JP2000063843A - Flame retardant composition and flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant composition which, when added to a resin, can impart excellent flame retardancy thereto without detriment to mechanical properties by incorporating a metal diphosphonate obtained by reacting a specified diphosphonic acid and a salt thereof with a divalent metal compound. SOLUTION: A 1-hydroxyethylylidene-1,1'-diphosphonic acid and a salt thereof (wherein M1 and R2 are each hydrogen or an alkali metal) are reacted with an oxy acid salt, such as a sulfate or a carbonate, a hydroxide, an oxide, or the like of a divalent metal such as Mg, Ca, Ba, or Zn in a solvent such as water or a water/acetone (alcohol) mixture to obtain a lowly volatile pungent-odor-free flame retardant composition. This composition can exhibit further improved flame-retardant effect when used in conjunction with other inorganic flame retardants such as antimony trioxide or a combination of a hydrated metal oxide with red phosphorus. The red phosphor is desirably one surface-modified with an organic substance and/or an inorganic substance and is added in an amount of 0.1-2.0 wt.% based on the flame retardant composition. The formulation amount of the flame detardant composition is 3-20 pts.wt. (in terms of the P atoms) 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 non-halogen type flame-retardant resin capable of imparting excellent flame retardancy to various resins while maintaining the original mechanical properties of the resins, with low smoke generation and no irritating odor. The present invention relates to a flame retardant composition and a flame retardant resin composition.

[0002]

2. Description of the Related Art Halides such as chlorine and bromine, phosphorus compounds, nitrogen compounds, antimony and boron inorganic compounds have been used as flame retardants for plastics.

However, in recent years, in all fields, the level of flame retardancy has become severe, and high flame retardant performance is required, and in particular, flame retardants containing bromine and chlorine are toxic to the human body even though they are trace amounts when they burn. Since it has been pointed out that dioxins may be generated, there is an increasing demand for non-halogen flame retardants.

Examples of the non-halogen flame retardant include, for example, a resin composition in which red phosphorus is mixed with a curable resin (Japanese Patent Publication No. 59-49942), and hydrated alumina as a flame retardant for epoxy resin (Japanese Patent Laid-Open Publication No. 05-29,051). No. 25369), surface-treated red phosphorus, hydrated alumina, silica powder (JP-A-58-198521), modified red phosphorus (JP-A-63-156860), and phenol resin to boron. Calcium acid and aluminum hydroxide or magnesium hydroxide (JP-A-05-43774), boric acid and antimony trioxide (JP-A-60-81244) for phenol resin, intramolecular for polyurethane resin A compound having three triazine structures (JP-A-53-21241) and the like have been proposed.

On the other hand, for a thermoplastic resin as a flame retardant, magnesium hydroxide for a polyamide resin (Japanese Patent Laid-Open Nos. 54-83952 and 54-13164).
5) and melamine cyanurate (JP-A-53-53).
No. 31759, Japanese Patent Laid-Open No. 54-91558),
Organic sulfonates for polycarbonate
0-98539, JP-A-50-98540),
Sulfide salts (Japanese Patent Publication No. 01-22304), phosphonate compounds for polyphenylene oxide and ammonium polyphosphate (JP-A-52-86449), phosphate compounds and antimony trioxide (JP-A-49-32947). Flame retardants such as polyphosphonates (US Pat. No. 3,719,727) for polyesters have been proposed.

However, since red phosphorus has a reddish brown color, the resin is colored by red phosphorus and coloring is impossible. In addition, the working environment is deteriorated due to the generation of phosphine gas during heat processing or incineration of the resin, and red phosphorus is coated with a coating agent to suppress this, but the generation of phosphine gas does not occur. It cannot be completely suppressed.

Also, with other flame retardants, it is difficult to impart excellent flame retardancy to various resins without impairing the color tone, mechanical physical properties and color tone of the resin, and also the smoke generation property during combustion and There is a problem of irritating odor.

[0008]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
As a non-halogen flame retardant, it has been particularly noted.
The flame-retardant mechanism is a highly volatile one, in which the phosphorus compound vaporized by heating is used as an inhibitor of combustion in the gas phase,
Combustion of plastic is suppressed by the effect of diluting oxygen gas, the effect of cooling the combustion system by volatilization, and the effect of suppressing the chemical reaction of combustion. On the other hand, those with low volatility are thermally decomposed by heating to generate phosphoric acid, which becomes metaphosphoric acid or polymetaphosphoric acid, which forms a non-volatile phosphoric acid polymer on the solid phase or molten layer surface of the plastic to be baked. To do. In addition, the plastic is carbonized by the dehydration reaction of phosphoric acid,
A carbonized layer is formed, thereby blocking the ingress of air and blocking the supply of thermal energy from the outside to suppress combustion.

At present, various phosphoric acid ester and phosphite compounds have been proposed as the organic phosphorus flame retardants, but most of these compounds are water-soluble and thus have a low affinity for resins. Since the amount is low, a large amount must be contained in the resin in order to enhance the flame retardant effect, which impairs mechanical properties.

1-Hydroxyethylidene-1,1'-diphosphonic acid and its derivatives are used in various fields as scale inhibitors, anticorrosive agents, metal surface treating agents, chelating agents, and JP-A-05-86081. In 1-
It is disclosed that the 4-melamine salt of hydroxyethylidene-1,1'-diphosphonic acid is an excellent flame retardant compound. However, a resin containing the compound as a flame retardant has a certain flame retardant effect, but has a drawback that the practical flame retardant effect is still insufficient and the mechanical properties of the resin are deteriorated.

In view of the above problems, the inventors of the present invention have conducted extensive studies on non-halogen flame retardants, and as a result, have focused on 1-hydroxyethylidene-1,1'-diphosphonic acid having a high P content, The inventors have found that the divalent metal salt of 1) can impart excellent flame retardancy to various resins without impairing mechanical properties, and have completed the present invention.

That is, the present invention provides a non-halogen flame retardant composition having low smoke emission and no irritating odor which can impart excellent flame retardancy to various resins without impairing mechanical properties, and excellent flame retardancy. An object is to provide a resin composition having flammability.

[0013]

The flame retardant composition to be provided by the present invention is represented by the following general formula (1):

[0014]

[Chemical 2] (In the formula, M ¹ and M ² represent a hydrogen atom or an alkali metal.) 1-hydroxyethylidene-1,
1-hydroxyethylidene-1, obtained by reacting 1'-diphosphonic acid or a salt thereof with a divalent metal compound,
It is characterized by containing a 1'-diphosphonic acid metal salt.

Further, the flame retardant composition of the present invention has the above-mentioned 1
-A composition containing a metal salt of hydroxyethylidene-1,1'-diphosphonic acid and a hydrated metal oxide, or the above-mentioned metal salt of 1-hydroxyethylidene-1,1'-diphosphonic acid and a hydrated metal oxide, and Compositions containing red phosphorus are preferred.

The flame-retardant resin composition to be provided by the present invention is characterized in that it contains a resin and the flame-retardant composition.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The flame retardant composition of the present invention has the following general formula (1)

[0018]

[Chemical 3] 1-hydroxyethylidene-1,1'-diphosphonic acid and a salt thereof represented by and a 1-hydroxyethylidene-1,1'-diphosphonic acid metal salt obtained by reacting with a divalent metal compound are contained. Characterize.

In the general formula (1), M ¹ and M ² represent a hydrogen atom or an alkali metal. As an alkali metal, L
i, Na and K are preferred.

1-hydroxyethylidene-1,1'-diphosphonic acid represented by the general formula (1) and a salt thereof and 2
1-hydroxyethylidene-reacted with a valent metal compound
The method for obtaining the 1,1′-diphosphonic acid metal salt is not particularly limited, and a known method can be used. For example, 1-hydroxyethylidene
It is carried out by a method of reacting 1,1'-diphosphonic acid or a salt thereof with a divalent metal compound in an aqueous solvent such as water, a mixed solvent of water-acetone or water-alcohol.

Examples of the divalent metal compound include divalent metal oxyacid salts, hydroxides, oxides and halides.
Examples of the valent metal oxyacid salt include sulfates, carbonates, phosphates, nitrates, and nitrites. Further, examples of the divalent metal include Mg, Ca, Ba, Sr and Zn.

In the reaction for obtaining the desired 1-hydroxyethylidene-1,1'-diphosphonic acid metal salt of the above reaction, 1-hydroxyethylidene-1,1'-diphosphone represented by the general formula (1) is used as a starting material. The ratio of the acid or its salt to the divalent metal compound is usually in the range of 1 to 2 mol of the divalent metal compound with respect to 1 mol of the phosphonic acid of the general formula (1) and its salt, and within the range, the target compound. The amount of the divalent metal compound to be introduced may be appropriately adjusted depending on the amount of the divalent metal compound introduced, for example, the amount of one or two divalent metal compounds.

The 1-hydroxyethylidene-1,1'-diphosphonic acid metal salt obtained by the reaction may be either an anhydride or a hydrate. Specific examples thereof include 1-hydroxyethylidene-1,1′-diphosphonic acid.
Magnesium salt 1-hydroxyethylidene-1,1'-diphosphonic acid
2-magnesium salt 1-hydroxyethylidene-1,1'-diphosphonic acid
Calcium salt 1-hydroxyethylidene-1,1'-diphosphonic acid
2-calcium salt 1-hydroxyethylidene-1,1'-diphosphonic acid
Barium salt 1-hydroxyethylidene-1,1'-diphosphonic acid
2 barium salt 1-hydroxyethylidene-1,1'-diphosphonic acid
Strontium salt 1-hydroxyethylidene-1,1'-diphosphonic acid
2-Strontium salt 1-hydroxyethylidene-1,1'-diphosphonic acid
Zinc salt 1-hydroxyethylidene-1,1'-diphosphonic acid
2 Zinc salt etc. are mentioned. Moreover, these compounds are used by 1 type (s) or 2 or more types.

In the flame retardant composition according to the present invention, the flame retardant effect can be further enhanced by using it together with another inorganic flame retardant. Other flame retardants include, for example, antimony trioxide, aluminum hydroxide, nitrogenated guanidine, antimony pentoxide, magnesium hydroxide, magnesium oxide, zinc borate, calcium borate, calcium hydroxide, barium hydroxide, basic carbonic acid. Inorganic flame retardants such as magnesium, dawsonite, aluminum polyphosphate, barium metaborate, zirconium oxide, titanium phosphate and the like can be mentioned. Among these, calcium hydroxide, magnesium hydroxide, basic having a combustion suppressing action by endothermic reaction. It is preferably used in combination with a hydrated metal oxide such as magnesium carbonate. These inorganic flame retardants may be used alone or in combination of two or more, and these inorganic flame retardants may be surface-treated.

In this case, the compounding ratio of the inorganic flame retardant is 1
The amount is usually 50 to 200 parts by weight, preferably 60 to 100 parts by weight, based on 100 parts by weight of hydroxyethylidene-1,1'-diphosphonic acid metal salt.

Further, in the flame retardant composition of the present invention, the combined use of hydrated metal oxide and red phosphorus can further enhance the flame retardant effect. In this case, red phosphorus whose surface is modified with an organic substance and / or an inorganic substance is preferable, and examples thereof include phenol resin, epoxy resin, ethylene-vinyl acetate copolymer, melamine-formaldehyde polycondensate, Mg, Ca, Ti. , Hydroxides of Al, Co, and Zr, and those surface-treated with one or more selected from these oxides, but not limited thereto. The mixing ratio of red phosphorus in the flame retardant composition is
Usually 0.1 to 2.0% by weight, preferably 0.5 to 1.0
It is desirable to blend in a weight percentage.

The flame retardant composition according to the present invention can impart excellent flame retardancy to various resins. Next, a flame-retardant resin composition obtained by blending a resin with the flame-retardant composition according to the present invention will be described.

The resin which can be used in the present invention is not particularly limited, and examples thereof include epoxy resin, phenol resin, polyurethane resin, melamine resin, urea resin, aniline resin, furan resin, alkyd resin, xylene resin, unsaturated resin. Curable resin such as polyester resin and diaryl phthalate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polycarbonate, polyphenylene oxide, polyphenylene ether, nylon 6, nylon 66, nylon 12, polyacetal, polyethylene, polypropylene, polybutadiene, polyacrylonitrile, polystyrene , Polymethylmethacrylate, polyethylene oxide, polytetramethylene oxide, thermoplastic polyurethane, phenoxy resin, polyamide, ethyl On / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene /
Non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer,
Examples of the thermoplastic resin include ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / propylene-g-maleic anhydride copolymer, polyester polyether elastomer, polytetrafluoroethylene and modified products thereof. These resins may be homopolymers or copolymers, and may be a mixture of two or more kinds.

Here, the curable resin has a three-dimensional network structure in which a cross-linking structure develops due to a chemical change caused by the action of heat, a catalyst, ultraviolet rays or the like to increase the molecular weight,
A synthetic resin that hardens semi-permanently to become insoluble and infusible. Further, the thermoplastic resin refers to a resin that exhibits fluidity when heated and can be shaped by this.

The blending ratio of the flame retardant composition to various resins is 3 to 20 parts by weight as P, preferably 5 to 15 parts by weight, based on 100 parts by weight of the resin. The reason for this is
If the compounding ratio is less than 3 parts by weight, it is difficult to obtain a sufficient flame retardant effect, while if it is more than 20 parts by weight, the flame retardant effect increases, but the mechanical properties of the molded product tend to deteriorate, which is not preferable.

As other components to be added to the resin, phosphorus, ionic, hindered phenolic and other antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, release agents, colorants including pigments , A cross-linking agent, a softening agent, a dispersant, and other usual additives.

If necessary, a fibrous and / or granular filler can be added to greatly improve the rigidity of the resin. Examples of such fillers include glass fiber, carbon fiber, metal fiber, aramid resin,
Asbestos, potassium titanate whiskers, wollastonite, glass flakes, glass beads, talc, mica,
Examples include clay, calcium carbonate, calcium silicate, barium sulfate, titanium oxide, fused silica, crystalline silica, magnesia, and aluminum oxide.

The flame retardant composition of the present invention can be incorporated into various resins by a generally known method. For example, in the case of a curable resin, a method of mixing the flame retardant composition of the present invention with the curable resin and other compounds at the same time, one of resin components
The flame retardant composition of the present invention is mixed in advance with a seed, a method of mixing it with a curable resin, and if it is a thermoplastic resin, a method of melt mixing the flame retardant composition of the present invention with an extruder, or Examples include a method in which the particulate materials are mechanically mixed uniformly and then molded simultaneously with mixing in an injection molding machine.

The flame-retardant resin composition of the present invention maintains the original mechanical properties of the resin and has a low smoke generation property upon combustion.
Since it does not generate halogenated gas, it is an extremely safe plastic material with no irritating odor and can be used for a wide range of applications such as electrical parts, building materials, transportation equipment such as automobiles, packaging materials, household daily necessities, and others.

[0035]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. <Preparation of 1-Hydroxyethylidene-1,1'-diphosphonic acid metal salt> Sample A; 1-Hydroxyethylidene-1,1'-diphosphonic acid 2Ca 15L tap water in a stainless steel container, calcium carbonate 1000.9g (10.00 mol) was added and stirred (slurry state). After heating this to 80 ° C., 1-hydroxyethylidene-1,1′-diphosphonic acid (hereinafter,
Abbreviated as HEDP) (60% aqueous solution) 1716.8 g
(5.00 mol) was added dropwise. After the dropwise addition, stirring was continued at 80 ° C. until the pH of the reaction solution became constant (about 3.4), and then centrifugal filtration was performed to obtain white crystals.
The crystals were dried at 200 ° C. for 24 hours and pulverized with a mixer to obtain 1442.0 g of the desired product. Yield 9
5.4% (yield based on HEDP). The obtained white crystals were dissolved in hydrochloric acid, and the concentrations of P and Ca were measured by ICP. As a result, P was 20.8% and Ca was 25.8%.

Sample B: 1-hydroxyethylidene-
15 L of tap water and 966.4 g (10.00 mol) of magnesium carbonate were added and stirred to a 1,1′-diphosphonic acid / 2Mg 15 L stainless steel container (slurry state). After heating this to 80 ℃, HED
P (60% aqueous solution) 1716.8 g (5.00 mol)
Was dripped. After the dropwise addition, stirring was continued at 80 ° C. until the pH of the reaction solution became constant (about 3.4), and then centrifugal filtration was performed to obtain white crystals. This crystal at 200 ℃
It was dried for 24 hours and pulverized with a mixer to obtain 1200 g of the target product. Yield 96.0% (vs. HED
P). The obtained white crystals were dissolved in hydrochloric acid, and the concentrations of P and Mg were measured by ICP. As a result, P; 23.6%, Mg; 1
It was 7.3%.

Examples 1 and 2 and Comparative Examples 1 to 3 Various additives were added to the ethylethylene acrylate resin at the compounding ratios shown in Table 1, and the mixture was heated at 120 to 130 ° C. on a hot roll to obtain 5 Kneaded for 10 minutes. Using a heating press, a molding pressure of 150 kg / cm ² , a pressing temperature of 5 minutes, a mold temperature of 115 ° C., a sheet having a thickness of 3 mm was prepared, and a test piece having a length of 125 mm and a width of 13 mm was prepared.

<Flame Retardancy Test> The flame retardancy test is a vertical combustion test (94) for materials classified as UL94 based on the resin prepared above and processed into a length of 125 mm, a width of 13 mm and a thickness of 3 mm.
V-0, 94V-1 and 94V-2). The results are shown in Table 3. Table 2 shows the UL 94 availability conditions.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3]

Examples 3 to 5 and Comparative Examples 4 to 5 Various additives were compounded in the compounding ratio shown in Table 4 to the novolac resin prepared at a molar ratio of formaldehyde / phenol = 0.9, Kneading was performed for 5 minutes on a hot roll set at 80 to 90 ° C. After crushing, a molding having a predetermined shape was prepared using a universal press at a molding pressure of 250 kg / cm ² , a pressing time of 60 seconds, and a mold temperature of 150 ° C.

The flame retardancy test was evaluated by the same operation method as in Examples 1 and 2, and the presence or absence of phosphine gas at the time of molding,
The surface properties of the molded products are shown in Table 5. The red phosphorus used had its surface modified with a phenol resin.

[0044]

[Table 4]

[0045]

[Table 5]

(Note 1) Generation of phosphine gas (PH ₃ ) was measured by a detector tube method. None: Less than 0.15 ppm Present: 0.15 ppm or more (Note 2) Surface properties were measured by touch.

From the results shown in Table 5, the phenol resin containing the flame retardant composition of the present invention has excellent flame retardancy, the surface of the molded product is smooth, and no phosphine gas is generated during molding. On the other hand, a composition containing calcium borate also exhibits excellent flame retardancy, but the surface of the molded product is rough. Further, the one containing red phosphorus also showed excellent flame retardancy, but phosphine gas was generated during processing.

Examples 5 to 6 and Comparative Examples 6 to 7 Various additives were added to the bisphenol A diglycidyl ether type epoxy resin in the mixing ratio shown in Table 6, and the additives were poured into a mold having a predetermined shape, and 105 It was cured at 0 ° C. for 10 hours.

The flammability of each sample based on UL94 and the presence or absence of phosphine generation during molding were measured, and the results are shown in Table 7. The red phosphorus used had its surface modified with a phenol resin.

[0050]

[Table 6]

[0051]

[Table 7]

Examples 7 to 15 Various resins shown in Table 8 were added to various resins to give 30 m
Tensile test pieces specified in ASTMD-638 were prepared by injection molding using an mΦ axial extruder, and the strength and elongation were measured. Further, similarly, a test piece for flame retardancy evaluation based on UL94 was prepared and the flammability was measured. The results are shown in Table 9.

The red phosphorus used was one whose surface was modified with aluminum hydroxide and titanium hydroxide. The melt extrusion, pellet drying, and injection molding conditions for each resin are shown below.

Polybutylene terephthalate (hereinafter P
Abbreviated as BT) Extrusion; 250 to 290 ° C./150 rpm drying; 110 ° C./12 hours molding; 250 to 290 ° C./mold 80 ° C. Nylon 6 extrusion; 250 to 300 ° C./150 rpm drying; 100 ° C./24 hours molding 250-300 / mold 80 ° C Polycarbonate extrusion; 260-320 ° C / 75 rpm drying; 120 ° C / 12 hours molding; 260-320 / mold 110 ° C

[0055]

[Table 8]

[0056]

[Table 9]

[0057]

As described above, the flame retardant composition of the present invention can impart an excellent flame retardant effect to various resins while maintaining the original mechanical properties of the resin, and has low smoke emission. Since it has no irritating odor, it is extremely useful as a non-halogen flame retardant.

Continued front page    (72) Inventor Takashi Nishimura             9-11 Kameido, Koto-ku, Tokyo Japanization             Gaku Kogyo Co., Ltd. (72) Inventor Nobuo Matsumoto             9-11 Kameido, Koto-ku, Tokyo Japanization             Gaku Kogyo Co., Ltd. F-term (reference) 4H028 AA10 AA35 AA42 BA06                 4J002 BB071 CC041 CD051 CF071                       CG011 CL011 DA058 DE067                       DE077 DE087 DE127 DE147                       DH057 DK007 EW126 FD136                       FD137 FD138

Claims (4)

[Claims] 1. The following general formula (1): (In the formula, M ¹ and M ² represent a hydrogen atom or an alkali metal.) 1-hydroxyethylidene-1,
1-hydroxyethylidene-1, obtained by reacting 1'-diphosphonic acid or a salt thereof with a divalent metal compound,
A flame retardant composition comprising a metal salt of 1'-diphosphonic acid. 2. The flame retardant composition according to claim 1, which contains the metal salt of 1-hydroxyethylidene-1,1′-diphosphonic acid according to claim 1 and a hydrated metal oxide. 3. The flame retardant composition according to claim 2, which further contains red phosphorus. 4. A flame-retardant resin composition comprising the flame-retardant composition according to any one of claims 1, 2 and 3.