JP2011132320A - Polyarylate resin, polyarylate resin composition and molded body comprising the polyarylate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyarylate resin composition which is excellent in moldability and flame retardancy while retaining impact and heat resistances. <P>SOLUTION: A polyarylate resin is provided comprising a bisphenol A residue, a tetrabromobisphenol A residue and a phthalic acid residue, wherein a molar ratio between the bisphenol A residue and the tetrabromobisphenol A residue is in the range of 9/1 to 4/6. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polyarylate resin and a polyarylate resin composition that are excellent in flame retardancy while maintaining impact resistance and heat resistance.

  Polyarylate resins composed of dihydric phenols and terephthalic acid and / or isophthalic acid are already well known as engineering plastics. Since the polyarylate resin has high heat resistance, excellent mechanical strength and dimensional stability, and is transparent, the molded product is widely used in fields such as electric / electric equipment, automobiles and machines.

  In the field of electrical and electronic equipment, there are many parts that require high flame retardance in order to meet safety requirements. Specifically, in the UL94 flammability test, high flame retardancy equivalent to V-0 or V-1 is often required for plastic materials. Conventionally, polyarylate resin has been used as a plastic material having self-digestibility, but it has not been sufficient for the demand for high flame retardancy in the electric and electronic equipment fields.

  In order to solve the above problem, a method for imparting flame retardancy to a polyarylate resin is known. As such a method, for example, a method of imparting flame retardancy by directly reacting bromine with a polyarylate resin (Patent Document 1) is known. However, in this case, a process and equipment for reacting bromine (that is, a process and equipment for once dissolving the polyarylate resin in a solvent and then reacting with a reagent such as bromine or bromine chloride) are necessary. In some cases, it was difficult to produce industrially. In this method, it is difficult to make the ratio of bromination of polyarylate constant, and the flame retardancy of the obtained brominated polyarylate tends to vary widely.

  In addition, a method for imparting flame retardancy by melting and kneading a brominated polycarbonate oligomer in a resin composition comprising a polyarylate resin and a polycarbonate resin is known (Patent Document 2). However, in this case, in order to impart flame retardancy, it is necessary to add a brominated polycarbonate oligomer in a certain amount. The polyarylate resin composition obtained thereby had a tendency to deteriorate mechanical properties such as impact resistance and thermal properties.

  Moreover, providing a flame retardance by mix | blending a flame retardant with polyarylate resin is a conventionally well-known method. Flame retardants include phosphorous compounds such as phosphate esters; inorganic metal hydrates such as aluminum hydroxide and magnesium hydroxide; nitrogen compounds such as melamine and melamine cyanurate; silicon compounds such as polyorganosiloxane; Inorganic fillers such as talc are being studied.

  When a phosphorus compound is used as a flame retardant, thermal decomposition occurs at the mixing temperature of the polyarylate resin (for example, 300 ° C. or higher), and thus it cannot be stably present in the polyarylate resin. The polyarylate resin composition may not have sufficient flame retardancy.

  In addition, when using an inorganic metal hydrate as a flame retardant, it is necessary to add a large amount of the inorganic metal hydrate in order to impart flame resistance that can withstand practical use. As a result, the transparency, which is one of the above, is significantly impaired. Therefore, there exists a problem that the commercial value of polyarylate resin falls. Moreover, there exists a problem that impact resistance falls remarkably by adding a large amount of inorganic fillers.

Moreover, when using a nitrogen compound as a flame retardant, there existed a problem that heat resistance fell.
Further, when a silicon compound is used as a flame retardant, there is a problem in that it is impossible to knead to an addition amount that stably exhibits flame retardancy because the compatibility between the polyarylate resin and the silicon compound is poor. .

  Further, when an inorganic filler is used as a flame retardant, there is a problem that impact resistance is remarkably lowered by adding a large amount of the inorganic filler.

JP-A-5-163338 JP-A-10-158491

  An object of the present invention is to solve the above problems and to provide a polyarylate resin excellent in flame retardancy while maintaining impact resistance and heat resistance. Moreover, it aims at providing the molded object formed by shape | molding the polyarylate resin composition using this polyarylate resin, and this polyarylate resin composition.

  As a result of studies to solve the above problems, the present inventors have found that the above object can be achieved by copolymerizing a bisphenol A residue, a phthalic acid residue, and tetrabromobisphenol A, and have reached the present invention. did.

That is, the gist of the present invention is as follows.
(1) A polyarylate resin (A) comprising a bisphenol A residue, a tetrabromobisphenol A residue and a phthalic acid residue and represented by the following formula (I):

なお、上記式（Ｉ）において、ｍ／ｎ＝９／１〜４／６である。
（２）インへレント粘度が０．５０〜１．００ｄｌ／ｇであり、かつ荷重１．８ＭＰａにおける荷重たわみ温度が１８５〜２２５℃であることを特徴とする（１）のポリアリレート樹脂（Ａ）。
（３）（１）又は（２）のポリアリレート樹脂（Ａ）とポリカーボネート樹脂（Ｂ）とを、質量比で（Ａ）／（Ｂ）＝１００／０〜３０／７０で配合することを特徴とするポリアリレート樹脂組成物。
（４）（３）のポリアリレート樹脂組成物を成形してなる成形体。

In the above formula (I), m / n = 9/1 to 4/6.
(2) Polyarylate resin (A) characterized in that the inherent viscosity is 0.50 to 1.00 dl / g and the deflection temperature under load at 1.8 MPa is 185 to 225 ° C. ).
(3) The polyarylate resin (A) of (1) or (2) and the polycarbonate resin (B) are blended at a mass ratio of (A) / (B) = 100/0 to 30/70. A polyarylate resin composition.
(4) A molded product obtained by molding the polyarylate resin composition of (3).

  According to the present invention, it is possible to provide a polyarylate resin excellent in flame retardancy while maintaining impact resistance and heat resistance. Moreover, the polyarylate resin composition using this polyarylate resin and the molded object formed by shape | molding this polyarylate resin composition can be provided.

Hereinafter, the present invention will be described in detail.
The polyarylate resin of the present invention comprises bisphenol A [2,2-bis (4-hydroxyphenyl) propane] residue, tetrabromobisphenol A [2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane. It is an aromatic polyester composed of a residue and a phthalic acid residue and represented by the following formula (I).

ビスフェノールＡは安価な化合物であり、ポリアリレート樹脂としたときの耐衝撃性に優れるという利点がある。

Bisphenol A is an inexpensive compound and has the advantage of excellent impact resistance when used as a polyarylate resin.

  In tetrabromobisphenol A, the substituent at the ortho position in the phenol structure of bisphenol A is bromine. Therefore, there exists an advantage that the flame retardance of polyarylate resin can be improved, maintaining the characteristic of bisphenol A.

  When the ortho-position substituent in the phenol structure of bisphenol A is a halogen other than bromine, an effect is recognized in terms of imparting flame retardancy, but there is a problem that the polymerizability is lowered. In addition, when bromine is substituted at the meta position or para position in the phenol structure of bisphenol A, there is no problem in polymerizability, but the resulting polyarylate is likely to be thermally decomposed and the molecular weight is lowered during melt kneading. There is.

  The copolymerization ratio of bisphenol A and tetrabromobisphenol A must be m / n = 9/1 to 4/6, where m is the number of moles of bisphenol A and n is the number of moles of tetrabromobisphenol A. Yes, preferably m / n = 8/2 to 5/5, and more preferably m / n = 8/2 to 6/4. When n is less than 1 (that is, when the ratio of tetrabromobisphenol A is less than 1), there is a problem that the obtained polyarylate resin has poor flame retardancy. On the other hand, when n exceeds 6 (that is, when the ratio of tetrabromobisphenol A exceeds 6), not only the effect of improving flame retardancy is saturated, but also the deflection of the obtained polyarylate resin at a load of 1.8 MPa. The temperature exceeds 225 ° C., and the processing temperature when mixed with the polycarbonate resin described later becomes a high temperature of 350 ° C. or higher, so that thermal decomposition occurs remarkably and the viscosity of the resulting polyarylate resin composition is greatly reduced. This is a practical problem because the impact resistance is lowered.

  In the present invention, a part of the bisphenol A and tetrabromobisphenol A may be replaced with other dihydric alcohols as long as the effects of the present invention are not inhibited. Other dihydric alcohols include, for example, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, dodecanediol, neopentylglycol, cyclohexanediol, 1,4-dihydroxymethylcyclohexanediol. Etc.

  Examples of the phthalic acid for obtaining the phthalic acid residue constituting the polyarylate resin of the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, or a mixture thereof. Especially, in order to advance a favorable synthesis reaction when synthesizing the polyarylate resin having the structure of the present invention, it is preferable to use a mixture of isophthalic acid and terephthalic acid.

  The mixing ratio of terephthalic acid and isophthalic acid is preferably terephthalic acid / isophthalic acid = 8/2 to 2/8, more preferably 7/3 to 3/7 in terms of molar ratio from the viewpoint of performance balance. It is a range. Most preferred is an equimolar mixture of both.

  Moreover, you may substitute a part of phthalic acid with other aliphatic dicarboxylic acids in the range which does not inhibit the effect of this invention. Examples of such aliphatic dicarboxylic acids include dicarboxymethylcyclohexane, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, glutaric acid, and dodecanedioic acid.

  In the present invention, examples of the method for polymerizing the polyarylate resin include an interfacial polymerization method, a solution polymerization method, a melt polymerization method, and the like, among which the interfacial polymerization method is preferable. According to the interfacial polymerization method, the reaction is faster than the solution polymerization method or the melt polymerization method, and hydrolysis of the phthalic acid halide, which is a raw material for polymerizing the phthalic acid component, can be minimized. A molecular weight polyarylate resin can be easily obtained. The interfacial polymerization method is a polymerization method that can impart excellent viscosity controllability, low impurity properties, and transparency to the obtained resin. Below, the manufacturing method of polyarylate resin by the general interfacial polymerization method is explained in full detail.

  In the interfacial polymerization method, an aqueous phase in which dihydric phenol is dissolved in an alkaline aqueous solution and an organic phase in which dicarboxylic acid halide, which is a raw material for polymerizing the dicarboxylic acid component, is dissolved in an organic solvent insoluble in water, By mixing in the presence of This method of interfacial polymerization is described in W.W. M.M. EARECKSON, J.A. Poly. Sci. XL399 (1959) and Japanese Patent Publication No. 40-1959.

  The interfacial polymerization method in the present invention will be specifically described below. First, an alkaline aqueous solution of bisphenol A and tetrabromobisphenol A is prepared as the aqueous phase, and then a polymerization catalyst and a molecular weight adjusting agent (end-capping agent) are added as necessary. Furthermore, the organic phase is prepared by mixing a phthalic acid halide, which is a raw material for polymerizing the phthalic acid component, with a solvent for preparing the organic phase described later. Then, a high molecular weight polyarylate resin can be obtained by mixing an organic phase solution with an aqueous phase solution and performing an interfacial polymerization reaction while stirring at 25 ° C. or lower for 1 to 5 hours.

  The phthalic acid halide is not particularly limited, but it is preferable to use phthalic acid chloride in order to promote a good synthesis reaction in synthesizing the polyarylate having the structure of the present invention.

  Examples of the alkali for preparing the alkaline aqueous solution include sodium hydroxide and potassium hydroxide. Of these, sodium hydroxide is preferred from the viewpoint of economical advantages and easy disposal of waste liquid.

  As a polymerization catalyst, tertiary amines such as trimethylamine, triethylamine, tri-n-butylamine, trihexylamine, tridodecylamine, N, N-dimethylcyclohexylamine, pyridine, quinoline, dimethylaniline; trimethylbenzylammonium halide, tributyl Quaternary ammonium salts such as benzylammonium halide, triethylbenzylammonium halide, tributylbenzylphosphonium halide, tetrabutylammonium halide; trimethylbenzylphosphonium halide, tributylbenzylphosphonium halide, triethylbenzylphosphonium halide, tetrabutylphosphonium halide, triphenylbenzylphosphonium 4th such as halide, tetraphenylphosphonium halide, etc. Such as phosphonium salts, and the like. Of these, tributylammonium halide, tetrabutylammonium halide, and tetrabutylphosphonium halide are preferred from the viewpoint of fast reaction rate and minimizing hydrolysis of phthalic acid halide.

  Examples of the molecular weight modifier include monofunctional compounds, and specific examples include phenol, cresol, p-tert-butylphenol, and the like. Of these, p-tert-butylphenol is preferable from the viewpoint of handleability. The molecular weight modifier is added during the polymerization of the polyarylate resin.

  Examples of the solvent for obtaining the organic phase include a solvent that is incompatible with water and dissolves the polyarylate resin. Specifically, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-dichlorobenzene, m-dichlorobenzene, Chlorine solvents such as p-dichlorobenzene; aromatic hydrocarbon solvents such as toluene, benzene and xylene; tetrahydrofuran, etc. are exemplified, and in particular, handling is possible even if the production equipment is not made explosion-proof specifications. From the viewpoint of goodness, dichloromethane is preferred. By dissolving phthalic acid halide in the above solvent, mixing this organic phase solution with the aforementioned aqueous phase solution, and performing interfacial polycondensation reaction with stirring at a temperature of 25 ° C. or lower for 1 to 5 hours. A high molecular weight polyarylate resin can be obtained.

  The inherent viscosity (ηinh) of the polyarylate resin of the present invention is preferably 0.50 to 1.00 dl / g, more preferably 0.50 to 0.90 dl / g, and still more preferably 0. .50 to 0.80 dl / g. If the inherent viscosity is less than 0.5 dl / g, the impact resistance of the polyarylate resin may be lowered. On the other hand, if the inherent viscosity exceeds 1.00 dl / g, the melt viscosity becomes very high, and the resin flow deteriorates when it is subjected to injection molding and extrusion molding to obtain a molded product, and it can withstand practical use. It may not be possible.

  In the present invention, in order to control the inherent viscosity within the above range, the weight average molecular weight may be in the range of 45,000 to 110,000. Examples of the method for controlling the molecular weight include a method of adding a molecular weight modifier.

  The deflection temperature under load of 1.8 MPa of the polyarylate resin of the present invention is preferably 185 to 220 ° C. More preferably, it is 190-215 degreeC, More preferably, it is 195-210 degreeC. If the deflection temperature under load is lower than 185 ° C., the heat resistance may be inferior. On the other hand, if the deflection temperature under load is higher than 220 ° C., the moldability may be inferior and thermal decomposition may occur.

  The polyarylate resin of the present invention may be mixed with a polycarbonate resin to form a polyarylate resin composition. Since the polycarbonate resin has a bisphenol residue unit similar to the polyarylate resin, it is preferable because it exhibits good compatibility with the polyarylate resin.

  The polycarbonate resin used in the present invention is preferably a polycarbonate represented by the following general formula (II).

なお、上記式（ＩＩ）中のＲ_１〜Ｒ_４は水素原子、または炭素数１〜４のアルキル基を示す。また、ｌは、ポリアリレートと溶融混練する場合に、適度な粘度範囲にできるという加工性の観点から、３０〜５０程度であることが好ましい。

In addition, R < ₁ > -R < ₄ > in the said formula (II) shows a hydrogen atom or a C1-C4 alkyl group. In addition, l is preferably about 30 to 50 from the viewpoint of workability that it can be in an appropriate viscosity range when melt kneaded with polyarylate.

The polycarbonate resin represented by the above formula (II) is a polycarbonate resin composed of a dihydric phenol residue and a carbonate residue.
Examples of bisphenols for introducing bisphenol residue units for constituting the polycarbonate resin include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (3,5-dibromo- 4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl) -4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 4,4-dihydroxydiphenyl ether, 4,4'-dithiodiphenol 4,4′-dihydroxy-3,3′-dichlorodiphenyl ether, 4,4′-di Examples include hydroxy-2,5-dihydroxydiphenyl ether. These may be used alone or in combination of two or more. Among these compounds, 2,2-bis (4-hydroxyphenyl) propane is most preferable from the viewpoint of excellent physical property balance and excellent compatibility with the polyarylate resin.

The inherent viscosity (ηinh) of the polycarbonate resin of the present invention is preferably 0.40 to 1.00 dl / g, more preferably 0.40 to 0.80 dl / g. If the inherent viscosity is less than 0.40 dl / g, the impact resistance of the polyarylate resin may be lowered when mixed with the polyarylate resin to obtain a resin composition. On the other hand, if the inherent viscosity exceeds 1.00 dl / g, the melt viscosity becomes very high, and the flow of the resin deteriorates during injection molding and extrusion molding, and may not be practically used. In order to achieve compatibility between the polyarylate resin and the polycarbonate resin, the difference in the inherent viscosity between the polyarylate resin and the polycarbonate resin is preferably small. For example, the difference is preferably 0.1 to 0.2 dl / g. . The polyarylate resin composition of the present invention having a small difference in inherent viscosity and sufficiently compatible can obtain higher impact resistance.
The polyarylate resin composition of the present invention has a Charpy impact value of 20 kJ / m ² or more and a deflection temperature under a load of 1.8 MPa in order to balance impact resistance, heat resistance and flame retardancy. It is preferable that it is 150-200 degreeC and a flame retardance level V-1 or more. Furthermore, it is more preferable that the Charpy impact value is 25 kJ / m ² or more, the deflection temperature under load of 1.8 MPa is 160 to 190 ° C., and the flame retardancy level is V-0 or more. For that purpose, it is preferable to obtain a polyarylate resin composition with a mixing ratio of the following polyarylate resin and polycarbonate resin.

  The mixing ratio of the polyarylate resin and the polycarbonate resin is preferably (polyarylate resin) / (polycarbonate resin) = 100/0 to 30/70, more preferably 90/10 to 40/60 by mass ratio. And particularly preferably in the range of 90/10 to 50/50. When the mixing ratio is less than 30/70, the resulting polyarylate resin composition has low heat resistance, and may easily be thermally deformed when formed into a molded body.

  The polyarylate resin or polyarylate resin composition of the present invention can be molded into various molded articles by any method. The molding method is not particularly limited, and a normal injection molding method, extrusion molding method, compression molding method, melt casting method, or the like is used. Among these, it is preferable to mold by an injection molding method because the characteristics of the polyarylate resin composition excellent in heat resistance, impact resistance and flame retardancy of the present invention can be fully utilized. Although it does not specifically limit as molding conditions in injection molding, It is preferable that cylinder temperature is 300-340 degreeC and mold temperature is 80-120 degreeC.

  The polyarylate resin or polyarylate resin composition of the present invention may contain a hindered amine light stabilizer from the viewpoint of further improving the heat discoloration when formed into a molded body. The content of the hindered amine light stabilizer is not particularly limited, and an appropriate amount can be used.

  In the polyarylate resin or polyarylate resin composition of the present invention, various additives such as an ultraviolet absorber, a bluing agent, a flame retardant, an antistatic agent, and a lubricant are added within the range in which the heat discoloration of the molded article does not deteriorate. It may be added.

The polyarylate resin composition thus obtained is particularly suitably used in fields where heat resistance, impact resistance and flame retardancy are required.
Specific examples of molded products made of polyarylate resin include peripheral parts of displays such as flat-screen TVs, personal computers, mobile phones, mobile devices, resin parts for electrical appliances such as housings, headlight covers, lamp covers, reflectors, etc. In addition to various automotive exterior resin parts, various illuminations around the instrument panel, indicator lights, warning lights, automotive interior resin parts such as ceilings, legs, and door side interior lights.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples.
1. Raw material (1) Phthalic acid halide
・ Terephthalic acid chloride (TPC) (Ihara Nikkei Chemical Industries, “Terephthaloyl chloride”)
・ Isophthalic acid chloride (IPC) (Ihara Nikkei Chemical Industry Co., Ltd., “Isophthaloyl chloride”)
(2) Aliphatic carboxylic acid halide / cyclohexanedicarboxylic acid chloride (CHDC)
(3) Bisphenol A (BPA)
・ 2,2-bis (4-hydroxyphenyl) propane (Mitsui Chemicals)
(4) Tetrabromobisphenol A (TBA)
2,2- (4-hydroxy-3,5-dibromophenyl) propane (manufactured by Tosoh Corporation, “Frame Cut 120G”)
(5) Tetrafluorobisphenol A (TFA)
(6) Hexabromobisphenol A (HBA)
2,2- (4-hydroxy-2,3,5-dibromophenyl) propane (7) bisphenol AP (BPAP)
1,1-bis (4-hydroxyphenyl) -1-phenylethane (Honshu Chemical Industries, “BisP-AP”)
(8) Polycarbonate resin B-1: (manufactured by Sumitomo Dow “Caliber 200-3”) (inherent viscosity 0.639 dl / g)
B-2: (manufactured by Sumitomo Dow, “Caliber 200-13”) (inherent viscosity 0.492 dl / g)
B-3: (manufactured by Sumitomo Dow, “Caliber 200-30”) (inherent viscosity 0.440 dl / g)
2. Various characteristic values in the test method examples were measured and evaluated as follows.
(1) Inherent viscosity 1,1,2,2-tetrachloroethane was used as a solvent, and the polyarylate resin obtained in Examples and Comparative Examples was dissolved in the solvent at a concentration of 1 g / dl to obtain a solution. . Under the condition of a temperature of 25 ° C., the viscosity [η] of the solvent and the viscosity [η ₀ ] of the solution were measured, and the inherent viscosity was calculated by the following formula.
(Inherent viscosity) = η / η ₀
(2) Deflection temperature under load The test piece conforming to ISO is molded under predetermined molding conditions using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., “EC100N type”). The deflection temperature under load at 8 MPa was measured.
(3) Impact resistance (Charpy impact value)
Using the above-described injection molding machine, ISO-compliant test pieces were molded from the polyarylate resins or polyarylate resin compositions obtained in Examples and Comparative Examples under predetermined molding conditions, and conformed to ISO 179-1. Measured. In the present invention, a Charpy impact value of 5 kJ / m ² is assumed to be practically usable.
(4) Flame retardancy Using the above-described injection molding machine, a strip type test having a thickness of 0.8 mm, a length of 125 mm, and a width of 12 mm from the polyarylate resin or the polyarylate resin composition obtained in Examples and Comparative Examples. After the piece was molded, evaluation was performed according to the UL94 flame retardant test. That is, the test piece was held vertically and the flame retardancy was evaluated by each afterflame time and drip property after the flame of the burner was contacted twice in 10 seconds, and classified as shown in Table 1. In the present invention, those above the V-1 level can withstand practical use, and those at the V-0 level are more preferred.

（製造例１）
攪拌容器を備えた反応容器中に、ビスフェノールＡを１４．８２ｋｇ（６５モル）、テトラブロモビスフェノールＡを３．８１ｋｇ（７モル）、分子量調整剤としてｐ−ｔｅｒｔ−ブチルフェノール（ＤＩＣ社製）７６５ｇ（５モル）、アルカリとして水酸化ナトリウム（東ソー社製）６．８４ｋｇ（１７１モル）、重合触媒としてベンジル−トリ−ｎ−ブチルアンモニウムクロライド（ライオンアクゾ社製、「ＢＴＢＡＣ−５０」）１５３ｇ、ハイドロサルファイトナトリウム（ＢＡＳＦ社製）１１８ｇを注入し、さらに反応容器中に水５９０Ｌを注入して溶解し、水相とした。

(Production Example 1)
In a reaction vessel equipped with a stirring vessel, 14.82 kg (65 mol) of bisphenol A, 3.81 kg (7 mol) of tetrabromobisphenol A, and 765 g of p-tert-butylphenol (manufactured by DIC) as a molecular weight regulator. 5 mol), sodium hydroxide (manufactured by Tosoh Corp.) 6.84 kg (171 mol) as alkali, 153 g of benzyl-tri-n-butylammonium chloride (manufactured by Lion Akzo, “BTBAC-50”) as a polymerization catalyst, hydrosal Phyto sodium (manufactured by BASF) (118 g) was injected, and 590 L of water was further injected into the reaction vessel to dissolve it to obtain an aqueous phase.

  Furthermore, in another reaction vessel, 347 L of dichloromethane (manufactured by Tokuyama Corporation, “methylene chloride”) and phthalic acid chloride (molar ratio = 50: 50) 15.26 kg, which is an equivalent mixture of isophthalic acid chloride and terephthalic acid chloride. (75 mol) was dissolved to obtain an organic phase. This organic phase was added to the already stirred aqueous phase solution with vigorous stirring, and the polymerization reaction was carried out for 2 hours while maintaining the temperature at 15 ° C. Thereafter, stirring was stopped, and the aqueous phase and the organic phase were separated by decantation. To the organic phase from which the aqueous phase had been removed, 1200 L of pure water and 100 mL of acetic acid were added to stop the reaction, and the mixture was further stirred at 15 ° C. for 30 minutes. The organic phase was washed 5 times with pure water, and the organic phase was added into 1000 L of hexane to precipitate a polymer. The precipitated polymer was separated from the organic phase and then dried at 120 ° C. for 1 day to obtain a polyarylate resin (A-1). The obtained polyarylate resin (A-1) was subjected to composition analysis using 1H-NMR (manufactured by JEOL Ltd., “ECA500 NMR”). As a result, bisphenol A component, tetrabromobisphenol A component, phthalic acid component It was confirmed that the polymerization ratio was the same as the charging ratio (mixing ratio). The results are shown in Table 2.

（製造例２）
ｐ−ｔｅｒｔ−ブチルフェノールの配合を４５９ｇ（３モル）とした以外は、製造例１と同様にして、ポリアリレート樹脂（Ａ−２）を得て、各分析を行った。その結果を表２に示す。

(Production Example 2)
A polyarylate resin (A-2) was obtained in the same manner as in Production Example 1 except that the amount of p-tert-butylphenol was changed to 459 g (3 mol), and each analysis was performed. The results are shown in Table 2.

(Production Example 3)
A polyarylate resin (A-2) was obtained and analyzed in the same manner as in Production Example 1 except that the amount of p-tert-butylphenol was changed to 306 g (2 mol). The results are shown in Table 2.

(Production Examples 4 to 16)
According to the composition shown in Table 2, polyarylate resins (A-4) to (A-16) were obtained in the same manner as in Production Example 1. The evaluation results are shown in Table 2.

Example 1
Using the above-described injection molding machine, the polyarylate resin (A-1) obtained in Production Example 1 has a cylinder temperature of 300 to 340 ° C. and a mold temperature of 100 ° C., a thickness of 4 mm, a length of 10 mm, and a width of 80 mm. The test piece was prepared and subjected to evaluation of impact resistance, heat resistance and flame retardancy. The evaluation results are shown in Table 3.

（実施例２〜８）
表３に示すように、ポリアリレート樹脂の種類を変えた以外は、実施例１と同様にして試験片を作製し、評価に付した。その評価結果を表３に示す。
（実施例９）
二軸押出機（東芝機械社製、「ＴＥＭ−４１ＳＳ型」）を用いて、製造例１で得られたポリアリレート樹脂（Ａ−１）とポリカーボネート樹脂（Ｂ−２）を、（Ａ−１）／（Ｂ−２）＝８０／２０（質量比）の混合比率で、シリンダー温度３００〜３４０℃、スクリュー回転３００ｒｐｍ、吐出量５０ｋｇ／ｈの条件で溶融混練を行った。その後、ストランド状に押し出して、冷却した後、カッティングして、ポリアリレート樹脂組成物ペレットを得た。得られたポリアリレート樹脂組成物を、上述の射出成形機を用いて、シリンダー温度３００〜３４０℃、金型温度１００℃にて、厚み４ｍｍ、長さ１０ｍｍ、幅８０ｍｍの試験片を作製し、評価に付した。その評価結果を表４に示す。

(Examples 2 to 8)
As shown in Table 3, a test piece was prepared and evaluated in the same manner as in Example 1 except that the type of polyarylate resin was changed. The evaluation results are shown in Table 3.
Example 9
Using a twin screw extruder (manufactured by Toshiba Machine Co., Ltd., “TEM-41SS type”), the polyarylate resin (A-1) and the polycarbonate resin (B-2) obtained in Production Example 1 are converted into (A-1 ) / (B-2) = 80/20 (mass ratio), and melt kneading was performed under conditions of a cylinder temperature of 300 to 340 ° C., a screw rotation of 300 rpm, and a discharge amount of 50 kg / h. Then, after extruding into a strand shape, cooling, and cutting, polyarylate resin composition pellets were obtained. Using the above-described injection molding machine, the obtained polyarylate resin composition was prepared at a cylinder temperature of 300 to 340 ° C. and a mold temperature of 100 ° C. to produce a test piece having a thickness of 4 mm, a length of 10 mm, and a width of 80 mm. It was attached to evaluation. The evaluation results are shown in Table 4.

（実施例１０〜２１）
ポリアリレート樹脂とポリカーボネート樹脂の種類、およびポリアリレート樹脂とポリカーボネート樹脂の混合比率を変えた以外は、実施例９と同様にして試験片を作製し、評価に付した。その評価結果を表４に示す。
（比較例１〜１３）
ポリアリレート樹脂とポリカーボネート樹脂の種類、およびポリアリレート樹脂とポリカーボネート樹脂の混合比率を変えた以外は、実施例９と同様にして試験片を作製し、評価に付した。その評価結果を表５に示す。

(Examples 10 to 21)
Test pieces were prepared and evaluated in the same manner as in Example 9 except that the types of polyarylate resin and polycarbonate resin and the mixing ratio of polyarylate resin and polycarbonate resin were changed. The evaluation results are shown in Table 4.
(Comparative Examples 1 to 13)
Test pieces were prepared and evaluated in the same manner as in Example 9 except that the types of polyarylate resin and polycarbonate resin and the mixing ratio of polyarylate resin and polycarbonate resin were changed. The evaluation results are shown in Table 5.

実施例１〜２１で得られたポリアリレート樹脂およびポリアリレート樹脂組成物は、耐衝撃性、耐熱性、難燃性のいずれにおいても優れていた。

The polyarylate resins and polyarylate resin compositions obtained in Examples 1 to 21 were excellent in any of impact resistance, heat resistance, and flame retardancy.

In Comparative Example 1, since the copolymerization ratio of tetrabromobisphenol A was low, the obtained polyarylate resin was inferior in heat resistance.
Since Comparative Example 2 did not use tetrabromobisphenol A, the obtained polyarylate resin was inferior in heat resistance and flame retardancy.

  In Comparative Example 3, since the copolymerization ratio of tetrabromobisphenol A was high, the processing temperature at the time of mixing and injection molding was high, thermal decomposition occurred, and the resulting polyarylate resin was inferior in impact resistance.

  Since Comparative Example 4 did not use bisphenol A, the resulting polyarylate resin had a deflection temperature under load higher than 225 ° C., a high processing temperature during mixing and injection molding, and thermal decomposition occurred. It was inferior.

Since Comparative Example 5 used tetrafluorobisphenol A instead of tetrabromobisphenol A used in Example 6, the resulting polyarylate resin was inferior in heat resistance.
Since Comparative Example 6 used hexabromobisphenol A instead of tetrabromobisphenol A used in Example 6, the resulting polyarylate resin was easily thermally decomposed, causing a decrease in molecular weight during melt-kneading, and impact resistance. It was inferior.

In Comparative Example 7, since cyclohexanedicarboxylic acid chloride was used instead of the phthalic acid used in Example 6, the polymerizability was inferior, and the impact resistance, heat resistance, and flame retardance were inferior.
In Comparative Example 8, since tetrabromobisphenol A and bisphenol AP were copolymerized and used, the resulting polyarylate resin had a load deflection temperature higher than 225 ° C. and was inferior in impact resistance.

Since the comparative example 9 used polyarylate resin with a low copolymerization ratio of tetrabromobisphenol A, the obtained polyarylate resin composition was inferior in heat resistance.
Since the comparative example 10 used the polyarylate resin which does not mix | blend tetrabromobisphenol A, the obtained polyarylate resin composition was inferior in a flame retardance.

  In Comparative Example 11, since a polyarylate resin having a high copolymerization ratio of tetrabromobisphenol A was used, the processing temperature at the time of mixing and injection molding was high and thermal decomposition occurred. It was inferior.

  Since the comparative example 12 used the polyarylate resin which does not mix | blend bisphenol A, the processing temperature at the time of mixing and injection molding was high, thermal decomposition occurred, and the obtained polyarylate resin composition was inferior in impact resistance. .

  Since the comparative example 13 uses the polyarylate resin which copolymerized tetrabromobisphenol A and bisphenol AP, the obtained polyarylate resin composition was inferior in impact resistance.

Claims (4)

A polyarylate resin (A) comprising a bisphenol A residue, a tetrabromobisphenol A residue and a phthalic acid residue and represented by the following formula (I):

In the above formula (I), m / n = 9/1 to 4/6.   The polyarylate resin (A) according to claim 1, wherein the inherent viscosity is 0.50 to 1.00 dl / g, and the deflection temperature under load at 1.8 MPa is 185 to 225 ° C.   The polyarylate characterized by blending the polyarylate resin (A) and the polycarbonate resin (B) according to claim 1 or 2 at a mass ratio of (A) / (B) = 100/0 to 30/70. Resin composition.   The molded object formed by shape | molding the polyarylate resin composition of Claim 3.