JP2001187843A - Flame retarder for resin and flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant resin composition which is excellent in flame retardancy, heat resistance and electric insulation property and doe not cause fuming at a molding process and pollution and corrosion on the dye by adding a phosphoric ester flame retardant having an excellent heat resistance. SOLUTION: The flame retarded resin composition comprises (A) a flame retardant for resins which retardant has a specific structure crosslinked with bisphenol A, contains not more than 1 wt.% of a diaryl phosphate and not more than 30 wt.ppm in total of metals and has a weight loss of not more than 15 wt.% in TGA when kept at 300 deg.C for 20 min and (B) a non-halogen synthetic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame retardant 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. In addition, carcinogenic properties have 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. Inorganic hydrates such as aluminum hydroxide and magnesium hydroxide are known as halogen-free flame retardants. However, these have a small flame-retardant effect and must be added in a large amount in order to obtain sufficient flame-retardant properties. Therefore, there is a disadvantage that the physical properties of the resin are impaired.

[0004] Phosphorus compounds, especially organic phosphoric esters, do not contain halogen and are widely used as flame retardants which provide good flame retardant effects. Representative organic phosphates include:
Triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylyl phosphate (T
XP) and the like. 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 esters having low volatility which solve these drawbacks include those described in US Pat. No. 252,090 and European Patent Application Publication Nos. 129824 and 12298.
No. 9825, No. 135726, Japanese Patent Publication No. 54-328
No. 18, Japanese Patent Publication No. 62-25706, Special Publication No. 2
A phosphate ester oligomer described in, for example, US Pat. Among these compounds, a phosphate ester oligomer represented by the following general formula (1) cross-linked by a residue of 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A) is resorcinol It is described in JP-A-7-258439 and the like that the heat resistance and the hydrolysis resistance are higher than those crosslinked with a monocyclic phenol residue such as
Particularly preferred.

[0006]

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. )

One of the important factors governing the thermal stability of the phosphoric acid ester oligomer is n = 0 in the general formula (1).
It is well known that the amount of triaryl phosphate having a low boiling point corresponding to the component of
Japanese Patent Publication No. 25706 discloses that the proportion of this component should be 40% by weight or less based on the whole composition. However, according to the study by 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 is caused by using the compound represented by the formula (1). However, this cannot be prevented only by regulating the content of the triaryl phosphate, and a problem often arises particularly when the resin is used for a so-called engineering plastic having a relatively high molding temperature, such as a polyphenylene ether resin or a polycarbonate resin. 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.

Japanese Patent Application Laid-Open No. Hei 5-1079 discloses a highly 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.

[0009]

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.

[0010]

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. As a result, the decomposition temperature and volatilization temperature of the phosphate ester oligomer itself are sufficiently high, but the diarylphosphoric acid represented by the following formula (2) by-produced at the time of synthesis and the metal component derived from the catalyst and the like are converted into the phosphate ester oligomer by heating. It has the effect of accelerating the reduction of molecular weight and the hydrolysis reaction by transesterification, and found that the resulting volatile components cause mold contamination. In order to greatly improve the thermal stability of the flame retardant, it is necessary that both the content of the metal and the content of the diarylphosphoric acid are each equal to or less than a specific value. 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) A mixture of a phosphate ester oligomer represented by the following general formula (1), the content of the diarylphosphoric acid represented by the following general formula (2) is 1% by weight or less, and the total content of the metal components is 30 ppm by weight or less and TGA
When the resin is heated to 300 ° C. at a rate of 100 ° C./min in an inert gas atmosphere and kept at that temperature, the rate of weight loss for 20 minutes from the start of heating is 15% by weight or less. A flame-retardant resin composition comprising a flame retardant and (B) a non-halogen synthetic resin.

[0012]

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. )

[0013]

Embedded image (In the formula, R1 and R2 are each independently a phenyl group, a tolyl group, or a xylyl group.)

2. (B) The flame-retardant resin composition according to the above item 1, 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. object. 3. (B) The flame-retardant resin composition according to the above item 1, wherein the non-halogen synthetic resin is a polyphenylene ether resin and / or a polystyrene resin. 4. (B) The flame-retardant resin composition according to the above item 1, wherein the non-halogen synthetic resin is a polycarbonate resin and an ABS resin.

Hereinafter, the present invention will be described in detail. First, the flame retardant for resin of the present invention will be described. The phosphate ester oligomer represented by the general formula (1) is disclosed in US Pat.
No. 90, JP-B-62-25706, JP-A-63-227632 and the like can be used. 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 dehydrated and dried after removing the chlorine content and the catalyst by washing and purification to obtain a product. The diarylphosphoric acid represented by the general formula (2) is obtained by the reaction of water contained in a catalyst or phenols with phosphorus oxychloride and monohydric phenols, and hydrolysis of a phosphoric ester caused by a washing step and the like. It is produced and its production amount varies depending on the manufacturing conditions.

The phosphoric ester composition containing a diaryl phosphoric acid can provide an antistatic property without deteriorating the physical properties of the resin composition together with the flame retardant action.
No. 706. However, according to the study of the present inventors, diarylphosphoric acid has a higher volatility than a phosphoric acid ester oligomer and has an effect of promoting the formation of a low molecular weight component and a gel-like substance by a disproportionation reaction of a phosphoric acid ester under heating conditions. It turned out that there is. 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, the content is 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 material is 600p based on the total amount of the raw material.
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 the electrical insulation of the flame retardant is mainly composed of magnesium and aluminum derived from the catalyst, and ions such as alkali and alkaline earth for cleaning and purification. 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 phosphoric ester flame retardant, JP-A-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 article of a polyphenylene ether composition. A method of using a phosphoric acid ester oligomer as a flame retardant is described. However, the present invention relates to 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. In addition, there is no description about metals other than magnesium, and it is not described that metals affect the thermal stability and electrical properties of the flame retardant.By regulating the total amount of metals, thermal stability and electrical insulation can be improved. There is no analogy that good flame retardants can be provided.

In order to ensure the thermal stability required for continuous molding of the flame retardant, the condition of 50 ppm by weight or less of magnesium relative to the composition disclosed in the above-mentioned patent documents is insufficient, and the It must be 30 ppm by weight or less, and more preferably 10 ppm by weight or less. The amount of the metal in the flame retardant 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 reduction 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 components contained in the flame retardant are used. Should be approximately 15% by 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 range of the invention. The flame-retardant resin composition of the present invention is a composition comprising (A) the above-described flame retardant and (B) a non-halogen synthetic resin containing no halogen element as essential components. Does not occur, causing smoke during molding, gelling, lowering the molecular weight of the resin, mold contamination,
There is no problem such as mold corrosion, and there is no decrease in electrical insulation.

As the synthetic resin, for example, a novolak type
Phenol resins such as resol type, epoxy resins such as glycidyl ether type, glycidyl ester type and glycidylamine type, unsaturated polyester resins such as orthophthalic acid type, isophthalic acid type, terephthalic acid type, bisphenol type and vinyl ester type, and 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, polyolefin resin such as high density polyethylene / low density polyethylene / polypropylene, 6-nylon・ 6,6-nylon ・
Polyamide resins such as 6,10-nylon and 12-nylon, thermoplastic polyurethanes such as polyester-based, polyether-based, adipate-based, and lactone-based, styrene-
Examples include thermoplastic elastomers such as butadiene block copolymers, ethylene-propylene elastomers, and ethylene ionomers, and combinations thereof. Among these, 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 including these is preferable, and a polyphenylene ether resin, a polycarbonate resin alone or a resin including these resins is included. The combination is particularly preferable because the effects of improving the flame retardancy, heat resistance, and electric properties when the resin composition is used are remarkable.

The amount of the flame retardant added to the synthetic resin depends on the type and use of the resin, and is not particularly limited.
% By weight, preferably 5 to 25% by weight. In general, if the amount of the flame retardant 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 deteriorate. 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 known flame retardants such as decabromodiphenyl ether, tetrabromobisphenol A, hexabromobenzene, perchlorocyclododecane and the like as long as the effects of the present invention are not impaired. Inorganic phosphorus compounds such as halides, 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 Such as 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, and tin oxide; polytetrafluoroethylene; It may be used in combination such as anti-drip agents such objects.

Further, other additives such as a plasticizer, a releasing agent, an ultraviolet absorber, an antioxidant, and a stabilizer such as a light stabilizer may be added to the resin composition of the present invention as long as the effects of the present invention are not impaired. Alternatively, a dye or pigment 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.

[0028]

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. Quantitative determination of product Composition by degree of condensation n: Tosoh GPC column Tosoh TSKgel G2000HXL 2 Tosoh TSKgel G3000HXL 1 in-line solvent THF flow = 1 ml / min Detector UV λ = 254 nm Sample THF 1000-fold dilution 5 μl absolute phosphorus analysis : Shimadzu LC-10A 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 times dilution 10 μl absolute calibration Line method

Determination of metal content: ICP method apparatus Seiko JY-38PII type sample MIBK 30-fold absolute calibration curve method Quantification of water content: Karl Fischer method apparatus Mitsubishi Kasei CA-05 trace water content analyzer TGA thermal stability Equipment Rigaku TAS-300 TG-DTA sample 20 ± 10mg D5mm * H2.5mm aluminum sample pan Measurement conditions 50 ° C → (temperature rise 100 ° C / min) → 300 ° C 1 hour

The resins and the like used in the examples 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] triphenyl phosphate (abbreviated as TPP)
And resorcinol bisdiphenyl phosphate (CR
733s) used by Daihachi Chemical Industry Co., Ltd.
Flame retardants 1 to 7 were produced by the methods of Examples 1 to 4 and Comparative Examples 1 to 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).

[0033]

Example 1 (Production of flame retardant 1) 100 parts by weight of bisphenol A dehydrated by vacuum drying (molar ratio 1.0, water 120 ppm by weight), 168 parts by weight of phosphorus oxychloride (molar ratio 2.5), and anhydrous 0.62 parts by weight of magnesium chloride (a molar ratio of 0.015, and a water content of 0.83% by weight) were charged into a stirrer, a reflux tube, and a reactor attached to a vacuum distillation facility,
The reaction was carried out at 70 to 120 ° C. for 5 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. The reactor was then cooled to 70 ° C. and dehydrated and dried phenol 165.
Parts by weight (molar ratio 4.0, water 30 ppm by weight)
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 284 parts by weight of a crude phosphoric ester.

100 weight parts of the crude phosphoric acid ester is jacketed,
Transfer to a stirring tank with a sight glass and add 0.1N hydrochloric acid 10
After adding 0 weight part and stirring at 80 degreeC for 1 hour, it left still for 30 minutes, and separated and removed the aqueous phase. 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. 3 additional rinses with pure water in the same manner
After repeating the process, water and residual phenol were distilled off by a thin film evaporator to obtain 96.4 parts by weight of "flame retardant 1". Table 2 shows the results of composition analysis and the results of evaluation by TGA. Also, T
The GA weight loss curve is shown in FIG.

[0035]

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

[0036]

Example 3 (Production of Flame Retardant 3) Bisphenol A10
0 parts by weight (molar ratio 1.0, water 123 ppm by weight), phosphorus oxychloride 269 parts by weight (molar ratio 4.0), and anhydrous magnesium chloride 0.64 parts by weight (molar ratio 0.015, water 1.7) % By weight) into a GL reactor equipped with a stirrer / reflux tube and a vacuum distillation facility, and the GL reactor is placed under a nitrogen stream at 70 to 12%.
The reaction was performed at 0 ° C. for 6 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. The reactor was then cooled to 70 ° C and 57 parts by weight of 2,6-xylenol (molar ratio 1.1,
Water (82 ppm by weight) and 1.1 parts by weight of aluminum chloride (molar ratio: 0.02, moisture: 2.3% by weight).
The reaction was performed at 0 to 150 ° C. for 6 hours.

The reactor was cooled to 70 ° C. again, and 125 parts by weight of phenol (a molar ratio of 3.1 and a water content of 35 ppm by weight) were used.
And heated to 100 to 150 ° C. to react 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". Composition analysis results and TGA
Table 2 shows the evaluation results.

[0038]

Example 4 (Production of Flame Retardant 4) 190 parts by weight of cresol instead of 164 parts by weight of phenol (molar ratio 4.0,
310 parts by weight of a crude phosphoric ester were obtained in the same manner as in Example 1, except that water (320 ppm by weight) was used. Using 100 parts by weight of the crude phosphate, washing, rinsing and distillation were carried out in the same manner as in Example 1, and "flame retardant 4" 9
6.2 parts by weight were obtained. Table 2 shows the results of composition analysis and the results of evaluation by TGA.

[0039]

Comparative Example 1 (Production of Flame Retardant 5) 100 parts by weight of a crude phosphoric ester synthesized by the method of Example 1 was transferred to a stirring tank, and 100 parts by weight of pure water was used instead of 0.1 N hydrochloric acid as washing water. After washing under the same operating conditions as in Example 1 until the pH of the washing water became 5 or more, the residue was distilled and dried to obtain 93.6 parts by weight of "flame retardant 5". Table 2 shows the results of composition analysis and the results of evaluation by TGA. FIG. 2 shows a weight change curve of TGA.

[0040]

Comparative Example 2 (Production of Flame Retardant 6) Bisphenol A10
0 parts by weight (molar ratio 1.0, water 1100 weight ppm),
176 parts by weight of phosphorus oxychloride (molar ratio 2.6), 1.0 part by weight of anhydrous magnesium chloride (molar ratio 0.025, water content 7.2% by weight), and 191 parts by weight of cresol (molar ratio 4.0, water content) 930 parts by weight), and 307 parts by weight of a crude phosphoric ester was obtained in the same apparatus and operating conditions as in Example 1. Using 100 parts by weight of this crude phosphate, washing and purification were carried out in the same manner as in Comparative Example 1 to obtain "flame retardant 6" 9
5.1 parts by weight were obtained. Table 2 shows the results of composition analysis and the results of evaluation by TGA.

[0041]

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

[0042]

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]

The flame retardant of the present invention has excellent thermal stability and electrical insulation, and the flame retardant resin composition of the present invention using the flame retardant has excellent flame retardancy, heat resistance and electrical insulation. It is very useful in industry because it does not cause 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

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[Procedure amendment]

[Submission date] April 9, 2001 (2001.4.9)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

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. )

Embedded image (In the formula, R1 and R2 are each independently a phenyl group, a tolyl group, or a xylyl group.)

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

[0010]

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. 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. In order to greatly improve the thermal stability of the flame retardant, it is necessary that both the content of the metal and the content of the diarylphosphoric acid are each equal to or less than a specific value. 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.

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That is, the present invention is as follows. 1. (A) represented by the following general formula (1), wherein n is from 0 to 10
Wherein the content of diarylphosphoric acid represented by the following general formula (2) is 1% by weight.
Below, the total content of the metal content is 30 ppm by weight or less, 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 (B) non-halogen A flame-retardant resin composition comprising a synthetic resin.

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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 dehydrated and dried after removing the chlorine content and the catalyst by washing and purification to obtain a product. The diaryl phosphoric acid represented by the general formula (2) is obtained by reacting water contained in a catalyst or phenol with phosphorus oxychloride and a monohydric phenol,
Further, it is produced by hydrolysis of a phosphoric acid ester caused in a washing step and the like, and the produced amount varies depending on production conditions.

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The phosphoric ester composition containing a diaryl phosphoric acid can provide an antistatic property without deteriorating the physical properties of the resin composition together with the flame retardant action.
No. 706. 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 is easy to release protons,
In addition to causing decomposition of the resin and causing corrosion during molding, it has a strong affinity with water and metals, and is preferable because it causes emulsification in cleaning and purification processes and causes deterioration in electrical properties. Absent. In order to ensure the thermal stability and electrical insulation of the flame retardant, the content of diarylphosphoric acid must be 1% by weight or less, and 0.5% by weight.
It is more preferable to set the following.

Claims (4)

[Claims] (A) a mixture of a phosphate ester oligomer represented by the following general formula (1), wherein the content of a 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 (B) non-halogen A flame-retardant resin composition comprising a synthetic resin. 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 non-halogen synthetic resin (B) 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. Flame-retardant resin composition. 3. The flame-retardant resin composition according to claim 1, wherein the non-halogen synthetic resin (B) is a polyphenylene ether resin and / or a polystyrene resin. 4. The flame-retardant resin composition according to claim 1, wherein the non-halogen synthetic resin (B) is a polycarbonate resin or an ABS resin.