JPH0913038A - Flame retardant composition - Google Patents

Abstract

PURPOSE: To obtain a flame retardant compsn. for synthetic resins which does not vaporize nor bleed during molding, has an excellent processibility, and gives a resin compsn. excellent in flame retardance while hardly degrading the heat resistance of the compsn. by using a specific phosphoric ester mixture. CONSTITUTION: This compsn. is a phosphoric ester mixture represented by formula I (wherein (n) is 0-10; R is a dihydric phenol group represented by formula II, III, or IV, and Ar1 to Ar4 are each a phenyl, tolyl, or xylyl), subject to the conditions that the total content of triaryl phosphates, i.e., compds. wherein (n) is 0, is 30wt.% or lower and that the ratios of the contents of condensed phosphoric esters wherein (n) is 1 and one, two, or three of Ar1 to Ar4 are 2,6-xylyl to the total content of condensed phosphoric esters wherein (n) is 1 and to the total amt. of the mixture are 50-100wt.% and 35-100wt.%, respectively. The compsn. is obtd. by the condensation of a phosphorus oxyhalide and monohydric and dihydric phenols.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention provides a resin composition which, when used in a resin, does not cause problems such as volatilization and bleeding during molding and has excellent fluidity and heat resistance balance and flame retardancy. It relates to a flame retardant composition.

[0002]

2. Description of the Related Art Synthetic resins are generally lightweight, have excellent water resistance, chemical resistance, electrical insulation, mechanical properties, etc., and are easy to mold, so they are used as building materials, electrical / electronic / home appliance materials. Widely used as automobile materials, textile materials, etc. On the other hand, synthetic resins are generally flammable, and various proposals have been made to impart flame retardancy. The most common means of making these flame-retardants are organic halogen compounds,
This is a method in which a flame retardant such as a phosphorus compound or an inorganic hydrate is added at the time of preparing a resin molded product.

Of the above flame retardants, organic halogen compounds are most widely used because they exhibit excellent flame retardant effects on many synthetic resins. However, halogen-containing compounds thermally decompose during resin molding to generate hydrogen halide, contaminating the work environment, corroding the mold,
There is a problem that causes coloring and gelation of the resin. further,
There is also a problem that a large amount of smoke is generated together with hydrogen halide gas, which is corrosive and harmful to the human body, when burned by a fire or the like.

Inorganic hydrates such as aluminum hydroxide and magnesium hydroxide are known as flame retardants containing no halogen. However, these have a small flame retardant effect,
In order to obtain sufficient flame retardancy, it is necessary to add a large amount, and there is a drawback that the original physical properties of the resin are impaired. Phosphorus compounds, especially organic phosphates, do not contain halogen and are widely used as flame retardants that can provide good flame retardant effects. Typical 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, and have drawbacks such as extrusion with resin and volatilization at the time of molding to cause contamination of the mold, and bleeding on the surface of the molded product to impair the appearance. There is also a problem that it acts as a plasticizer and greatly reduces the heat resistance of the resin composition.

As the phosphoric acid ester having low volatility, condensed phosphoric acid esters described in JP-B-51-39271, JP-B-54-32818, JP-B-62-25706, JP-B-2-18336 and the like are disclosed. There is. However, these compounds are inferior in flame retardancy to the above-mentioned triaryl phosphate ester, and also have no effect of improving the heat resistance of the resin composition.

As the phosphoric acid ester having low volatility and not impairing heat resistance, US Pat. No. 4,134,876, and
No. 5122556, JP-A No. 5-1079,
There is a condensed phosphoric acid ester having a substituent at all ortho positions of a monovalent phenol residue described in JP-A-7-11119. However, these compounds are resinous solids or solids, and thus have problems that they are inferior in dispersibility in resins and molding processability, and inferior in flame retardancy to triaryl phosphates.

[0007]

DISCLOSURE OF THE INVENTION The present invention is a synthetic resin which has no volatilization or bleeding during molding, is excellent in moldability, has a small decrease in heat resistance of the resin composition, and has excellent flame retardancy. It is an object of the present invention to provide a flame retardant composition for resins.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that xylyl groups other than phenyl group, tolyl group and 2,6-xylyl group containing two phosphorus atoms in the molecule. A phosphoric acid ester composition mainly containing a condensed phosphoric acid ester having any one of them and a 2,6-xylyl group in the molecule is disclosed in U.S. Pat. No. 4,134,876, U.S. Pat. In addition to providing the resin composition with heat resistance equivalent to that of the condensed phosphoric acid ester having a substituent at all ortho positions of the monohydric phenol residue described in JP-A-1079, it has excellent moldability and is surprisingly triaryl. They have found that they exhibit excellent flame retardant performance that surpasses phosphate esters, and have completed the present invention.

That is, the present invention provides a mixture of phosphoric acid esters represented by the following general formula (1),

[0010]

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(In the formula, n is an integer of 0 to 10, R is an aromatic group represented by the following chemical formula 4 and is derived from a divalent phenol, and Ar1 to Ar4 are each independently a phenyl group. , A tolyl group or a xylyl group. When n is 2 or more, a plurality of Ar4 may be the same or different.

[0012]

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The triaryl phosphoric acid ester represented by n = 0 is contained in an amount of 30% by weight or less based on the whole mixture, and n = 1.
The total content of compounds in which one to three of Ar1 to Ar4 of the condensed phosphoric acid ester represented by 2 is a 2,6-xylyl group is 50 to 10 with respect to the entire compound represented by n = 1.
0% by weight and 35 to 10 with respect to the whole phosphoric acid ester
It provides a flame retardant composition in the range of 0% by weight.

The compounds which are the main components of the flame retardant composition of the present invention are represented by the following chemical formulas.

[0015]

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(Wherein R represents the same aromatic group as in the general formula (1), Ar 1 to Ar 3 are the same or different,
A xylyl group other than a phenyl group, a tolyl group, or a 2,6-xylyl group. ) Examples of the divalent phenols, which are raw materials for inducing R in the general formula (1) of the flame retardant composition of the present invention, include hydroquinone, resorcinol, catechol, 4,4′-bisphenol, and 2,2-bis (4). -Hydroxyphenyl) propane [commonly called bisphenol A] is mentioned, and bisphenol A is particularly preferable.

The monovalent aromatic group represented by Ar1 to Ar4 in the general formula (1) of the flame retardant composition of the present invention is any one of a phenyl group, a tolyl group and a xylyl group,
Particularly, the compounds (A) to (D), which are the main components,
It contains at least one of a 2,6-xylyl group and other substituents. These aromatic groups are derived from the corresponding phenols: phenol, cresol, and xylenol.

The flame retardant composition of the present invention can be produced by a known method of condensing a monohydric phenol and a dihydric phenol with phosphorus oxyhalide. For example, JP-B-62-25706 discloses a method in which phosphorus oxyhalide and monohydric phenols and dihydric phenols are charged together and the reaction is carried out. No. 1079 discloses a method of reacting phosphorus oxyhalide with monohydric phenol and then adding dihydric phenol to complete the reaction.
JP-A-227632 discloses a method of reacting phosphorus oxyhalide with dihydric phenols and then adding monohydric phenols to complete the reaction. But,
As a method for producing an active ingredient, a condensed phosphoric acid ester having both a 2,6-xylyl group and other aromatic groups at an arbitrary ratio, after reacting phosphorus oxyhalide with a dihydric phenol, 2 , 6-xylenol is reacted,
Furthermore, a 3-step synthetic method in which a monohydric phenol other than 2,6-xylenol is added to complete the reaction is preferable.

That is, in the first step, in the presence of a catalyst such as a Lewis acid, 1.5 times or more, preferably 2 times or more, moles of phosphorus oxyhalide is reacted with the dihydric phenol to react with the phosphorus dimer. Is synthesized as a main component, and unreacted phosphorus oxyhalide is removed by a method such as distillation, if necessary, to prevent by-production of triaryl phosphate ester. In the next step, depending on the intended product composition, the dihydric phenols used in the first step,
Usually, 1 to 3 times mol of 2,6-xylenol is reacted. Then, in the final step, an amount of 1 or more other than 2,6-xylenol, which is equivalent to or more than the residual unreacted halogen,
After the unreacted monohydric phenols have been removed by distillation, etc., the reaction is completed by adding dihydric phenols, and then the catalyst and residual halogen components are removed by methods such as washing and filtration to obtain the desired product. obtain.

The proportion of the triaryl phosphates in the flame retardant composition of the present invention is 30% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less.
When it exceeds 30% by weight, the heat resistance of the resin composition is lowered, and problems such as volatilization and bleeding during extrusion / molding with the resin are caused. The effective component in the flame retardant composition of the present invention is a condensed phosphoric acid having in the molecule thereof a 2,6-xylyl group and either a phenyl group, a tolyl group or a xylyl group other than the 2,6-xylyl group. Among the esters, the condensed phosphoric acid ester represented by n = 1 in the general formula (1) is particularly excellent in both flame retardancy and heat resistance retention when mixed with a resin. Generally, when the value of n increases, the flame retardant performance tends to decrease.

Therefore, in order for the flame retardant composition to exert the above-mentioned unique effect, the compound having 1 to 3 2,6-xylyl groups among the condensed phosphoric acid ester represented by n = 1 is 50 to 50 in total for all compounds represented by n = 1
100% by weight and 3 based on the total amount of phosphoric acid ester
It is necessary to contain 5 to 100% by weight, preferably 60 to 100% by weight with respect to the whole compound represented by n = 1 and 50 to 100% by weight with respect to the whole phosphoric acid ester, and n = 1 to 70 to 100% by weight based on the whole compound and 5 to the whole phosphoric acid ester
It is more preferable to contain 5 to 100% by weight.

When the content of these is less than the above values,
When n = 1 and a large amount of a compound not containing a 2,6-xylyl group are contained, heat resistance cannot be obtained, and n = 1 and all monovalent aromatic groups are 2,6-xylyl groups. When a certain compound and a compound of n ≧ 2 are contained in a large amount, the moldability is deteriorated, and in any case, the flame retardancy is deteriorated. With the flame retardant composition of the present invention, the physical properties of the resin composition can be adjusted by the composition thereof. That is, heat resistance is further improved by increasing the proportion of the 2,6-xylyl group contained in the condensed phosphoric acid ester represented by n = 1 while maintaining excellent heat resistance, moldability and flame retardancy. If you reduce it, you can improve the liquidity.

The flame retardant composition of the present invention exerts the above-mentioned excellent effects on various synthetic resins. Examples of the synthetic resin include novolac type / resole type phenolic resin, glycidyl ether type / glycidyl ester type /
Glycidylamine type epoxy resin, orthophthalic acid type / isophthalic acid type / terephthalic acid type / bisphenol type / vinyl ester type unsaturated polyester resin, vinyl chloride resin, polyphenylene ether resin, polycarbonate resin, polyethylene terephthalate / polybutylene terephthalate Polyester resin such as polystyrene, rubber modified polystyrene, AS resin, ABS
Polystyrene resin such as resin, high density polyethylene, low density polyethylene, polyolefin resin such as polypropylene, 6-nylon-6,6-nylon-6,10-
Polyamide resin such as nylon-12-nylon, thermoplastic polyurethane such as polyester / polyether / adipate / lactone, styrene-butadiene block copolymer / ethylene-propylene elastomer / ethylene ionomer / thermoplastic elastomer and Examples thereof include a combination thereof, but a thermoplastic resin composed of one kind or a combination of two or more kinds selected from polyphenylene ether resin, polycarbonate resin, polyester resin, polystyrene resin, and thermoplastic elastomer is preferable, and polyphenylene ether resin and Particularly preferred are polystyrene resins and resins consisting of a combination of polycarbonate resin and polystyrene resin.

The addition amount of the flame retardant for resin of the present invention to the resin is not particularly limited as long as the effects of the invention can be sufficiently exerted, but it is usually difficult to add the flame retardant for resin to 100 parts by weight of the resin component. 1 to 50 parts by weight, preferably 2 to 40
Parts by weight, more preferably 5 to 30 parts by weight. If the proportion of the flame retardant component for resin is less than 1 part by weight, the flame retardancy is insufficient, and if it exceeds 50 parts by weight, the characteristics inherent to the resin such as mechanical properties are lost.

Further, the resin composition of the present invention contains other flame retardants within the range not impairing the effects of the invention, for example, known organic halogens such as decabromodiphenyl ether, tetrabromobisphenol A, hexabromobenzene and perchlorocyclododecane. Compounds, inorganic phosphorus compounds such as red phosphorus, polyphosphoric acid, ammonium phosphate, halogen-containing phosphorus compounds such as tris (halopropyl) phosphate, 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 and tin oxide, polytetrafluoroethylene, siloxane compounds And anti-drip agents, such as may be used in combination.

[0026]

The present invention will be described below in detail with reference to examples. The resins 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 0.52 measured at 30 ° C. in chloroform was used. [Polycarbonate resin (abbreviated as PC)] Panlite L1250 manufactured by Teijin Chemicals was used. [Polystyrene resin (abbreviated as GPPS)] Asahi Kasei Polystyrene 685 manufactured by Asahi Kasei Corporation was used. [High-impact polystyrene resin (abbreviated as HIPS)] Asahi Kasei Polystyrene 9405 manufactured by Asahi Kasei Corporation was used. [ABS resin (abbreviated as ABS)] Styrac 6920 (rubber component 30% by weight) manufactured by Asahi Kasei Corporation was used. [Polytetrafluoroethylene (abbreviated as PTFE)]
Daiflon F201L manufactured by Daikin Industries, Ltd. was used. [Flame Retardant Composition] Table 1 shows. In addition, Examples 1 to 3 show the method for producing the compositions 1 to 3. -Composition 4: Triphenyl phosphate-Composition 5: Resorcinol poly (phenyl phosphate) -Composition 6: Hydroquinone bis (2,6-xylyl) phosphate The analysis method of the flame retardant composition is shown below. 1. Quantification 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 200 times diluted 5 μl Absolute calibration curve method Composition of (n = 1 component): Shimadzu LC-1OA column Tosoh TSKgel ODS-80T solvent methanol / water = 90/10 flow = 0.5 ml / min detector UV λ = 254 nm sample methanol 100-fold dilution 10 μl area ratio 2. Identification of components Measuring device = LC-MS (Hitachi API type) column Tosoh TSKgel ODS-80T solvent methanol / water = 95/5 flow = 1 ml / min sample methanol 100-fold dilution 10 µl ionization drift voltage 750 atomization chamber 280 ° C desolvent Chamber 350 ° C. Measuring range m / e 200 to 1000 The evaluation method of the resin composition is shown below. 1. Volatility during molding The amount of smoke emitted from the nozzle during injection molding was visually observed and judged. 2. Excretion of Flame Retardant on Composition Surface and Presence or Absence of Molding Failure The appearance of the surface of the injection-molded product was visually observed and judged. 3. Impact resistance: Measured using a 1/8 inch test piece according to the Izod test method specified in ASTM D256. 4. Heat resistance Heat distortion temperature (HDT) according to ASTM D648
Was measured. 5. Flame-retardant performance Measured according to the UL94 standard vertical combustion test (thickness 1/16 inch).

[0027]

Example 1 <Production of Composition 1> 114 g of bisphenol A (0.5
Mol), phosphorus oxychloride 192 g (1.25 mol), and anhydrous magnesium chloride 1.4 g (0.015 mol),
The mixture was placed in a 500 ml four-necked flask equipped with a stirrer / reflux tube, and reacted at 70 to 140 ° C. for 4 hours under a nitrogen stream (first reaction step). After completion of the reaction, while maintaining the reaction temperature, the pressure of the flask was reduced to 200 mmHg or less by a vacuum pump, and unreacted phosphorus oxychloride was collected by a trap. Then, the flask was cooled to room temperature, 122 g (1.0 mol) of 2,6-xylenol and 2.0 g (0.015 mol) of anhydrous aluminum chloride were added, and the temperature was 100 to 150 ° C.
The mixture was heated to room temperature and reacted for 4 hours (second reaction step). Then, the flask was cooled to room temperature, 94 g (1 mol) of phenol was added, heated to 100 ° C. to 150 ° C. and held for 4 hours to complete the reaction (third reaction step). The pressure was reduced to 1 mmHg at the same temperature, and unreacted phenols were distilled off. Hydrogen chloride gas generated during the reaction was collected with an aqueous sodium hydroxide solution, and the amount of the generated hydrogen chloride was measured by neutralization titration to monitor the progress of the reaction. The produced crude phosphate ester was washed with distilled water, and then the solid content was removed with filter paper (# 131 manufactured by Advantech). After vacuum drying, a pale yellow transparent composition was obtained. Table 1 shows the results of the composition analysis.

[0028]

Example 2 <Production of Composition 2> Bisphenol A was used in the first reaction step.
55 g (0.5 mol) of resorcinol instead of 2nd
In the reaction step, 159 g (1.3 mol) of 2,6-xylenol and in the third reaction step 76 g of m-cresol (0.7
A light yellow transparent composition was obtained by the same method as in Example 1 except that (mol) was used. Table 1 shows the results of the composition analysis.

[0029]

Example 3 <Production of Composition 3> Phosphorus oxychloride 154 was used in the first reaction step.
g (1.0 mol), the same as Example 1 except that 61 g (0.5 mol) of 2,6-xylenol was used in the second reaction step and 141 g (1.5 mol) of phenol was used in the third reaction step. By the method, a pale yellow transparent composition was obtained. Table 1 shows the results of the composition analysis.

[0030]

Examples 4 to 6 and Comparative Examples 1 to 3 75 parts by weight of PC resin, 25 parts by weight of ABS resin, 15 parts by weight of flame retardant shown in Table 1, and 0.3 parts by weight of PTFE were used at a cylinder temperature of 2
Melt-kneading into pellets with a twin-screw extruder set at 40 ° C, and then injection molding machine (cylinder temperature 250 ° C)
Was used to obtain a test piece for measuring physical properties and for a combustion test. Table 2 shows the evaluation results obtained by the above method using the obtained test pieces.

[0031]

[Examples 7-9 and Comparative Examples 4-6] 60 parts by weight of PPE resin, 20 parts by weight of HIPS resin, 20 parts by weight of GPPS resin, and 10 parts by weight of the flame retardant shown in Table 1 were set at a cylinder temperature of 300 ° C. After being melt-kneaded into pellets by the twin-screw extruder, the injection molding machine (cylinder temperature 3
(00 ° C.) was used to obtain test pieces for measuring physical properties and for a combustion test. Table 3 shows the evaluation results obtained by the above-mentioned method using the obtained test pieces.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

EFFECTS OF THE INVENTION The flame retardant composition of the present invention can impart excellent flame retardancy without lowering the heat resistance of the resin, and has problems such as volatilization during molding, bleeding and molding defects. Since it does not occur, it is very useful in industry.

Claims (1)

[Claims] 1. A mixture of phosphoric acid esters represented by the following general formula (1), wherein: (In the formula, n is an integer of 0 to 10, R is an aromatic group represented by the following chemical formula 2, derived from a divalent phenol, and Ar1 to Ar4 are each independently a phenyl group or a tolyl group. Or a xylyl group. When n is 2 or more, a plurality of Ar4 may be the same or different.) A triaryl phosphate represented by n = 0 is contained in an amount of 30% by weight or less based on the total amount of the mixture, and 1 to 3 of Ar 1 to Ar 4 of the condensed phosphate represented by n = 1 are 2,6-xylyl. The total content of the compounds as the group is n =
50 to 100% by weight based on the whole compound represented by 1.
And 35 to 100% by weight with respect to the whole phosphoric acid ester
Flame retardant composition in the range of.