JP2003238580A - New phosphoric acid ester amide compound and flame- retardant resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new phosphoric acid ester amide compound which has excellent compatibility with various kinds of synthetic resins such as a polyphenylene ether resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyamide resin, excellent heat resistance and hydrolytic resistance and is suitable as a nonhalogen-based flame retardant capable of reducing the generation of phosphine gas having strong toxicity in kneading with a resin under heating and in molding and processing of a resin composition obtained therefrom and a flame-retardant resin composition obtained by incorporating the phosphoric acid ester amide compound. <P>SOLUTION: The new phosphoric acid ester amide compound represented by the formula and useful as a flame retardant is synthesized. The flame- retardant resin composition is obtained by incorporating the phosphoric acid ester amide compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phosphoric acid ester amide compound which is suitable as a flame retardant and has a particularly high heat resistance, and includes a polyphenylene ether resin, a polycarbonate resin, a polyethylene terephthalate resin and a polybutylene terephthalate resin. The present invention relates to a flame-retardant resin composition in which the above phosphoric acid ester amide compound is mixed with various synthetic resins such as polyamide resin.

[0002]

2. Description of the Related Art Flame-retardant resin compositions are widely used in fields of application such as electric parts and automobile parts, but those containing a halogen-containing compound known as a flame retardant and antimony oxide have hitherto been known. However, since it emits a harmful corrosive halogen-based gas when it burns, it has recently been demanded to improve the flame-retardant property by using a non-halogen-based flame retardant.

As a non-halogen flame retardant, JP-A-53 is recommended
-73248, phosphoric acid esters such as triphenyl phosphate, JP-A-60-106853, condensed phosphoric acid amide (condensation product of ammonium phosphate), JP-A-63-235363, phenyl phosphoric acid ester monoamide. , Those containing phenylphosphoric acid ester diamide are disclosed respectively.

However, these compounds tend to reduce the hydrolysis resistance of the resin, and further, decomposition occurs during heating and kneading with the resin, and phosphine gas that deteriorates the working environment is liable to be generated. , Not always satisfactory.

Further, Japanese Patent Laid-Open No. 54-19919, Japanese Patent Laid-Open No. 10-175985, and US Pat. No. 59730.
Japanese Patent Laid-Open No. 4 proposes a phosphoric acid ester amide compound represented by the general formula of Chemical formula 2.

[0006]

[Chemical 2]

Further, the phosphoric acid ester compound represented by the general formula of Chemical formula 3 is proposed in the above-mentioned Japanese Patent Laid-Open No. 54-19919 and European Patent No. 1067153, but the heat resistance temperature is still low. However, there is a problem in that it is difficult to apply to resins that require molding at high temperatures, such as engineering plastics.

[0008]

[Chemical 3]

[0009]

In view of the above circumstances, the present invention has good compatibility with various synthetic resins such as polyphenylene ether resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, and polyamide resin. A novel phosphoric acid ester having excellent heat resistance and hydrolysis resistance, which can reduce generation of highly toxic phosphine gas during heating and kneading with a resin and during molding of the obtained resin composition, and is suitable as a halogen-free flame retardant. It is an object to provide an amide compound and a flame-retardant resin composition containing the phosphoric acid ester amide compound.

[0010]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that the phosphoric acid ester amide compound represented by Chemical formula 4 can achieve the intended purpose. They have found that they have an excellent flame retardant effect, and have completed the present invention.

[0011]

[Chemical 4] (In the formula, R ₁ and R ₂ are the same or different and represent a hydrogen atom or a C ₁ -C ₄ alkyl group.)

That is, the present invention relates to a novel phosphoric acid ester compound represented by Chemical Formula 4 suitable as a flame retardant and a flame retardant resin composition containing the compound.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The phosphoric acid ester amide compound of the present invention can be synthesized by a condensation reaction of diarylphosphorochloridate and diaminodiphenylmethane. Further, the phosphoric acid ester amide compound of the present invention, as a flame retardant, can be suitably blended with synthetic resins such as polyphenylene ether resin, polyphenylene ether resin, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polyamide, but other applications Possible resins include thermosetting resins such as phenol resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, polystyrene, expanded polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene- Butadiene copolymer (hereinafter abbreviated as ABS resin), petroleum resin, polymethylmethacrylate, polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene α- olefin copolymers,
Examples thereof include polyolefin resins such as ethylene-acrylic acid copolymer and ethylene-acrylic acid copolymer.

The amount of the phosphoric acid ester amide compound used in the practice of the present invention is usually 1 to 40 parts by weight, preferably 5 to 30 parts by weight based on 100 parts by weight of the synthetic resin.
It should be added in parts by weight. If the compounding amount of the phosphoric acid ester amide compound with respect to the synthetic resin is less than the above range, the desired flame retardant effect cannot be obtained, and it may be compounded in excess of this range. However, the addition of these would only result in higher costs.

The flame-retardant resin composition of the present invention contains various additives which are usually added to these resins, for example, ultraviolet absorbers, light stabilizers, antistatic agents, copper damage inhibitors, lubricants and neutralizing agents. , Inorganic fillers, pigments, peroxides and the like can be used in combination.

The method for producing the flame-retardant resin composition of the present invention comprises:
Although not particularly limited, a predetermined amount of each component described above is charged into a stirring and mixing device such as a Henschel mixer, a super mixer or a tumbler mixer, and the mixture is stirred and mixed for 1 to 10 minutes, and the obtained mixture is a roll kneader or an extruder. It can be obtained by melt-kneading using, for example, and pelletizing.

[0017]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The resins and test methods used in the examples of the present invention are as follows.

[Resin] Polycarbonate resin [Product name: Iupilon S-20
0F, manufactured by Mitsubishi Engineering Plastics] ABS resin [trade name: K3272, manufactured by Sumitomo Dow] Polycarbonate / ABS alloy resin: A mixture of the above polycarbonate resin and ABS resin in a ratio of 7: 3 (weight) was used. Modified polyphenylene ether resin [Product name: Noryl 1
15-7001, made by Nippon GE] High-impact polystyrene resin [Brand name: Dick Styrene GH-6300-1, made by Dainippon Ink] Polybutylene terephthalate resin [Brand name: Planac BT-1000, made by Dainippon Ink] Polyester resin [Product name: Hyperlight 815
0, manufactured by Kanegafuchi Chemical Industry Co., Ltd.] Polyamide resin [trade name: Novamid 1020, manufactured by Mitsubishi Engineering Plastics]

[Flame Retardancy Test] The flame retardancy test was carried out in accordance with the vertical flammability test defined in UL Subject 94 (Underwriter Laboratories, Inc.) "Combustion test of plastic materials for parts of equipment".

[Hydrolysis resistance test] 2.5 mmol of a flame retardant was added to an aqueous methanol solution (methanol / water = 100/5,
V / V) was dissolved in 5 ml, 0.1 mol of sodium hydroxide was added to the flame retardant, the mixture was allowed to stand overnight, and the hydrolysis rate (%) of the flame retardant was measured by high performance liquid chromatography. The lower the hydrolysis rate, the better the hydrolysis resistance was evaluated.

Example 1 Synthesis of 4,4′-bis (diphenylphosphorylamidophenyl) methane In a flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel, 364 g (3.5 mol) of triethylamine, 4 ，
99.1 g (0.5 mol) of 4'-diaminodiphenylmethane and 2000 ml of dichloroethane were charged, and the internal temperature was 5
268.6 g (1 mol) of diphenylphosphorochloridate was added dropwise over 10 minutes while cooling so that the temperature was maintained at 0 ° C. or lower, and stirring was continued at room temperature for 3 hours, and then an internal temperature of 85 ° C.
Hold for 1 hour. The reaction product was concentrated under reduced pressure, 1000 ml of water was added, the mixture was stirred for 30 minutes, the precipitate was collected by filtration, the cake was washed with 100 ml of water, and the white powdery solid taken out was recrystallized and purified with acetone. After that, it was dried under reduced pressure (yield 576 g, yield 87.0%). The obtained product was confirmed to be 4,4′-bis (diphenylphosphorylamidophenyl) methane from the analysis results of NMR and MS spectra.

[Spectral data] ¹ H-NMR (acetone-d ₆ ): δ: 2.86 (2H, s, CH2), 3.88 (2H, s, NH), 7.14-7.27 (2
0H, m, Ph), 7.35 (8H, t, J = 8Hz, Ph) ・¹³ C-NMR (acetone-d ₆ ): δ: 40.9 (1C), 119.1 (4C), 121.2 (12C), 126.0 (4C ), 13
0.4 (2C), 130.6 (8C), 136.2 (2C), 138.7 (2C), 151.6 (2
C) ・ MASS (FAB +): 663 (M + 1), 662 (M +) 338 (M- ・ Ph
-NH-P (O) (-OPh) 2) [Physical properties] mp 194 ° C. White or pale yellow powder. Soluble in acetone, methyl ethyl ketone, and methanol. Insoluble in water, hexane and toluene.

[Examples 2 to 8] Resin 100 described in Table 1
Based on the weight, the flame retardant synthesized in Example 1 is shown in Table 1.
Was mixed in a ratio as described in, and 0.2 parts by weight of PTFE [trade name: Polyflon MPAFA500, manufactured by Daikin Industries, Ltd.] was mixed using a tumbler blender, and then melt-kneaded at a predetermined temperature, It was extruded from an extruder having a diameter of 30 mm to obtain a pellet-shaped resin composition. Then, injection molding machine [cylinder temperature 230-280 ℃,
Using a mold temperature of 60 ° C.], a test piece having a thickness of 1/16 inch was produced from the pellet resin composition. A flame retardance test was conducted on the obtained test pieces, and the test results were as shown in Table 1. It was confirmed that the novel phosphoric acid ester amide compound of the present invention stably exists without being decomposed during the above-mentioned melt-kneading and injection molding, and is excellent in heat resistance.

[0024]

[Table 1]

From these test results, it was confirmed that the novel phosphoric acid ester amide compound of the present invention can impart excellent flame retardancy to the resin.

Example 9, Comparative Example 1 The hydrolysis resistance of the flame retardant synthesized in Example 1 and the commercially available flame retardant triphenyl phosphate was examined. The test results obtained were as shown in Table 2.

[0027]

[Table 2]

From these test results, it was confirmed that the phosphoric acid ester amide compound of the present invention is stable without being hydrolyzed and therefore has excellent hydrolysis resistance. .

[0029]

INDUSTRIAL APPLICABILITY The novel phosphoric acid ester amide compound of the present invention is excellent in heat resistance and hydrolysis resistance and can impart excellent flame retardancy to synthetic resins. The blended flame-retardant resin composition can suppress the generation of harmful phosphine gas at the time of molding processing, so that the working environment is improved and the practical effects are great.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H028 AA29 AA38 BA06                 4H050 AA01 AB99                 4J002 BA011 BB031 BB051 BB061                       BB081 BB151 BC031 BC061                       BG061 BN151 CC001 CC161                       CC181 CD001 CF061 CF071                       CF211 CG001 CH071 CL001                       EW156 FD136 GN00 GQ00

Claims (2)

[Claims] 1. A novel phosphoric acid ester amide compound represented by Chemical formula 1. [Chemical 1] (In the formula, R ₁ and R ₂ are the same or different and represent a hydrogen atom or a C ₁ -C ₄ alkyl group.) 2. A flame-retardant resin composition containing the phosphoric acid ester amide compound according to claim 1.