JP3192983B2 - Flame retardant for resin and flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame retardant containing no halogen element, and more particularly to a phosphoric ester flame retardant having excellent heat stability, and a flame retardant resin composition obtained by adding the flame retardant. .

[0002]

2. Description of the Related Art Synthetic resins are generally light, excellent in water resistance, chemical resistance, electrical insulation, mechanical properties, etc., and are easy to mold. It is widely used as a material for automobiles and a fiber material. On the other hand, synthetic resins are generally flammable, and various proposals have been made for imparting flame retardancy. The most common means of flame retardation is a method of blending a flame retardant such as an organic halogen compound, a phosphorus compound, or an inorganic hydrate at the time of preparing a resin molded product.

[0003] Among the above flame retardants, organic halogen compounds,
In particular, bromine compounds are most widely used because they exhibit excellent flame retardant effects on many synthetic resins. However, this flame retardant has the problem that the weather resistance and the electrical properties of the resin composition, especially the electrical insulation, are reduced due to the liberated halogen,
There is a problem that thermal decomposition occurs during resin molding to generate hydrogen halide, thereby contaminating the working environment, causing mold corrosion, resin coloring, and gelling. In addition, there is also a problem that a large amount of smoke is generated together with a hydrogen halide gas which is corrosive and harmful to the human body upon burning by a fire or the like. Furthermore, carcinogenicity has been pointed out for antimony oxide, which is usually added as a flame-retardant aid to dramatically increase the flame-retardant effect of organic halogen compounds. Have been.

As a halogen-free flame retardant, inorganic hydrates such as aluminum hydroxide and magnesium hydroxide are known. However, these have small flame retardant effects,
In order to obtain sufficient flame retardancy, it is necessary to add a large amount, and there is a disadvantage that the physical properties of the resin are impaired. Phosphorus compounds, especially organic phosphoric esters, do not contain halogen and are widely used as flame retardants that provide good flame retardant effects. Representative organic phosphates include triaryl phosphates such as triphenyl phosphate (TPP), tricresyl phosphate (TCP), and trixylyl phosphate (TXP). However, these compounds have relatively low boiling points, extruding with the resin, volatilizing during molding and contaminating the working environment, causing contamination of the mold, and exuding on the surface of the molded product to impair the appearance. there were. In particular, mold contamination can cause serious problems such as improper molding and transfer of contaminants to molded products, causing stress cracks if left as it is, so it is necessary to take measures such as interrupting molding work and cleaning the mold. In this case, the productivity was significantly reduced.

[0005] Phosphoric acid esters having low volatility which solve these drawbacks include US Pat. No. 252,090 and European Patent Publication Nos. 129824 and 129.
No. 825, No. 135726, Japanese Patent Publication No. 54-3281
No. 8, Japanese Patent Publication No. 62-25706, Special Publication No. 2-
A phosphoric ester oligomer described in, for example, JP-A-18336 is already known.

Among these compounds, a phosphoric ester oligomer represented by the following general formula (1), which is cross-linked by a residue of 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A) Has higher heat resistance and hydrolysis resistance than those crosslinked with monocyclic phenol residues such as resorcinol.
No. 8539, etc., and particularly preferred.

[0007]

Embedded image

(Wherein n is an integer of 0 to 10;
To R4 are each independently a phenyl group, a tolyl group or a xylyl group. When n is 2 or more, a plurality of R4s may be the same or different. It is well known that one of the important factors governing the thermal stability of a phosphate ester oligomer is the amount of a low-boiling triaryl phosphate corresponding to the n = 0 component of the general formula (1). For example, Japanese Patent Publication No. 62-25706
The publication states that the proportion of this component should be 40% by weight or less based on the whole composition.

However, according to the study of the present inventors, the thermal stability of the phosphate ester oligomer greatly varies depending on the production conditions. For example, mold contamination, which is a major problem in continuous molding, requires the compound represented by the formula (1). Even when used, it cannot be prevented only by specifying the content of the triaryl phosphate, and often causes a problem particularly when used for a so-called engineering plastic having a relatively high molding temperature, such as a polyphenylene ether resin or a polycarbonate resin. There is. In addition, the flame retardant with severe mold contamination tends to cause corrosion of the molding machine and the mold at the same time, and furthermore, the electric insulation of the resin composition tends to decrease.

JP-A-5-1079 discloses a high heat-resistant organic phosphoric acid ester having a high-purity aromatic diphosphate having a substituent of a monohydric phenol residue having an alkyl group at the 2- and 6-positions. The manufacturing method is shown. However, this compound is a crystalline solid having a high melting point, and has a problem that molding processability is inferior to a liquid phosphate ester oligomer composition having compatibility with a resin. Therefore, development of a flame retardant of stable quality which has compatibility with resin, has excellent thermal stability and does not cause problems such as mold contamination has been eagerly desired.

[0011]

DISCLOSURE OF THE INVENTION The present invention relates to a phosphate ester flame retardant having excellent heat resistance, and a flame-retardant, heat-resistant, and electrically insulating material obtained by adding the flame retardant. An object of the present invention is to provide a flame-retardant resin composition that does not cause smoke, mold contamination, and corrosion at the time.

[0012]

Means for Solving the Problems In order to solve the above problems, the present inventors have studied what causes the decrease in the thermal stability of the flame retardant composition. As a result, although the decomposition temperature and the volatilization temperature of the phosphate ester itself are sufficiently high, the diarylphosphoric acid represented by the following formula (2) by-produced during the synthesis and the metal derived from the catalyst and the like transesterify the phosphate ester during heating. It has been found that it has the effect of accelerating the reduction of molecular weight and the hydrolysis reaction by the reaction, and the resulting volatile components cause mold contamination. And
In order to significantly improve the thermal stability of the flame retardant composition, it is necessary that both the content of the metal and the content of the diarylphosphoric acid be below a specific value, respectively. The inventors have found that problems such as corrosion, corrosion, and a decrease in the electrical insulation of the resin composition can be solved, and have completed the present invention.

That is, the present invention is as follows. 1. A mixture of phosphoric esters represented by the following general formula (1), wherein n is an integer of 0 to 10, wherein the content of the diarylphosphoric acid represented by the following general formula (2) is 1% by weight or less, Is not more than 30 ppm by weight, and 100 ° C. in an inert gas atmosphere by TGA.
A flame retardant for a resin that has a weight loss rate of 15% by weight or less for 20 minutes from the start of heating when heated to 300 ° C. at a rate of temperature rise per minute and maintained at that temperature.

[0014]

Embedded image

(Wherein n is an integer of 0 to 10;
To R4 are each independently a phenyl group, a tolyl group or a xylyl group. When n is 2 or more, a plurality of R4s may be the same or different. )

[0016]

Embedded image

(In the formula, R1 and R2 are each independently a phenyl group, a tolyl group or a xylyl group.) 2. The flame retardant for a resin according to the above 1, wherein the content of diarylphosphoric acid is 0.5% by weight or less and the total content of metals is 10% by weight or less. 3. (A) A flame-retardant resin composition comprising the flame retardant according to 1 or 2 and (B) a non-halogen synthetic resin. 4. 4. The flame-retardant resin composition according to the above item 3, wherein the non-halogen synthetic resin is one selected from a polyphenylene ether resin, a polycarbonate resin, a polystyrene resin, a polyester resin, and a polyamide resin, or a combination of a plurality of resins containing these.

Hereinafter, the present invention will be described in detail. First, the flame retardant for resin of the present invention will be described. Phosphoric esters represented by the above general formula (1) are disclosed in U.S. Pat. No. 252,090, JP-B-62-25706, and JP-A-63-22.
It can be manufactured by a known method described in, for example, U.S. Pat. That is, it is synthesized by reacting phosphorus oxychloride with bisphenol A and a monohydric phenol in the presence of a Lewis acid catalyst such as magnesium chloride or aluminum chloride. As the monohydric phenols, phenol, cresol, and xylenol can be reacted alone or in a mixture or in a stepwise manner. The synthesized crude phosphoric acid ester is usually washed and purified to remove chlorine and catalyst, and then dehydrated and dried to obtain a product.

The diarylphosphoric acid represented by the above general formula (2) is obtained by reacting water contained in a catalyst or phenol with phosphorus oxychloride and a monohydric phenol, and a phosphate ester produced in a washing step and the like. It is produced by hydrolysis, and the amount produced varies depending on the production conditions. It is described in JP-B-62-25706 that a phosphoric ester composition containing diarylphosphoric acid imparts an antistatic property without deteriorating the physical properties of the resin composition, in addition to the flame retardant action. However, according to the study of the present inventors, diarylphosphoric acid has a higher volatility than a phosphoric acid ester and has an effect of promoting the formation of a low molecular weight component and a gel-like substance by a disproportionation reaction of the phosphoric acid ester under heating conditions. It turned out to be. In addition, it easily releases protons, causing decomposition of the resin, causing corrosion during molding, and has a strong affinity for water and metals. It is not preferable because it causes a decrease. In order to ensure the thermal stability and electrical insulation of the flame retardant, the content of diarylphosphoric acid needs to be 1% by weight or less, more preferably 0.5% by weight or less.

As methods for limiting the amount of diarylphosphoric acid in the flame retardant, there are a method of reducing the amount produced during synthesis and a method of separating from the crude phosphoric acid ester in the purification step. The former is
After suppressing the water content of the raw materials for synthesis, a method is used in which phenols are excessively charged to phosphorus oxychloride to complete the reaction.
The amount of water contained in the raw materials is 600p based on the total amount of raw materials
pm or less, and more preferably 300 ppm or less. On the other hand, the latter is a method of extracting diarylphosphoric acid into an aqueous phase in a washing and purification step,
For example, this can be achieved by using an alkaline cleaning solution.
In particular, the former method is preferable because the quality of the product can be easily controlled and the amount of organic phosphorus in the wastewater is small.

The metal which is another cause of lowering the thermal stability and electric insulation of the flame retardant is mainly composed of magnesium and aluminum derived from a catalyst, and ions such as alkali and alkaline earth for cleaning and refining. When an aqueous solution containing is used, sodium, potassium, calcium and the like contained therein can be mentioned. These metals reduce the electric resistance of the flame retardant and the resin composition containing the same, and also act as a catalyst for the decomposition or disproportionation of the phosphate ester at a high temperature, and significantly lower the thermal stability of the flame retardant. This has been found by the present inventors' research.

Regarding the effect of the catalyst on the phosphate ester flame retardant, Japanese Patent Application Laid-Open No. 7-011121 discloses that the amount of magnesium as an impurity is 50 ppm by weight or less in order to prevent discoloration of the surface of a molded product of a polyphenylene ether composition. A method of using a phosphoric acid ester oligomer as a flame retardant is described. However, this patent claims 6-14
Compound (1), which is a phosphate ester oligomer cross-linked with a divalent aryl residue, an alkyl-substituted aryl residue, and an aralkyl residue having the following carbon number: Is not included. There is no description about metals other than magnesium, nor is it described that metal affects the thermal stability and electrical properties of the flame retardant composition. It cannot be inferred that a flame retardant composition having excellent properties can be provided.

In order to ensure the thermal stability required for continuous molding of the flame retardant composition, the conditions shown in the above patents, in which the content of magnesium is 50 ppm by weight or less relative to the composition, are insufficient, and the total metal content Should be 30 ppm by weight or less, and more preferably 10 ppm by weight or less. The metal content in the above flame retardant composition is usually difficult to achieve only by washing with warm water, but can be achieved by extraction with an acid or alkali, or a method of removing the metal as a precipitate.

As a simple method for evaluating the thermal stability of a flame retardant,
A method is known in which heating is performed at a constant rate of temperature increase using a thermobalance and the amount of weight loss when a specific temperature is reached is evaluated. For example, Japanese Patent Publication No. 62-25706 and Japanese Patent Application Laid-Open No.
-236353, JP-A-5-186681, and the like. However, although this method is effective as an index of the phenomenon derived from the volatilization of low boiling components such as the above-mentioned triaryl phosphate, the chemical change of the phosphate due to the disproportionation reaction or the promotion of thermal decomposition and the accompanying change However, it cannot be used as an indicator of problems such as smoke and mold contamination during molding.

The present inventors have found that the temperature of a flame retardant is rapidly raised to a specific temperature in an inert atmosphere by a thermobalance (TGA) and then maintained at that temperature for a certain period of time. Was found to be an indicator of the above problem. That is, 20 ± 10 mg of the flame retardant
When heated to 300 ° C. at a rate of 100 ° C./min in a stream of nitrogen or helium and then held for 1 hour,
If the weight loss for 20 minutes from the start of heating with respect to the charged amount is defined as the initial weight reduction rate, and the weight loss rate at the equilibrium is defined as three times the weight loss rate for 40 minutes to 60 minutes after the start of heating, the former is 15%. % By weight or less, the latter being 4% by weight / hour or less, and more preferably the former being 10% by weight or less and the latter being 3% by weight / hour or less, such as problems such as smoke and mold contamination during molding. Does not appear.

The initial weight loss rate mainly reflects the amount of low-boiling components such as triaryl phosphate and diaryl phosphoric acid. To reduce this value to 15% by weight or less, the low-boiling point contained in the flame retardant is required. What is necessary is just to make the amount of a component into about 15 weight% or less. On the other hand, the rate of weight loss at equilibrium mainly reflects the disproportionation reaction of the ester by the diarylphosphoric acid and the metal and the action of promoting thermal decomposition. Normally, 4% by weight / hour or less can be achieved within the scope of the invention.

The flame-retardant resin composition of the present invention comprises (A) the above-mentioned flame retardant composition and (B) a synthetic resin containing no halogen element as essential components. Since there is no decrease in the electrical properties, there is no problem such as smoke, gelation, low molecular weight of resin, mold contamination, mold corrosion and the like during molding, and there is no decrease in electrical insulation. Synthetic resins include, for example, phenolic resins such as novolak type and resol type, epoxy resins such as glycidyl ether type, glycidyl ester type and glycidylamine type, orthophthalic acid type, isophthalic acid type, terephthalic acid type, bisphenol type and vinyl ester type. Such as unsaturated polyester resin, polyphenylene ether resin, polycarbonate resin, polyester resin such as polyethylene terephthalate / polybutylene terephthalate, polystyrene resin such as polystyrene / rubber-modified polystyrene / AS resin, ABS resin, high density polyethylene / low density polyethylene / polypropylene Polyolefin resin such as 6
-Nylon-6,6-Nylon-6,10-Nylon-
Polyamide resins such as 12-nylon, thermoplastic polyurethanes such as polyester-based, polyether-based, adipate-based, and lactone-based thermoplastic elastomers such as styrene-butadiene block copolymers, ethylene-propylene elastomers, and ethylene-based ionomers; Combinations can be mentioned.

Of these, one selected from polyphenylene ether resins, polycarbonate resins, polystyrene resins, polyester resins, and polyamide resins or a combination of a plurality of resins containing these resins is preferred. Polyphenylene ether resins, polycarbonate resins alone, or resins of these resins are preferred. Combination containing, when the resin composition and the flame retardancy, heat resistance, the effect of improving the electrical properties is remarkable,
Particularly preferred.

The amount of the flame retardant composition added to the synthetic resin depends on the type and application of the resin, and is not particularly limited.
-40% by weight, preferably 5-25% by weight. In general, if the amount of the flame retardant composition is less than 1% by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 40% by weight, the mechanical properties of the resin composition tend to decrease. Although the method for producing the flame-retardant resin composition of the present invention is not particularly limited, for a thermoplastic resin, for example, a generally known extruder, a heating roll, a kneader, a kneader such as a Banbury mixer is used. Can be manufactured. Further, the thermosetting resin can be produced by a method of performing a polymerization reaction after mixing with a resin material before polymerization.

The resin composition of the present invention may contain other flame retardants such as known organic halogens such as decabromodiphenyl ether, tetrabromobisphenol A, hexabromobenzene and perchlorocyclododecane as long as the effects of the present invention are not impaired. Compounds, inorganic phosphorus compounds such as red phosphorus, polyphosphoric acid, and ammonium phosphate; halogen-containing phosphorus compounds such as tris (halopropyl) phosphate and tris (haloethyl) phosphate; melamine, urea, methylolmelamine, dicyandiamide, melamine resin, urea resin, etc. Nitrogen-containing compounds, inorganic hydroxides such as aluminum hydroxide and magnesium hydroxide, inorganic compounds such as antimony oxide, molybdenum oxide, ammonium molybdate, zinc oxide, zinc borate, tin oxide, polytetrafluoroethylene, and siloxane compounds. And anti-drip agents, such as may be used in combination.

Further, other additives such as a plasticizer, a release agent, and the like may be added to the resin composition of the present invention within a range not to impair the effects of the present invention.
Stabilizers such as ultraviolet absorbers, antioxidants, and light stabilizers, or dyes and pigments can be contained. Further, fillers such as glass fibers, glass chips, glass beads, carbon fibers, wollastonite, calcium carbonate, talc, mica, wood powder, slate powder, and fibrous asbestos can also be added.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples. First, a method for analyzing a flame retardant will be described below. 1. Quantification of product Composition based on condensation degree n: Tosoh GPC column Tosoh TSKgel G2000HXL 2 Tosoh TSKgel G3000HXL 1 in series Solvent THF flow = 1ml / min Detector UV λ = 254nm sample : Shimadzu LC-1OA column JASCO Finepak SIL C18S 1 pc. Tosoh TSKgel ODS-80T 1 pc. Series solvent methanol / water = 90/10 flow = 1.0 ml / min Detector UV λ = 254 nm sample methanol 50-fold dilution 10 μl absolute calibration Linear method Determination of metal content: ICP method equipment Seiko JY-38PII type sample MIBK 30-fold dilution absolute calibration curve method Quantitation of water content: Karl Fischer method equipment Mitsubishi Kasei CA-05 trace amount Minute measuring device TGA thermal stability device Rigaku TAS-300 TG-DTA sample 20 ± 10mg D5mm * H2.5mm aluminum sample pan Measurement condition 50 ℃ → (heating 100 ℃ / min) → 300 ℃ 1 hour For working example Resins and the like are shown below. [Polyphenylene ether resin (abbreviated as PPE)] Poly 2,6-dimethyl-1,4-phenylene ether having an intrinsic viscosity of 0.53 measured at 30 ° C. in chloroform was used. [Polystyrene resin (abbreviated as GPPS)] Asahi Kasei Polystyrene 685 manufactured by Asahi Kasei Corporation was used. [Impact-resistant polystyrene resin (abbreviated as HIPS)] Asahi Kasei Polystyrene 9405 manufactured by Asahi Kasei Kogyo Co., Ltd. was used. [ABS resin (abbreviated as ABS)] manufactured by Asahi Kasei Corporation
Styrac 6920 (30% by weight of rubber component) was used. [Polycarbonate resin (abbreviated as PC)] Panlite L1250 manufactured by Teijin Chemicals Ltd. was used. [Polytetrafluoroethylene (abbreviated as PTFE)] Daiflon F201L manufactured by Daikin Industries, Ltd. was used. [Flame retardant composition] As for triphenyl phosphate (abbreviated as TPP) and resorcinol bisdiphenyl phosphate (abbreviated as CR733s), Daihachi Chemical Industry Co., Ltd. was used. Further, the flame retardants 1 to 7 were obtained in Examples 1 to 4 and Comparative Example 1.
-3. Table 1 shows each structural formula, and Table 2 shows composition analysis values.

The evaluation method of the resin composition is shown below. 1. Volatility during molding processing The amount of smoke generated at the nozzle during injection molding was visually observed and judged. 2. Mold Contamination During Molding Using the mold shown in FIG. 1, continuous molding was performed up to 30,000 shots, and the number of shots until the vent portion of the mold was closed was counted. With respect to the material that did not cause blockage, the state of attachment of volatile matter to the vent after completion of the test was observed. Further, the corrosion state of the mold at the end of the test was visually determined. 3. Electrical properties In accordance with JIS C2110, the dielectric breakdown strength was measured by a counter electrode, short-time method. 4. Flame retardant performance Measured in accordance with the UL94 standard vertical combustion test (1/16 inch thickness).

[0034]

Example 1 (Production of Flame Retardant 1) 100 parts by weight of bisphenol A dehydrated by vacuum drying (molar ratio 1.0, water 120 parts by weight p)
pm), 168 parts by weight of phosphorus oxychloride (molar ratio 2.5),
And 0.62 parts by weight of anhydrous magnesium chloride (molar ratio: 0.1
015, 0.83% by weight of water) into a reactor equipped with a stirrer / reflux tube and a vacuum distillation apparatus, and then stirred for 7 hours under a nitrogen stream.
The reaction was performed at 0 to 120 ° C for 5 hours. After the completion of the reaction, the pressure in the reactor was reduced to 50 mmHg while maintaining the reaction temperature, and unreacted phosphorus oxychloride was recovered. Then, the reactor was cooled to 70 ° C., and 165 parts by weight of dehydrated and dried phenol (molar ratio 4.0, water 30 ppm by weight) was added, and 100 to 15
The mixture was heated to 0 ° C. and reacted for 7 hours. 1 at the same temperature
The pressure was reduced to 0 mmHg, and unreacted phenols were distilled off to obtain 284 parts by weight of a crude phosphoric ester. 100 parts by weight of the crude phosphoric acid ester was transferred to a stirring tank equipped with a jacket and a sight glass, and 100 parts by weight of 0.1 N hydrochloric acid was added thereto. Next, 100 parts by weight of pure water was added, and the mixture was stirred at 80 ° C. for 1 hour and left standing for 30 minutes to separate and remove an aqueous phase. After rinsing with pure water three more times in the same manner, water and residual phenol are distilled off by a thin film evaporator, and “flame retardant 1”
96.4 parts by weight were obtained. Table 2 shows the results of composition analysis and the results of evaluation by TGA. FIG. 2 shows a weight loss curve of TGA.

[0035]

Example 2 (Production of Flame Retardant 2) Except that 100 parts by weight of a crude phosphoric ester synthesized by the method of Example 1 was used, and 100 parts by weight of a 1N aqueous sodium hydroxide solution was used instead of 0.1 N hydrochloric acid. Was subjected to washing and purification in the same manner as in Example 1,
89.2 parts by weight of flame retardant 2 ″ were obtained.
Table 2 shows the results of evaluation by GA. FIG. 2 shows a weight loss curve of TGA.

[0036]

Example 3 (Production of Flame Retardant 3) Bisphenol A 100 parts by weight (molar ratio 1.0, water 123 ppm by weight), phosphorus oxychloride 2
69 parts by weight (molar ratio: 4.0) and 0.64 parts by weight of anhydrous magnesium chloride (molar ratio: 0.015, water: 1.7% by weight) were mixed with a stirrer / reflux tube and vacuum distillation equipment attached.
The L reactor was charged and reacted at 70 to 120 ° C. for 6 hours under a nitrogen stream. After the completion of the reaction, the pressure in the reactor was reduced to 50 mmHg while maintaining the reaction temperature, and unreacted phosphorus oxychloride was recovered. Then, the reactor was cooled to 70 ° C., and 57 parts by weight of 2,6-xylenol (molar ratio: 1.1, water: 82 parts by weight)
pm) and 1.1 parts by weight of aluminum chloride (molar ratio of 0,1).
02, 2.3% by weight of water) and reacted at 110 to 150 ° C. for 6 hours. The reactor was cooled again to 70 ° C., and 125 parts by weight of phenol (a molar ratio of 3.1 and a water content of 35 parts by weight
pm), and the mixture was heated to 100 to 150 ° C. and reacted for 7 hours. The pressure was reduced to 10 mmHg at the same temperature, and unreacted phenols were distilled off to obtain 310 parts by weight of a crude phosphoric ester. Using 100 parts by weight of the crude phosphate, washing, rinsing and distillation were carried out in the same manner as in Example 1 to obtain 95.8 parts by weight of "flame retardant 3". Table 2 shows the results of composition analysis and the results of evaluation by TGA.

[0037]

Example 4 (Production of Flame Retardant 4) Crude phosphoric acid was produced in the same manner as in Example 1 except that 190 parts by weight of cresol (molar ratio 4.0, water 320 ppm by weight) was used instead of 164 parts by weight of phenol. 310 parts by weight of the ester were obtained. Using 100 parts by weight of this crude phosphate, washing, rinsing and distillation were carried out in the same manner as in Example 1 to obtain 96.2 parts by weight of "flame retardant 4". Table 2 shows the composition analysis results and the TGA evaluation results.
Shown in

[0038]

Comparative Example 1 (Production of Flame Retardant 5) 100 parts by weight of the crude phosphoric acid ester synthesized by the method of Example 1 was transferred to a stirring tank and used as a washing water.
Washing was carried out under the same operating conditions as in Example 1 except that 100 parts by weight of pure water was used instead of 1 N hydrochloric acid until the pH of the washing water became 5 or more, followed by distillation and drying to obtain "flame retardant 5". 93.6 parts by weight. Table 2 shows the results of composition analysis and the results of evaluation by TGA. FIG. 2 shows a weight change curve of TGA.

[0039]

Comparative Example 2 (Production of Flame Retardant 6) 100 parts by weight of bisphenol A (molar ratio 1.0, water 1100 ppm by weight), 176 parts by weight of phosphorus oxychloride (molar ratio 2.6), 1.0 part of anhydrous magnesium chloride Parts (molar ratio 0.025, water content 7.2% by weight) and cresol 191 parts by weight (molar ratio 4.0, water content 930 ppm by weight),
Under operating conditions, 307 parts by weight of a crude phosphoric ester were obtained. Using 100 parts by weight of the crude phosphoric acid ester, washing and purification were carried out in the same manner as in Comparative Example 1 to obtain 95.1 parts by weight of "flame retardant 6". Table 2 shows the composition analysis results and the TGA evaluation results.
Shown in

[0040]

Comparative Example 3 (Production of composition 7) Example 1 except that 149 parts by weight of phenol (molar ratio 3.6, water 30 ppm by weight) were used.
282 parts by weight of a crude phosphoric ester was obtained under the same apparatus and operating conditions as in the above. 100 parts by weight of this crude phosphoric acid ester was transferred to a stirring tank and washed and purified in the same manner as in Example 1 to obtain 94.8 parts by weight of "flame retardant 7". Composition analysis results and TGA
Table 2 shows the measurement results of the thermal stability according to the above. FIG. 2 shows a TGA weight change curve.

[0041]

Examples 5 to 8 and Comparative Examples 4 to 8 60 parts by weight of PPE,
21 parts by weight of HIPS, 9 parts by weight of GPPS, and flame retardant 1
After 0 parts by weight were melt-kneaded with a twin-screw extruder set at a cylinder temperature of 300 ° C. to form pellets, a test piece for measuring physical properties was prepared using an injection molding machine, and a continuous shot test was performed.

Table 3 shows the results of the evaluation performed by the above-described method.

[0043]

Examples 9-12 and Comparative Examples 9-12 PC 75 parts by weight, ABS 25 parts by weight, flame retardant 15 parts by weight, and PTF
E0.3 parts by weight was melt-kneaded with a twin-screw extruder set at a cylinder temperature of 240 ° C. to form pellets. Then, a test piece for measuring the flame retardancy was measured using an injection molding machine, and a continuous shot test was performed. Carried out. Table 4 shows the results of the evaluation performed by the above-described method.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

[Table 4]

[0048]

Industrial Applicability The flame retardant composition of the present invention has excellent thermal stability and electrical insulation, and the flame retardant resin composition of the present invention using the composition has excellent flame retardant performance, heat resistance, and electric resistance. It is very useful in industry because it has insulating properties and does not cause various problems such as smoke during extrusion and molding, mold contamination and corrosion.

[Brief description of the drawings]

FIG. 1 is a schematic view of a mold used for a continuous molding test.

FIG. 2 is a TGA weight loss curve of the flame retardants and TPP obtained in Examples 1 and 2 and Comparative Examples 1 and 3.

[Explanation of symbols]

 1: TGA weight loss curve of flame retardant 1 2: TGA weight loss curve of flame retardant 2 3: TGA weight loss curve of flame retardant 5 4: TGA weight loss curve of flame retardant 7 5: TGA weight loss curve of CR733s 6: Curve showing temperature

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-8-67685 (JP, A) JP-A-8-12811 (JP, A) JP-A-6-263977 (JP, A) 151493 (JP, A) JP-A-8-325409 (JP, A) JP-A-9-52977 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101 / 16 C08K 3/00-13/08 C09K 21/12-21/14

Claims (2)

(57) [Claims] (A) A mixture of a phosphoric ester represented by the following general formula (1), wherein n is an integer of 0 to 10, wherein the content of the diarylphosphoric acid represented by the following general formula (2) is 1% by weight or less and total content of metal is 30% by weight
pm or less, and when heated to 300 ° C. in an inert gas atmosphere at a rate of 100 ° C./min in an inert gas atmosphere and maintained at that temperature, the weight loss rate for 20 minutes from the start of heating is 15%. Flame retardant for resins that is less than wt%. Embedded image (In the formula, n is an integer of 0 to 10, and R1 to R4 are each independently a phenyl group, a tolyl group, or a xylyl group.
When n is 2 or more, a plurality of R4s may be the same or different. ) (In the formula, R1 and R2 are each independently a phenyl group, a tolyl group, or a xylyl group.) 2. The content of diaryl phosphoric acid is 0.5% by weight.
The flame retardant for a resin according to claim 1, wherein the total content of the metal components is 10 ppm by weight or less.