediamine phosphate of the present invention comprises
It is manufactured through the steps of crystallization, filtration, washing and drying of zinc ethylenediamine phosphate.

Crystallization of EDA-ZP1 is performed by mixing an aqueous zinc phosphate solution and an aqueous ethylenediamine solution.

The aqueous zinc phosphate solution is prepared by mixing a zinc compound and phosphoric acid in an amount such that the zinc / phosphorus ratio (molar ratio) is 0.1 to 0.4, and dissolving the mixture uniformly. Examples of the zinc compound include, but are not particularly limited to, zinc hydroxide, zinc oxide, zinc hydrogen phosphate, zinc dihydrogen phosphate, and the like, and water-soluble salts such as zinc chloride and zinc nitrate. The concentration of phosphoric acid is not particularly limited, and may be performed at a concentration of 14 to 85 wt%.

The zinc phosphate aqueous solution and ethylenediamine are mixed at an ethylenediamine / phosphorus ratio (molar ratio) of 0.5.
Mix in an amount of ~ 2.0. The concentration of ethylenediamine is not particularly limited, and may be a concentration of 5 to 100% by weight. Mixing methods include, but are not limited to, mixing methods such as adding an aqueous solution of ethylene diamine to an aqueous solution of zinc phosphate, adding an aqueous solution of zinc phosphate to an aqueous solution of ethylene diamine, and continuously adding an aqueous solution of zinc phosphate and an aqueous solution of ethylene diamine to a reaction vessel. Not done. Mixing is preferably performed with stirring to make the inside of the reaction tank uniform. It is sufficient that the temperature at the time of mixing is 5 to 90 ° C. and the homogenization time is about 5 minutes to 3 days.

The crystallization of EDA-ZP2 is carried out by mixing a zinc salt aqueous solution and ethylenediamine to form a trisethylenediamine zinc complex, and reacting the trisethylenediamine zinc complex with phosphoric acid.

The trisethylenediamine zinc complex is [Zn
(H ₂ NC ₂ H ₄ NH ₂ ) ₃ ] ²⁺ is a complex in which ethylenediamine is coordinated with Zn ^{2+ in} a octahedral hexacoordinate. The method for producing the trisethylenediamine-zinc complex is not particularly limited. For example, it can be obtained by mixing a zinc salt aqueous solution and ethylenediamine at a molar ratio of 0.33 while stirring at a temperature of 5 to 90 ° C. The concentration of the aqueous zinc salt solution is several mol / l, and examples of the zinc salt include water-soluble salts such as zinc nitrate, zinc chloride, and zinc sulfate.

The reaction of the trisethylenediamine zinc complex with phosphoric acid may be carried out at a mixing ratio of trisethylenediamine zinc complex / phosphoric acid of about 0.5 to 2.0 (molar ratio). Mixing is preferably performed with stirring to make the inside of the reaction tank uniform. It is sufficient that the temperature at the time of mixing is 5 to 90 ° C. and the homogenization time is about 5 minutes to 3 days.

The crystallized zinc zinc ethylenediamine is
After solid-liquid separation, wash. The method of solid-liquid separation is not particularly limited, and examples thereof include a nutsche, a drum filter, a filter press, and a belt filter. The amount of washing water is not particularly limited, and washing may be performed until unreacted phosphoric acid and ethylenediamine are removed.

Next, the zinc ethylenediamine phosphate crystals are dried. The temperature at the time of drying is not particularly limited.
What is necessary is just to carry out at 50 degreeC.

The ethylenediamine zinc phosphate may be ground if necessary. Examples of the grinding method include an automatic mortar and a hammer mill, but are not particularly limited.

[0031] Zinc ethylenediamine phosphate can be produced by the above method.

The halogen-based flame retardant used in the flame retardant of the present invention is not particularly limited. For example, the following general formula (1)

[0033]

Embedded image

(Wherein, A represents an alkylene group, a carbonyl group or an ether group; X represents a bromine or chlorine atom.
a and b represent integers satisfying a + b = 1 to 10. A) a halogenated diphenyl compound represented by the following general formula (2)

[0035]

Embedded image

(Wherein B represents an alkylene group, a carbonyl group, an ether group, a thioether group or a sulfone group, and X represents a bromine or chlorine atom), a halogenated bisphenol compound represented by the following general formula (3) )

[0037]

Embedded image

(Wherein B represents an alkylene group, a carbonyl group, an ether group, a thioether group, or a sulfone group; X represents a bromine or chlorine atom; c and d are c + d =
Represents an integer satisfying 1 to 8. Y represents an alkyl halide represented by C _n H _{2n + 1-z} X _z , and n and z represent n = 1 to 8
And an integer satisfying z = 1 to 2n + 1. A) a halogenated bisphenol bis (alkyl ether) compound represented by the following general formula (4):

[0039]

Embedded image

(Wherein C represents an alkylene group, an alkyl ether group, a diphenylsulfone group, a diphenyl ketone group or a diphenyl ether group. X represents a bromine or chlorine atom. C and d satisfy c + d = 1 to 8). Represented by an integer.), Or one or more selected from the group consisting of halogenated phthalimide-based compounds represented by the formula:

Examples of the halogenated diphenyl compound represented by the general formula (1) include, for example, pentabromodiphenyl ether, hexabromodiphenyl ether, heptabromodiphenyl ether, octabromodiphenyl ether, nonabromodiphenyl ether, decabromodiphenyl ether, pentachlorodiphenyl ether, hexa Chlorodiphenyl ether, heptachlordiphenylether, octachlorodiphenylether,
Nonachlorodiphenyl ether, halogenated diphenyl ether compounds such as decachlor diphenyl ether,
Halogenated diphenylketone compounds such as dibromodiphenylketone, tribromodiphenylketone, tetrabromodiphenylketone, dichlorodiphenylketone, trichlorodiphenylketone, tetrachlorodiphenylketone, monobromodiphenylmethane, dibromodiphenylmethane, tribromodiphenylmethane, tetrabromodiphenylmethane , Pentabromodiphenylmethane,
Hexabromodiphenylmethane, heptabromodiphenylmethane, octabromodiphenylmethane, nonabromodiphenylmethane, decabromodiphenylmethane, monochlorodiphenylmethane, dichlorodiphenylmethane,
Trichlorodiphenylmethane, tetrachlorodiphenylmethane, pentachlorodiphenylmethane, hexachlorodiphenylmethane, heptachlorodiphenylmethane, octachlorodiphenylmethane, nonachlorodiphenylmethane, decachlorodiphenylmethane, monobromodiphenylethane, dibromodiphenylethane, tribromodiphenylethane, tetrabromodiphenylethane, penta Bromodiphenylethane, hexabromodiphenylethane, heptabromodiphenylethane, octabromodiphenylethane, nonabromodiphenylethane, decabromodiphenylethane, monochlorodiphenylethane,
Dichlorodiphenylethane, trichlorodiphenylethane, tetrachlorodiphenylethane, pentachlorodiphenylethane, hexachlorodiphenylethane, heptachlorodiphenylethane, octachlorodiphenylethane, nonachlorodiphenylethane, decachlorodiphenylethane, monobromodiphenylpropane, dibromodiphenylpropane , Tribromodiphenylpropane, tetrabromodiphenylpropane, pentabromodiphenylpropane, hexabromodiphenylpropane, heptabromodiphenylpropane, octabromodiphenylpropane, nanobromodiphenylpropane, decabromophenylpropane, monobromodiphenylpropane, dichlorodiphenylpropane, Trichlorodiphenylpropane, tetrachloro Phenylpropane, pentachlorophenol diphenyl propane, hexachloro-diphenyl propane,
Halogenated diphenylalkanes such as heptachlorodiphenylpropane, octachlorodiphenylpropane, nonachlorodiphenylpropane, and decachlorodiphenylpropane, and the like.Of these, decabromodiphenyl ether is particularly preferable in that it has excellent flame retardancy and price. It is.

As the halogenated bisphenol compound represented by the general formula (2), for example, bis (3,5)
-Dibromo-4-hydroxyphenyl) -2- (3-
Bromo-4-hydroxyphenyl) methane, 1-
(3,5-dibromo-4-hydroxyphenyl) -2
-(3-bromo-4-hydroxyphenyl) ethane,
1- (3,5-dibromo-4-hydroxyphenyl)
-3- (3-Bromo-4-hydroxyphenyl) propane, bis (3,5-dichloro-4-hydroxyphenyl) -2- (3-chloro-4-hydroxyphenyl) methane, 1- (3,5- Dichloro-4-hydroxyphenyl) -2- (3-chloro-4-hydroxyphenyl) ethane, 1- (3,5-dichloro-4-hydroxyphenyl) -3- (3-chloro-4-hydroxyphenyl) propane , Bis (3,5-dibromo-4-
Hydroxyphenyl) methane, 1,2-bis (3,5
-Dibromo-4-hydroxyphenyl) ethane, 1,
3-bis (3,5-dichloro-4-hydroxyphenyl) propane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 1,2-bis (3,5-dichloro-4-hydroxyphenyl) ethane Bisphenylalkanes such as 1,3-bis (3,5-dichloro-4-hydroxyphenyl) propane and bis (3,5-dibromo-4-hydroxyphenyl) -2
-(3-bromo-4-hydroxyphenyl) ketone,
Bis (3,5-dichloro-4-hydroxyphenyl)
-2- (3-chloro-4-hydroxyphenyl) ketone, bis (3,5-dibromo-4-hydroxyphenyl) ketone, bis (3,5-dichloro-4-hydroxyphenyl) ketone, bis (3,5 -Dibromo-4-hydroxyphenyl) -2- (3-bromo-4-hydroxyphenyl) ether, bis (3,5-dichloro-
4-hydroxyphenyl) -2- (3-chloro-4-
Halogenated bisphenyl ethers such as hydroxyphenyl) ether, bis (3,5-dibromo-4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) ether, bis (3,5-dibromo) -4-hydroxyphenyl) -2
-(3-bromo-4-hydroxyphenyl) thioether, bis (3,5-dichloro-4-hydroxyphenyl) -2- (3-chloro-4-hydroxyphenyl) thioether, bis (3,5-dibromo-4) Halogenated bisphenylthioethers such as -hydroxyphenyl) thioether and bis (3,5-dichloro-4-hydroxyphenyl) thioether;
Dibromo-4-hydroxyphenyl) -2- (3-bromo-4-hydroxyphenyl) sulfone, bis (3,5-dichloro-4-hydroxyphenyl) -2
Halogenated bisphenylsulfones such as-(3-chloro-4-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, bis (3,5-dichloro-4-hydroxyphenyl) sulfone Among them, bis (3,5-dibromo-4-hydroxyphenyl) sulfone is particularly preferable because of its excellent flame retardancy, price and the like.

Examples of the halogenated bisphenol bis (alkyl ether) compound represented by the general formula (3) include, for example, bis (3,5-dibromo-4-2,3 dibromopropoxyphenyl) -2- (3- Bromo-4-
2,3-dibromopropoxyphenyl) methane, 1-
(3,5-dibromo-4-2,3 dibromopropoxyphenyl) -2- (3-bromo-4-2,3 dibromopropoxyphenyl) ethane, 1- (3,5-dibromo-4)
-2,3 dibromopropoxyphenyl) -3- (3-bromo-4-2,3 dibromopropoxyphenyl) propane, bis (3,5-dichloro-4-2,3 dibromopropoxyphenyl) -2- (3- Chloro-4-2,3 dibromopropoxyphenyl) methane, 1- (3,5-dichloro-4-2,3 dibromopropoxyphenyl) -2-
(3-chloro-4-2,3 dibromopropoxyphenyl) ethane, 1- (3,5-dichloro-4-2,3 dibromopropoxyphenyl) -3- (3-chloro-4-
2,3 dibromopropoxyphenyl) propane, bis (3,5-dibromo-4-2,3 dibromopropoxyphenyl) methane, 1,2-bis (3,5-dibromo-4)
-2,3 dibromopropoxyphenyl) ethane, 1,3
-Bis (3,5-dibromo-4-2,3 dibromopropoxyphenyl) propane, bis (3,5-dichloro-4)
−2,3 dibromopropoxyphenyl) methane, 1,2
-Bis (3,5-dichloro-4-2,3 dibromopropoxyphenyl) ethane, 1,3-bis (3,5-dichloro-4-2,3 dibromopropoxyphenyl) propane, bis (3,5-dibromo -4-2,3 dibromopropoxyphenyl) -2- (3-bromo-4-2,3 dibromopropoxyphenyl) ketone, bis (3,5-dichloro-4-2,3 dibromopropoxyphenyl) -2-
(3-chloro-4-2,3 dibromopropoxyphenyl) ketone, bis (3,5-dibromo-4-2,3 dibromopropoxyphenyl) ketone, bis (3,5-dichloro-4-2,3 dibromopropoxy) Phenyl) ketone, bis (3,5-dibromo-4-2,3 dibromopropoxyphenyl) -2- (3-bromo-4-2,3 dibromopropoxyphenyl) ether, bis (3,5-dichloro-4- 2,3 dibromopropoxyphenyl) -2
-(3-chloro-4-2,3 dibromopropoxyphenyl) ether, bis (3,5-dibromo-4-2,3 dibromopropoxyphenyl) ether, bis (3,5-
Dichloro-4-2,3 dibromopropoxyphenyl) ether, bis (3,5-dibromo-4-2,3 dibromopropoxyphenyl) -2- (3-bromo-4-2,3
Dibromopropoxyphenyl) thioether, bis (3,5-dichloro-4-2,3dibromopropoxyphenyl) -2- (3-chloro-4-2,3dibromopropoxyphenyl) thioether, bis (3,5-dibromo- 4-2,3 dibromopropoxyphenyl) thioether, bis (3,5-dichloro-4-2,3 dibromopropoxyphenyl) thioether, bis (3,5-dibromo-4-2,3 dibromopropoxyphenyl) -2-
(3-bromo-4-2,3 dibromopropoxyphenyl) sulfone, bis (3,5-dichloro-4-2,3
Dibromopropoxyphenyl) -2- (3-chloro-4
-2,3 dibromopropoxyphenyl) sulfone, bis (3,5-dibromo-4-2,3 dibromopropoxyphenyl) sulfone, bis (3,5-dichloro-4-)
2,3-dibromopropoxyphenyl) sulfone, among which 2,2-bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) is particularly preferred.
Propane is preferred in that it is excellent in flame retardancy, price and the like.

Examples of the halogenated phthalimide compound represented by the general formula (4) include N, N '-(bistetrabromophthalimide) ethane, N, N'-(bistetrabromophthalimide) propane, N'-
(Bistetrabromophthalimide) butane, N, N'-
(Bistetrachlorophthalimide) ethane, N, N'-
(Bistetrachlorophthalimide) propane, N, N '
-(Bistetrachlorophthalimide) butane, N, N '
-(Bistetrabromophthalimide) diethyl ether, N, N '-(bistetrabromophthalimide) dipropyl ether, N, N'-(bistetrabromophthalimide) dibutylether, N, N '-(bistetrachlorophthalimide) Diethyl ether, N, N '-(bistetrachlorophthalimide) dipropyl ether,
N, N '-(bistetrachlorophthalimide) dibutyl ether, N, N'-(bistetrabromophthalimide) diphenylsulfone, N, N '-(bistetrachlorophthalimide) diphenylsulfone, N, N'-
(Bistetrabromophthalimide) diphenyl ketone,
N, N '-(bistetrachlorophthalimide) diphenyl ketone, N, N'-(bistetrabromophthalimide) diphenyl ether, N, N '-(bistetrachlorophthalimide) diphenyl ether, and the like. N ′-(bistetrabromophthalimide) ethane is preferred because it is excellent in flame retardancy, price, and the like.

The mixing ratio of the halogen-based flame retardant and the ethylenediamine zinc phosphate in the flame retardant of the present invention is not particularly limited, but the ratio (weight ratio) between the halogen content and the zinc content is as follows. Usually, it is 1 to 15, and 4 to 13 is particularly preferable because it shows a very excellent flame retardant effect.

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

The flame-retardant resin composition of the present invention comprises a resin 100
It is a composition in which 5 to 100 parts by weight, particularly preferably 30 to 80 parts by weight, of the flame retardant of the present invention is blended with respect to parts by weight.
If the amount of the flame retardant of the present invention is less than 10 parts by weight, the flame retardant effect is insufficient, which is not preferred. If it exceeds 100 parts by weight, the mechanical properties of the resin are undesirably reduced.

The resin can be used without any particular limitation depending on the application. For example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene monomer terpolymer, ethylene-ethyl acrylate copolymer, homopolymer of olefin-based monomers such as ethylene-vinyl acetate copolymer or Homopolymers or copolymers mainly composed of vinyl aromatic monomers such as polyolefins, homopolymers of styrene, rubber-modified polystyrene, graft polymers of rubber and acrylonitrile or (meth) acrylate and styrene, which are copolymers Certain polystyrene, poly (meth) acrylic resin, polyester such as polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyamide such as 6-nylon, 6,6-nylon, 12-nylon, 46-nylon, aromatic polyamide, poly Phenylene ether, modified polyphenylene ether, polyether such as polyoxymethylene, polycarbonate, styrene-conjugated diene copolymer, polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer, rubber such as polychloroprene, polyvinyl chloride and the like. Can be Further, a thermosetting resin such as a phenol resin, an epoxy resin, an unsaturated polyester, and a polyurethane is also used. These resins may be used alone or in combination of two or more.

The method of blending the flame retardant of the present invention with a resin is as follows.
A method of blending a master batch containing a halogen-based flame retardant and ethylenediamine zinc phosphate at a high concentration, a method of blending a flame retardant in which a halogen-based flame retardant and ethylenediamine zinc phosphate are preliminarily compounded into a resin, a method of blending a halogen-based flame retardant, A method of separately mixing zinc ethylenediamine phosphate with the resin is exemplified, but is not particularly limited. The method of compounding the halogen-based flame retardant and ethylenediamine zinc phosphate is not particularly limited, but examples thereof include a ball mill or vibration mill using a ball such as zirconia and urethane resin, a V-type blender, a raker, and the like. And a wet or dry method. A mixing time of several hours to several tens hours is sufficient.

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

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

The flame-retardant resin composition of the present invention may contain any other additives as necessary. Additives include other flame retardants, flame retardant aids, plasticizers, lubricants, fillers, antioxidants, heat stabilizers, crosslinking agents, crosslinking aids, antistatic agents, compatibilizers, light stabilizers, Pigments, foaming agents, anti-bleeding agents, fungicides and the like can be mentioned.

[0053]

The flame retardant of the present invention comprising a halogen-based flame retardant and ethylenediamine zinc phosphate is excellent in flame retardant effect, and the flame retardant resin composition of the present invention containing the flame retardant has flame retardancy.
It is excellent in low smoke emission and high performance in which generation of harmful gas is suppressed.

[0054]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Preparation Example 1 Preparation of EDA-ZP1 A zinc phosphate aqueous solution was prepared by dissolving 81.4 g of zinc oxide with stirring in a phosphoric acid aqueous solution prepared by adding 327 g of 75% phosphoric acid to 700 g of water.

An aqueous solution of ethylenediamine prepared by adding 75 g of ethylenediamine to 658 g of water was added to the above aqueous solution of zinc phosphate, and the slurry was homogenized at 25 ° C. for 3 hours to crystallize zinc ethylenediaminephosphate. After crystallization,
After solid-liquid separation by Nutsche filtration, washing with 3000 g of water, and drying at 110 ° C. for 16 hours, EDA-ZP1 was prepared. The X-ray diffraction of EDA-ZP1 appears at the positions shown in Table 1, and the X-ray diffraction pattern is shown in FIG.

Preparation Example 2 Preparation of EDA-ZP2 59.5 g of zinc nitrate hexahydrate was dissolved in 540 g of water.
36 g of ethylenediamine was added to the zinc nitrate aqueous solution to prepare a trisethylenediamine zinc complex aqueous solution.

An aqueous phosphoric acid solution prepared by adding 23.1 g of 85% phosphoric acid to 180 g of water was added to the above aqueous solution of trisethylenediamine zinc complex, and the slurry was homogenized at 30 ° C. for 1 hour to crystallize EDA-ZP2. Was. After crystallization, solid-liquid separation was performed by Nutsche filtration, washed with 3000 g of water, and dried at 110 ° C. for 16 hours to prepare EDA-ZP2. The X-ray diffraction of EDA-ZP2 appears at the positions shown in Table 2, and the X-ray diffraction pattern is shown in FIG.

Preparation Example 3 Preparation of Flame Retardant (1) EDA-ZP1 prepared in Preparation Example 1 and decabromodiphenyl ether (trade name “Frame Cut 610R” manufactured by Tosoh) in a weight ratio of 1: 5, respectively, as a halogen-containing compound. , 1: 3, 1: 2, and ball-mixing for 16 hours in a dry system using urethane resin balls to obtain a flame retardant 1,
Flame retardant 2 and flame retardant 3 were prepared. The ratio (weight ratio) between the halogen content and the zinc content of the flame retardant 1, the flame retardant 2, and the flame retardant 3 is 12.3, 5.1, and 4.9, respectively.

Preparation Example 4 Preparation of Flame Retardant (2) EDA-ZP2 prepared in Preparation Example 2 and decabromodiphenyl ether (trade name “Frame Cut 610R” manufactured by Tosoh) in a weight ratio of 1: 5, respectively, as a halogen-containing compound. , 1: 3, 1: 2, and ball mill mixing for 16 hours in a dry system using urethane resin balls to obtain a flame retardant 4,
Flame retardant 5 and flame retardant 6 were prepared. The ratio (weight ratio) between the halogen content and the zinc content of the flame retardant 4, flame retardant 5, and flame retardant 6 is 12.3, 5.1, and 4.9, respectively.

Example 1 Evaluation of Flame Retardancy with Low-Density Polyethylene Low-density polyethylene (trade name “Petrocene 2” manufactured by Tosoh Corporation
02 "), a predetermined amount of a flame retardant was roll-kneaded at a temperature of 105 ° C and then press-molded at a temperature of 150 ° C to prepare a flame-retardant resin composition.

The flame retardancy was evaluated in accordance with the combustion test method for polymer materials by the oxygen index method standardized in JIS K7201.

Table 3 shows the amounts of the respective flame retardants and the results of evaluation of the flame retardancy of the flame retardant resin composition.

[0064]

[Table 3]

Example 2 Evaluation of Flame Retardancy with Polypropylene 20 parts by weight of 2,2-bis (3,5-dibromo-4) was added to 100 parts by weight of a polypropylene resin (manufactured by Union Polymer, trade name "UP Polypro J7030B"). − (2,3-
Dibromopropoxy) phenyl) propane (Tosoh,
Product name “Frame Cut 121R”), 10 parts by weight of E
DA-ZP1 was added, these were mixed with a Henschel mixer, and extruded at a resin temperature of 200 ° C. with a twin-screw kneading extruder to produce pellets. Next, a test piece of the flame-retardant resin composition was prepared using an injection molding machine at a cylinder installation temperature of 210 ° C.

The flame retardancy was evaluated in the same manner as in Example 1, and the oxygen index was 32.

Comparative Example 1 Evaluation of Flame Retardancy with Low-Density Polyethylene 100 parts by weight of low-density polyethylene (trade name “Petrocene 202” manufactured by Tosoh Corporation) was added to decabromodiphenyl ether (trade name “Frame Cut 610R” manufactured by Tosoh Corporation) 6.
0 parts by weight was blended in the same manner as in Example 1 to prepare a flame-retardant resin composition.

The flame retardancy of the flame retardant resin composition was measured in the same manner as in Example 1, and the oxygen index was 26.

Comparative Example 2 Evaluation of Flame Retardancy with Low-Density Polyethylene 100 parts by weight of low-density polyethylene (trade name “Petrocene 202” manufactured by Tosoh Corporation) was prepared by using 60 parts by weight of zinc ethylenediamine phosphate prepared in Preparation Example 1. In the same manner as in Example 1, a flame-retardant resin composition was prepared.

The flame retardancy of the flame retardant resin composition was measured in the same manner as in Example 1, and the oxygen index was 23.

Comparative Example 3 Evaluation of Flame Retardancy with Polypropylene 100 parts by weight of a polypropylene resin (manufactured by Union Polymer, trade name "UP Polypro J7030B") was mixed with 30 parts by weight of tetrabromobisphenol A bis (2.3 dibromopropyl ether). ) (Trade name: “Frame Cut 121R” manufactured by Tosoh Corporation) was added, and a test piece of the flame-retardant resin composition was prepared in the same manner as in Example 2.

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

Comparative Example 4 Evaluation of Flame Retardancy with Polypropylene 30 parts by weight of EDA-ZP1 was added to 100 parts by weight of a polypropylene resin (manufactured by Union Polymer, trade name “UP Polypro J7030B”). Test pieces of the flame-retardant resin composition were prepared by the method.

The flame retardancy was evaluated in the same manner as in Example 1, and the oxygen index was 23.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction diagram of EDA-ZP1 obtained in Preparation Example 1.

FIG. 2 is an X-ray diffraction diagram of EDA-ZP2 obtained in Preparation Example 2.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 21/08 C09K 21/08 21/12 21/12

Claims (7)

[Claims] 1. A flame retardant comprising a halogen-based flame retardant and zinc ethylenediamine phosphate. 2. Zinc ethylenediaminephosphate having the general formula Z
represented by _{n 2 P 2 O 8 C 2} N 2 H 10, and Claim 1, X-ray diffraction pattern of the ethylenediamine zinc phosphate is characterized in that including a surface intervals indicated in at least the following Flame retardant. 3. The flame retardant according to claim 1, wherein the X-ray diffraction pattern of the ethylenediamine zinc phosphate contains at least the following spacing. 4. A halogenated flame retardant represented by the following general formula (1): (Wherein, A represents an alkylene group, a carbonyl group or an ether group; X represents a bromine or chlorine atom; a and b are a +
b represents an integer satisfying 1 to 10. A) a halogenated diphenyl compound represented by the following general formula (2): (In the formula, B represents an alkylene group, a carbonyl group, an ether group, a thioether group, or a sulfone group. X represents a bromine or chlorine atom. C and d represent integers satisfying c + d = 1 to 8.) A halogenated bisphenol compound represented by the following general formula (3): (In the formula, B represents an alkylene group, a carbonyl group, an ether group, a thioether group or a sulfone group. X represents a bromine or chlorine atom. C and d each represent an integer satisfying c + d = 1 to 8. Y represents _Represents an alkyl halide represented by C _n H _{2n + 1-z} X _z , wherein n and z are n = 1 to 8 and z = 1 to 2
represents an integer satisfying n + 1. A) a halogenated bisphenol bis (alkyl ether) -based compound represented by the following general formula (4): (In the formula, D represents an alkylene group, an alkyl ether group, a diphenyl sulfone group, a diphenyl ketone group, or a diphenyl ether group. X represents a bromine or chlorine atom.
c and d represent integers satisfying c + d = 1 to 8. 4. The flame retardant according to claim 1, wherein the flame retardant is at least one member selected from the group consisting of halogenated phthalimide-based compounds represented by the formula (1). 5. The halogen-based flame retardant is represented by the following general formula (1): (Wherein, A represents an alkylene group, a carbonyl group or an ether group; X represents a bromine or chlorine atom; a and b are a +
b represents an integer satisfying 1 to 10. And / or a halogenated diphenyl compound represented by the following general formula (3): (In the formula, B represents an alkylene group, a carbonyl group, an ether group, a thioether group or a sulfone group. X represents a bromine or chlorine atom. C and d each represent an integer satisfying c + d = 1 to 8. Y represents _Represents an alkyl halide represented by C _n H _{2n + 1-z} X _z , wherein n and z are n = 1 to 8 and z = 1 to 2
represents an integer satisfying n + 1. The flame retardant according to any one of claims 1 to 3, wherein the flame retardant is a halogenated bisphenol bis (alkyl ether) compound represented by the following formula: 6. The method according to claim 1, wherein the ratio (weight ratio) between the halogen content and the zinc content is 1 to 15.
The flame retardant according to any one of claims 1 to 5. 7. A flame-retardant resin composition comprising 5 to 100 parts by weight of the flame retardant according to claim 1 based on 100 parts by weight of the resin.