JPH08269230A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE: To obtain a flame-retardant resin composition being excellent in flame retardancy, not forming noxious gases, reduced in smoke formation and having high performance and usability for many purposes by adding a specified amount of a specified flame retardant to a resin. CONSTITUTION: This flame-retardant resin composition is prepared by adding 5-200 pts.wt. amine-containing zinc phosphate to 100 pts.wt. resin. The amine- containing zinc phosphate means a compound of an amine combined with zinc phosphate. Its example is a compound prepared by occluding protonated cations of an amine in a three-dimensional open skeleton composed of a combination of at least one kind of ion selected from among PO4 <3-> , HPO4 <2-> , and H2 PO4 <-> with Zn<2+> . Examples of the anions includes ZnPO4 <-> , Zn2 (HPO4 )3 <2-> and Zn4 (PO4 )2 (HPO4 )2 <2-> . It is desirable that the amine has at least two amino groups in the molecule. It is desirable that this composition is used in conjunction with 1,3,5-triazine derivative.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition obtained by adding amine-containing zinc phosphate to a resin.

Flame-retardant resin compositions are widely used as materials for various electric parts, automobile parts, building materials, cables and the like.

[0003]

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 are widely used because of their excellent flame retardancy.

[0004]

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.

The 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 technology together with the 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 provide a new flame-retardant resin composition which does not generate harmful gas and emits a small amount of smoke.

[0008]

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 intensive studies, a flame-retardant resin composition containing an amine-containing zinc phosphate in a resin is a flame-retardant resin composition having excellent flame-retardant effect, harmful gas generation suppressing effect, and low smoke generating effect. This has led to the completion of the present invention.

That is, the present invention is a flame-retardant resin composition obtained by adding 5 to 200 parts by weight of amine-containing zinc phosphate to 100 parts by weight of the resin.

Hereinafter, the present invention will be described in detail.

The amine-containing zinc phosphate of the present invention is a compound of amine and zinc phosphate, and is not particularly limited as long as it is a compound having phosphorus, zinc, oxygen, hydrogen and nitrogen as a basic composition. Absent. For example, PO ₄ ^3- , HPO ₄ ^2-
And a compound in which a protonated cation of an amine is occluded in a three-dimensional open skeleton composed of a combination of one or more ions selected from the group consisting of H ₂ PO ₄ ⁻ and Zn ^2+. Can be mentioned.

A three-dimensional open skeleton composed of a combination of Zn ²⁺ and one or more ions selected from the group consisting of PO ₄ ³⁻ , HPO ₄ ²⁻ and H ₂ PO ₄ ⁻ is concrete. Is ZnP
_{^{O 4 -, Zn 2 (HPO}} 4) 3 2-, Zn 4 (PO 4) 2 (HPO
Anions such as ₄ ) ₂ ²⁻ and Zn (HPO ₄ ) (H ₂ PO ₄ ) ₂ ²⁻ are exemplified.

The amine occluded in the three-dimensional open skeleton is not particularly limited, but one having two or more amino groups in one molecule is preferable from the viewpoint of thermal stability, and it is easily available industrially. From ethylenediamine, propylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, diethylenetriamine, triethylenetetramine,
Triethylenediamine, hexamethylenetetramine and the like are suitable.

The amount of amine occluded is determined by the valency of the anion cage and the valence of the protonated cation of the amine, and the amine is occluded in an amount sufficient to maintain electrical neutrality.

The secondary particle size of the amine-containing zinc phosphate of the present invention is preferably 20 μm or less from the viewpoint of dispersibility in the flame-retardant compounding resin. The BET specific surface area of the amine-containing zinc phosphate of the present invention is not particularly limited, but is usually about 0.1 to ²⁰ m ² / g.

The present invention will be described in more detail below by taking Zn ₂ P ₂ O ₈ C ₂ N ₂ H ₁₀ as an example.

Zn ₂ P ₂ O ₈ C ₂ N ₂ H ₁₀ is a compound of R. H. Jo
It is a material synthesized by Nes et al. (Studie
s in Surface Science and
Catalysis, Zeolites and Re
Lated Microporous Material
ls, Vol. 84, p. 2229 (1994), El
sevier Science B. V. ).

[0018] This compound anion ZnPO ₄ formed by the tetrahedral ZnO ₄ tetrahedra PO ₄ network
^-In the three-dimensional open skeleton of the cation H ₃ N (CH ₂ ) ₂ NH ₃
^It has a structure in which ²⁺ is occluded. Also, X-ray diffraction peaks appear at the spacings shown in Table 2,

[0019]

[Table 2]

The X-ray diffraction pattern measured using CuKα rays is as shown in FIG.

Since H ₂ N (CH ₂ ) ₂ NH ₂ is occluded in the cage, it exists stably even at a boiling point of 117 ° C. or higher and is retained in the cage up to about 400 ° C. At about 800 ° C., thermal decomposition proceeds, dehydration condensation occurs, and the structure changes to Zn 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 amine-containing zinc phosphate of the present invention has a decomposition temperature as high as 400 ° C. as compared with conventional inorganic flame retardants, and is used as a flame retardant even for resins that cannot be applied due to high processing temperatures. It is a material with high versatility.

The method for producing the amine-containing zinc phosphate for resin addition of the present invention is not particularly limited, but Zn ₂ P ₂
A preferred embodiment will be described by taking O ₈ C ₂ N ₂ H ₁₀ as an example.

Zn ₂ P ₂ O ₈ C ₂ N ₂ H ₁₀ is prepared by preparing an aqueous zinc phosphate solution, forming a gel by mixing an aqueous zinc phosphate solution and an ethylenediamine solution, crystallization of the produced gel, filtration, washing, and drying. It is manufactured in the crushing process.

The aqueous solution of zinc phosphate contains a zinc compound and H ₃ P 2.
It is prepared by mixing O _{4 in an amount such} that the Zn / P ratio (molar ratio) is 1/10 to 2/5 and uniformly dissolving it. Examples of the zinc compound include zinc hydroxide, zinc oxide, zinc hydrogen phosphate, and zinc dihydrogen phosphate, but are not particularly limited. The concentration of H ₃ PO ₄ is not particularly limited and may be 14
It may be carried out at a concentration of up to 85% by weight.

The aqueous solution of zinc phosphate and ethylenediamine have an H ₂ N (CH ₂ ) ₂ NH ₂ / P ratio (molar ratio) of 2/1 to
Mix in half. The concentration of ethylenediamine is not particularly limited and may be 5 to 100% by weight. The mixing method is not particularly limited, for example, a method of adding an ethylenediamine aqueous solution to a zinc phosphate aqueous solution, a method of adding a zinc phosphate aqueous solution to an ethylenediamine aqueous solution, a zinc phosphate aqueous solution and an ethylenediamine aqueous solution in a reaction tank. A mixing method such as a method of continuously adding is mentioned. Mixing is preferably performed with stirring in order to make the inside of the reaction vessel uniform.

A gel is formed by mixing an aqueous solution of zinc phosphate and ethylenediamine.

Zn ₂ P ₂ O ₈ C ₂ N ₂ H ₁₀ is produced by crystallizing the resulting gel. The temperature during crystallization is 5 to 90
C. and time of 5 minutes to 3 days are sufficient. The crystallization is preferably carried out with stirring in order to make the inside of the reaction vessel uniform.

Zn ₂ P ₂ O ₈ C ₂ N ₂ H formed by crystallization
₁₀ is washed after solid-liquid separation. The solid-liquid separation method is not particularly limited, and examples thereof include Nutsche, a drum filter, a filter press, and a belt filter. The amount of washing water is not particularly limited, and unreacted H ₃ P
It may be washed until O ₄ and H ₂ N (CH ₂ ) ₂ NH ₂ are removed.

Next, the Zn ₂ P ₂ O ₈ C ₂ N ₂ H ₁₀ crystal is dried. The drying temperature is not particularly limited, and may be 6
It may be carried out at 0 to 250 ° C.

Further, the dried Zn ₂ P ₂ O ₈ C ₂ N ₂ H ₁₀ is lightly ground. Examples of the pulverization method include, but are not limited to, pulverization methods such as an automatic mortar and a hammer mill.

Zn ₂ P ₂ O ₈ C ₂ N ₂ H ₁₀ can be produced by the above method.

The flame-retardant resin composition of the present invention is a composition obtained by adding 5 to 200 parts by weight, particularly preferably 50 to 150 parts by weight, of amine-containing zinc phosphate to 100 parts by weight of the resin. When the addition amount of the amine-containing zinc phosphate is less than 5 parts by weight, the flame retardant effect is insufficient, which is not preferable, and when it exceeds 200 parts by weight, the mechanical properties of the resin may be deteriorated, which may not be preferable.

The resin can be used without particular limitation depending on the application. For example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene monomer terpolymer, ethylene-ethyl acrylate copolymer, homopolymer of olefinic monomers such as ethylene-vinyl acetate copolymer, Alternatively, a polyolefin such as a copolymer, a homopolymer of styrene, a rubber-modified polystyrene, a homopolymer mainly composed of a vinyl aromatic monomer such as a graft polymer of rubber and acrylonitrile or (meth) acrylate and styrene, or a copolymer Polyester such as polystyrene, poly (meth) acrylic resin, polyethylene terephthalate, polybutylene terephthalate, polyarylate, etc. which are combined, 6-nylon, 6,6-nylon, 12-nylon, 46-nylon, aromatic polyamide, etc. Polyamide, polyphenylene ether, modified polyphenylene ether, polyether such as polyoxymethylene, polycarbonate, styrene-conjugated diene copolymer, polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer, rubber such as polychloroprene, polyvinyl chloride, etc. Can be mentioned. Further, a thermosetting resin such as a phenol resin, an epoxy resin, an unsaturated polyester, or a polyurethane can 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.

The amine-containing zinc phosphate of the present invention has 1,3
The flame retardancy is further improved by using a 5-triazine derivative together.

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 5 to 200 parts by weight, particularly preferably 50 to 150 parts by weight of amine-containing zinc phosphate based on 100 parts by weight of the resin. 2 parts by weight of 1,3,5-triazine derivative, particularly preferably 15 parts by weight.
~ 45 parts by weight.

If desired, other additives may be added to the flame-retardant resin composition of the present invention.

As the additives, other flame retardants, flame retardant aids,
Examples thereof include plasticizers, lubricants, fillers, antioxidants, and UV inhibitors. Further, a cross-linking agent, a cross-linking auxiliary agent or the like can be used.

[0042]

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 zinc phosphate aqueous solution prepared by dissolving zinc oxide in an amount such that the Zn / P molar ratio was 2/5 was added to H ₂ NC ₂
After adding ethylenediamine in an amount such that the H ₄ NH ₂ / P molar ratio is 1/2 and crystallizing the resulting gel at 25 ° C. for 3 hours, solid-liquid separation, washing and drying are performed to obtain Zn ₂ P ₂ O. ₈ C ₂ N ₂ H
₁₀ was prepared (hereinafter, this amine-containing zinc phosphate powder is abbreviated as "flame retardant 1"). The flame retardant 1 had a BET specific surface area of 0.9 m ² / g and a secondary particle size of 2.0 μm.
The X-ray diffraction pattern of flame retardant 1 is shown in FIG.

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.

Further, by observation with an electron microscope, no significant aggregation of the flame retardant 1 was observed in this flame retardant resin composition.

Example 2 An aqueous zinc phosphate solution prepared by dissolving zinc oxide in an amount of 2/5 Zn / P molar ratio in an aqueous phosphoric acid solution was added to H ₂ NC ₂
Zn ₄ P ₂ O was added to ethylenediamine in an amount such that the H ₄ NH ₂ / P molar ratio was 1/2, and the resulting gel was crystallized at 25 ° C. for 1 hour, followed by solid-liquid separation, washing and drying. ₈ C ₂ N ₂ H
₁₀ was prepared (hereinafter, this amine-containing zinc phosphate powder is abbreviated as "flame retardant 2"). The flame retardant 2 had a BET specific surface area of 1.0 m ² / g and a secondary particle size of 2.2 μm.

A flame-retardant resin composition was prepared in the same manner as in Example 1 by adding 100 parts by weight of the flame retardant 2 to 100 parts by weight of low-density polyethylene (trade name “PETROSEN 202” manufactured by Tosoh Corporation). did.

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

Example 3 Low density polyethylene (manufactured by Tosoh Corporation, trade name "Petrosene 2"
02 ") 50 parts by weight of Zn ₂ P ₂ O ₈ C ₂ N ₂ H ₁₀ having a secondary particle size of 25 μm was mixed with 100 parts by weight of Example 1
A flame-retardant resin composition was prepared by the same method.

The oxygen index measured by the same method as in Example 1 was 21. Further, the flame-retardant resin composition contains Zn ₂
Aggregation of _{P 2 O 8 C 2 N 2} H 10 was observed.

Example 4 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 in the same manner as in Example 1. As a result, the oxygen index was 29.

Example 5 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 in the same manner as in Example 1. As a result, the oxygen index was 29.

Comparative Example 1 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.) was added, 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, and the effect of imparting flame retardancy to zinc phosphate was not recognized.

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

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

Comparative Example 3 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 20, and no synergistic effect between zinc phosphate and melamine was observed.

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 between magnesium hydroxide and melamine was observed.

[0064]

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. Further, since the amine-containing zinc phosphate of the present invention has a higher decomposition temperature than conventional inorganic flame retardants, it can be used as a flame retardant even for resins that cannot be applied due to high processing temperatures. It is a highly versatile material.

[0065]

[Brief description of drawings]

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

Claims (6)

[Claims] 1. A flame-retardant resin composition obtained by adding 5 to 200 parts by weight of an amine-containing zinc phosphate to 100 parts by weight of a resin. 2. A flame-retardant resin composition obtained by adding 2 to 100 parts by weight of a 1,3,5-triazine derivative to the flame-retardant resin composition according to claim 1. 3. 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 2, wherein 4. The amine-containing zinc phosphate is PO ₄ ³⁻ , H
A protonated cation of an amine is occluded in a three-dimensional open skeleton composed of a combination of one or more ions selected from the group consisting of PO ₄ ²⁻ and H ₂ PO ₄ ⁻ and Zn ²⁺ . The flame-retardant resin composition according to claim 1, which is a resin. 5. The amine-containing zinc phosphate has a general formula of Zn
The flame-retardant resin composition according to claim 4, wherein the flame-retardant resin composition is ₂ P ₂ O ₈ C ₂ N ₂ H ₁₀ and has the X-ray diffraction pattern shown in Table 1. [Table 1] 6. The secondary particle size of the amine-containing zinc phosphate is 20.
It is less than or equal to μm.
The flame-retardant resin composition according to any one of 1.