JP2011144304A - Resin composition and molded body comprising the resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in transparency, tensile strength and solvent resistance, and to provide molded bodies thereof. <P>SOLUTION: The resin composition comprises [a polyarylate resin represented by formula (I)]/[a polyester resin represented by formula (II)] in a mass ratio of 50/50 to 5/95. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition excellent in transparency, solvent resistance and tensile strength, and a molded article comprising the resin composition.

  Polyarylate resins composed of dihydric phenols, particularly 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes referred to as bisphenol A) and terephthalic acid and / or isophthalic acid are used as engineering plastics. Already well known. This polyarylate resin has high heat resistance, excellent mechanical properties such as impact resistance and dimensional stability, and is transparent, so the molded product is widely used in fields such as electrical and electrical equipment, automobiles, and machinery. ing.

  The polyarylate resin composition may be used as a resin composition with other polyester resins such as polyethylene terephthalate for the purpose of improving moldability and solvent resistance. However, in such a case, although the molding processability is improved, the heat resistance is remarkably lowered, so that its application is greatly limited.

  For example, when the blending ratio of the polyester resin is increased in order to improve the solvent resistance, the heat resistance is remarkably lowered, and when the heat resistance is emphasized, the solvent resistance may be insufficient. Moreover, when heat resistance falls notably, it will become difficult to set the conditions of the preliminary drying at the time of manufacture of this resin composition, and handling will become remarkably difficult.

  Secondary batteries such as lithium-ion batteries are mainly used as power sources for electronic devices such as mobile phones, portable notebook personal computers and mobile devices. In recent years, a small fuel cell with high output and no need for charging has been expected as a new power source due to an increase in power consumption associated with higher functionality of these electronic devices and a demand for longer use. There are various types of fuel cells. In particular, a direct methanol fuel cell using a methanol solution as a fuel is easier to handle than a fuel cell using hydrogen as a fuel. Since the system is simple because it can be used continuously without being charged, it is attracting attention as a power source for electronic devices.

  Furthermore, weight reduction is strongly demanded for portable electronic devices, and weight reduction is also desired for fuel cells used in portable electronic devices. In a direct methanol fuel cell, it is necessary to store or supply a methanol solution. Therefore, in order to reduce the weight, it is considered to use a non-metallic material for a container or a distribution pipe. In particular, the use of plastic has been studied from the viewpoint of moldability. In a methanol solution storage unit or the like, since the remaining amount of the methanol solution can be visually confirmed, it is preferable to use a material having excellent transparency. However, a plastic material having excellent transparency is generally amorphous, and is inferior in durability to methanol, that is, solvent resistance, compared to a crystalline plastic material. Therefore, a plastic material that satisfies both transparency and solvent resistance is required.

  In response to the above requirements, a resin composition comprising a polyarylate resin and a polyester resin having a terephthalic acid residue and a 1,4-cyclohexanedimethanol residue has been proposed (for example, Patent Document 1). This resin composition is superior in heat resistance and impact resistance as compared with a resin composition comprising a polyarylate resin and polyethylene terephthalate, but has insufficient solvent resistance. When the solvent resistance is insufficient, there is a problem that the mechanical properties and transparency of the molded product are remarkably lowered by contact with a solvent such as methanol.

JP 2002-302596 A

  The object of the present invention is to solve the above-mentioned problems and to provide a resin composition excellent in transparency, solvent resistance and tensile strength. Furthermore, it aims at providing the molded object formed by shape | molding this resin composition.

  As a result of investigations to solve the above problems, the present inventors have found that a resin composition containing a specific polyarylate resin and a specific polyester resin is excellent in transparency, solvent resistance and tensile strength. The present invention has been reached.

That is, the gist of the present invention is as follows.
(1) The polyarylate resin represented by the following formula (I) and the polyester resin represented by the following formula (II) are (polyarylate resin) / (polyester resin) = 50 / 50-5 / 95. A resin composition comprising a ratio of 95.

上記式（Ｉ）中、ｇは正の整数を示す。Ｒ^ａは炭素原子数が１〜１０であるアルキレン基、炭素原子数が１〜１０であるアルキリデン基、炭素原子数が１〜１０であるアリルアルキリデン基、炭素原子数が１〜１０であるシクロアルキレン基、炭素原子数が１〜１０であるシクロアルキリデン基から選ばれる二価の飽和または不飽和脂肪族炭化水素基、オキシ基、チオ基、スルホニル基、Ｎ−フェニルフタルイミジン基から選ばれた少なくとも１種を表す。Ｒ^１、Ｒ^２、Ｒ^３は塩素、臭素、フッ素、ニトロ基、シアノ基、炭素原子数が１〜１０であるアルキル基、炭素原子数が１〜１０であるシクロアルキル基、炭素原子数が１〜１０であるアリル基から選ばれた少なくとも１種の置換基であって、互いに同じであってもよいし異なっていてもよい。ｄ、ｅ、ｆは０〜４の整数であって、互いに同じであってもよいし異なっていてもよい。

In the above formula (I), g represents a positive integer. R ^a is an alkylene group having 1 to 10 carbon atoms, an alkylidene group having 1 to 10 carbon atoms, an allylalkylidene group having 1 to 10 carbon atoms, or a cyclohexane having 1 to 10 carbon atoms. Selected from an alkylene group, a divalent saturated or unsaturated aliphatic hydrocarbon group selected from a cycloalkylidene group having 1 to 10 carbon atoms, an oxy group, a thio group, a sulfonyl group, and an N-phenylphthalimidine group Represents at least one kind. R ¹ , R ² and R ³ are chlorine, bromine, fluorine, nitro group, cyano group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 10 carbon atoms, and the number of carbon atoms. It is at least 1 sort (s) of substituent selected from the allyl group which is 1-10, Comprising: You may mutually be same or different. d, e, and f are integers of 0 to 4, and may be the same or different from each other.

上記式（ＩＩ）中、ｊは正の整数を示す。Ｒ^ｂは炭素原子数が１〜１０であるアルキレン基、炭素原子数が１〜１０であるシクロアルキレン基、炭素原子数が１〜１０であるシクロアルキリデン基から選ばれる二価の飽和または不飽和脂肪族炭化水素基から選ばれた少なくとも１種を表す。Ｒ^４およびＲ^５は、塩素、臭素、フッ素、ニトロ基、シアノ基、炭素原子数が１〜１０であるアルキル基、炭素原子数が１〜１０であるシクロアルキル基、炭素原子数が１〜１０であるアリル基から選ばれた少なくとも１種の置換基であって、互いに同じであってもよいし異なっていてもよい。ｈおよびｉは０〜３の整数であって、互いに同じであってもよいし異なっていてもよい。
（２）ポリアリレート樹脂とポリエステル樹脂の合計１００質量部に対して、有機酸金属塩が０．００１〜０．１質量部含有されることを特徴とする（１）の樹脂組成物。
（３）（１）または（２）の樹脂組成物であって、該樹脂組成物を成形して得られた厚み３ｍｍの成形体における全光線透過率が８０〜９０％であり、かつ該樹脂組成物を成形して得られた厚み３ｍｍの成形体におけるヘーズが１〜１０であることを特徴とする樹脂組成物。
（４）（１）〜（３）のいずれかの樹脂組成物であって、該樹脂組成物を、示差走査熱量計で、昇温速度１０℃／分で３０℃から３００℃まで昇温した後、降温速度１０℃／分で３０℃まで降温した際に、昇温過程と降温過程のいずれにおいても結晶化潜熱に由来する発熱ピークを示さないことを特徴とする樹脂組成物。
（５）ポリアリレート樹脂を構成するジカルボン酸残基が、少なくともテレフタル酸残基およびイソフタル酸残基を含み、かつテレフタル酸残基とイソフタル酸残基のモル比率が、（テレフタル酸残基）／（イソフタル酸残基）＝６０／４０〜２５／７５であることを特徴とする（１）〜（４）のいずれかの樹脂組成物。
（６）ポリアリレート樹脂を構成する二価フェノール残基が、２，２−ビス（４−ヒドロキシフェニル）プロパン、１−フェニル−１，１−ビス（４−ヒドロキシフェニル）エタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、３，３，５−トリメチル−１，１−ビス（４−ヒドロキシフェニル）シクロへキサンから選ばれた少なくとも１種であることを特徴とする（１）〜（５）のいずれかの樹脂組成物。
（７）ポリエステル樹脂を構成するジカルボン酸残基が、１，５−ナフタレンジカルボン酸残基、２，６−ナフタレンジカルボン酸残基から選ばれた少なくとも１種であり、かつ、ポリエステル樹脂を構成するジオール残基が、エチレングリコール、１，４−ブタンジオールから選ばれた少なくとも１種であることを特徴とする（１）〜（６）のいずれかの樹脂組成物。
（８）（１）〜（７）のいずれかの樹脂組成物を成形してなる成形体。

In the above formula (II), j represents a positive integer. R ^b is a divalent saturated or unsaturated group selected from an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, and a cycloalkylidene group having 1 to 10 carbon atoms. It represents at least one selected from aliphatic hydrocarbon groups. R ⁴ and R ⁵ are chlorine, bromine, fluorine, nitro group, cyano group, alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 1 to 10 carbon atoms, or 1 to 1 carbon atoms. And at least one substituent selected from an allyl group of 10, which may be the same as or different from each other. h and i are integers of 0 to 3, and may be the same or different from each other.
(2) The resin composition according to (1), wherein the organic acid metal salt is contained in an amount of 0.001 to 0.1 parts by mass with respect to a total of 100 parts by mass of the polyarylate resin and the polyester resin.
(3) The resin composition according to (1) or (2), wherein a total light transmittance in a molded product having a thickness of 3 mm obtained by molding the resin composition is 80 to 90%, and the resin A resin composition characterized by having a haze of 1 to 10 in a molded product having a thickness of 3 mm obtained by molding the composition.
(4) The resin composition according to any one of (1) to (3), wherein the temperature of the resin composition is increased from 30 ° C. to 300 ° C. at a temperature increase rate of 10 ° C./min with a differential scanning calorimeter. Thereafter, when the temperature is lowered to 30 ° C. at a temperature lowering rate of 10 ° C./min, the resin composition does not show an exothermic peak derived from latent heat of crystallization in both the temperature raising process and the temperature lowering process.
(5) The dicarboxylic acid residue constituting the polyarylate resin contains at least a terephthalic acid residue and an isophthalic acid residue, and the molar ratio of the terephthalic acid residue to the isophthalic acid residue is (terephthalic acid residue) / (Isophthalic acid residue) = 60/40 to 25/75, The resin composition according to any one of (1) to (4).
(6) The dihydric phenol residue constituting the polyarylate resin is 2,2-bis (4-hydroxyphenyl) propane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,1- (1) to (1), which are at least one selected from bis (4-hydroxyphenyl) cyclohexane and 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane The resin composition according to any one of 5).
(7) The dicarboxylic acid residue constituting the polyester resin is at least one selected from 1,5-naphthalenedicarboxylic acid residue and 2,6-naphthalenedicarboxylic acid residue, and constitutes the polyester resin. The resin composition according to any one of (1) to (6), wherein the diol residue is at least one selected from ethylene glycol and 1,4-butanediol.
(8) A molded product obtained by molding the resin composition according to any one of (1) to (7).

  According to the present invention, a resin composition excellent in transparency, solvent resistance and tensile strength can be provided. And the molded object obtained from this resin composition can be provided.

Hereinafter, the present invention will be described in detail.
The resin composition of the present invention contains a polyarylate resin and a polyester resin.
The polyarylate resin used in the present invention is an aromatic polyester represented by the following formula (I), and is composed of a dihydric phenol or a derivative thereof and an aromatic dicarboxylic acid or a derivative thereof.

上記式（Ｉ）中、ｇは正の整数を示すものである。

In the above formula (I), g represents a positive integer.

R ^a is an alkylene group having 1 to 10 carbon atoms, an alkylidene group having 1 to 10 carbon atoms, an allylalkylidene group having 1 to 10 carbon atoms, or a cyclohexane having 1 to 10 carbon atoms. Selected from an alkylene group, a divalent saturated or unsaturated aliphatic hydrocarbon group selected from a cycloalkylidene group having 1 to 10 carbon atoms, an oxy group, a thio group, a sulfonyl group, and an N-phenylphthalimidine group Represents at least one kind.

Among the above, the R ^a, in terms of versatility and economy, an alkylene group, an allyl alkylidene group, a cycloalkylene group.
In the case where ^Ra is at least one selected from an alkylene group, an alkylidene group, an allylalkylidene group, a cycloalkylene group, and a cycloalkylidene group, the number of carbon atoms is 1 to 10 is preferable.

R ¹ , R ² and R ³ may be the same or different, and are chlorine, bromine, fluorine, nitro group, cyano group, alkyl group having 1 to 10 carbon atoms, or 1 to 1 carbon atoms. 10 represents at least one substituent selected from a cycloalkyl group having 10 and an allyl group having 1 to 10 carbon atoms. Especially, as R < ¹ >, R < ² >, R < ³ >, a methyl group is preferable from a heat resistant stability viewpoint.

When R ¹ , R ² and R ³ are at least one selected from an alkyl group, a cycloalkyl group, and an allyl group, the number of carbon atoms is 1 to 6 from the viewpoints of versatility and economy. It is preferable.
d, e, and f represent integers of 0 to 4, and may be the same as or different from each other. In particular, from the viewpoint of heat resistance stability, 0 is preferable.

  Examples of the raw material for introducing the dihydric phenol residue include bisphenols. Specific examples of bisphenols include resorcinol, 2,2-bis (4-hydroxyphenyl) propane (generic name: bisphenol A), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2 , 2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) ) Propane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane (generic name: bisphenol F), 1,1-bis (4-hydroxyphenyl) -1- Phenylethane (generic name: bisphenol AP), 4-methyl-2,2-bis (4-hydroxyphenyl) Nyl) pentane, 2-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine, 1,1-bis (4-hydroxyphenyl) cyclohexane (generic name: bisphenol Z), 3,3,5-trimethyl-1 , 1-bis (4-hydroxyphenyl) cyclohexane (generic name: bisphenol TMC), 1,1,3,3,3-hexafluoro-2,2-bis (4-hydroxyphenyl) propane and the like. . These may be used singly or in combination of two or more.

  Among these, it is preferable to use bisphenol A, bisphenol AP, bisphenol Z, bisphenol TMC alone or in combination of two or more from the viewpoint of versatility and cost, and heat resistance of the resulting polyarylate. It is more preferable to use it alone.

  Bisphenol A has the advantage of excellent mechanical properties, versatility, and cost merit. Bisphenol AP, bisphenol Z, and bisphenol TMC have the advantage of superior heat resistance compared to bisphenol A.

  In the present invention, part of the dihydric phenol is ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, dodecanediol, neopentylglycol, cyclohexanediol, 1,4-dihydroxymethylcyclohexane. Dihydric alcohols such as diols; 4,4′-dihydroxybiphenyl, 1,4-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroquinaphthalene may be substituted.

  Preferred examples of the raw material for introducing the aromatic dicarboxylic acid residue constituting the polyarylate resin include terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6 -Naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, methyl terephthalic acid, 4,4'-biphenyl dicarboxylic acid, 2,2'-biphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid Acid, 4,4'-diphenylmethanecarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4,4'-diphenylisopropylidenedicarboxylic acid, 1,2-bis (4-carboxyphenoxy) ethane, 5-sodium sulfoisophthalate Acids, and derivatives thereof. These compounds can be used alone or in combination of two or more. Examples of the aromatic dicarboxylic acid derivative include acid chlorides and alkyl esters.

  Among these, terephthalic acid, isophthalic acid, and derivatives thereof are preferable from the viewpoint of melt processability and mechanical properties such as tensile strength. In particular, it is particularly preferable to use a mixture of terephthalic acid and derivatives thereof and isophthalic acid and derivatives thereof.

  When the terephthalic acid and their derivatives are mixed with isophthalic acid and their derivatives, the mixing ratio is (terephthalic acid) / (isophthalic acid) = 60/40 to 25/75 in terms of molar ratio. Preferably, it is 55/45 to 30/70. By setting it as such a range, the polyarylate resin obtained becomes amorphous and excellent in transparency.

  In the present invention, a part of the above-mentioned aromatic dicarboxylic acid may be replaced with another aliphatic dicarboxylic acid as long as the effects of the present invention are not impaired. Examples of such aliphatic dicarboxylic acids include dicarboxymethylcyclohexane, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, glutaric acid, dodecanedioic acid and the like.

  In the present invention, the polyarylate resin has a terminal having phenol, o, m, p-cresol, dimethylphenol, o, m, p-ethylphenol, o, m, pn-propylphenol, o, m, p. Isopropylphenol, o, m, p-n-butylphenol, o, m, p-isobutylphenol, o, m, p-sec-butylphenol, o, m, p-tert-butylphenol, o, m, p-c Monohydric phenol residues such as milphenol; monohydric alcohol residues such as methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, phenethyl alcohol; acetic acid, propionic acid , Octanoic acid, cyclohexanecarbo Acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butylbenzoic acid, may be blocked in such a monovalent carboxylic acid residue such as p- methoxyphenyl acetate. There is an advantage that the molecular weight can be controlled by blocking the end of the polyarylate resin.

  Examples of the method for producing the polyarylate resin include known methods such as a solution polymerization method, a melt polymerization method, and an interfacial polymerization method. Of these, the interfacial polymerization method is preferred. 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 phenols are dissolved in an alkaline aqueous solution and an organic phase in which dicarboxylic acid halide, which is a raw material for polymerizing a dicarboxylic acid component, is dissolved in an organic solvent insoluble in water, This is done by mixing in the presence of a catalyst. 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 described in detail below. First, an alkaline aqueous solution of bisphenols is prepared as the aqueous phase, and then a polymerization catalyst and, if necessary, a molecular weight adjusting agent (end-capping agent) are added. 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.

  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.

  Polymerization catalysts include trimethylamine, triethylamine, tri-n-butylamine, trihexylamine, tridodecylamine, N, N-dimethylcyclohexylamine, tertiary amines such as 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, tributylbenzylammonium 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 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. Dissolve phthalic acid halide in the above solvent, mix this organic phase solution with the above aqueous phase solution, and perform interfacial polycondensation reaction at a temperature of 2 to 80 ° C. with stirring for 1 to 5 hours. Thus, a high molecular weight polyarylate resin can be easily obtained.

In the polyarylate resin used in the present invention, a solution in which 1.0 g of polyarylate resin is dissolved in 100 ml of a mixture of phenol / 1,1,2,2-tetrachloroethane (mass ratio) = 60/40 has a temperature of 25. The intrinsic viscosity at 0 ° C. is preferably 0.40 to 0.70 dl / g, and more preferably 0.45 to 0.65 dl / g. The intrinsic viscosity is calculated by the following formula (1).
Intrinsic viscosity = limc → 0 [(η _rel −1) / c] (1)
Here, η indicates a relative viscosity, and c indicates a solution concentration (unit: g / dl).

  When the intrinsic viscosity of the polyarylate resin is less than 0.40 dl / g, when the resin composition of the present invention is formed into a molded product, the mechanical properties are inferior or the heat resistance is reduced. There is. Further, when the intrinsic viscosity of the polyarylate resin exceeds 0.70 dl / g, the melt viscosity becomes high and the fluidity becomes inferior, and when the resin composition is produced, the obtained resin composition is molded. When using the body, it may not be practical. The intrinsic viscosity is an index of molecular weight. The smaller the molecular weight, the lower the intrinsic viscosity, while the larger the molecular weight, the higher the intrinsic viscosity.

  The polyarylate resin thus obtained is amorphous and excellent in transparency. In the present invention, the term “amorphous” means that the resin or resin composition is not crystallized from the molten state when cooled and solidified. A specific definition of the amorphous property will be described later.

  The resin composition of the present invention is obtained by mixing a polyarylate resin and a polyester resin. Since the polyester resin has crystallinity and good chemical resistance, when it is made into a resin composition, the chemical resistance can be improved without significantly impairing the transparency of the obtained molded article.

  The polyester resin used in the present invention comprises a diol residue and a dicarboxylic acid residue having a naphthalene skeleton, as represented by the following formula (II). By having such a structure, the chemical resistance of the resulting resin composition can be greatly improved as compared with conventional polyester resins.

上記式（ＩＩ）中、ｊは正の整数を示す。

In the above formula (II), j represents a positive integer.

R ^b is a divalent saturated or unsaturated group selected from an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, and a cycloalkylidene group having 1 to 10 carbon atoms. It represents at least one substituent selected from an aliphatic hydrocarbon group. Especially, as ^Rb , it is preferable that they are an ethylene group and a butylene group from a heat resistant viewpoint of the resin composition obtained. When R ^b is at least one selected from an alkylene group, a cycloalkylene group, and a cycloalkylidene group, the number of carbon atoms is preferably 2 to 8 from the viewpoints of versatility and economy. .

R ⁴ and R ⁵ may be the same or different, and are chlorine, bromine, fluorine, nitro group, cyano group, alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. It represents at least one substituent selected from a cycloalkyl group and an allyl group having 1 to 10 carbon atoms. When R ⁴ and R ⁵ are at least one selected from an alkyl group, a cycloalkyl group, and an allyl group, the number of carbon atoms is 1 to 6 from the viewpoint of chemical resistance and heat resistance. Is preferred.
h and i represent an integer of 0 to 3, and may be the same or different from each other. In particular, from the viewpoint of versatility and economy, it is preferably 0.

  The polyester resin can be produced by polymerizing a diol compound or a derivative thereof and naphthalenedicarboxylic acid or a derivative thereof by a transesterification reaction or the like.

  Raw materials for introducing the diol residue constituting the polyester resin include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,4-butanediol. 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, polytetramethylene glycol, 1,4-cyclohexanedimethanol and mixtures thereof. It is done. Among these, ethylene glycol and 1,4-butanediol are preferable from the viewpoints of heat resistance and solvent resistance.

  Here, the mixing molar ratio (that is, 1,4-cyclohexanemethanol / 1,4-butanediol / ethylene glycol) can be arbitrarily selected, but the molar fraction of 1,4-cyclohexanemethanol is: From the viewpoint of oil resistance and solvent resistance, it is preferably 20 to 100 mol%.

  Moreover, as for the molar fraction of 1, 4- butanediol in said mixture, 0-30 mol% is preferable. When 1,4-butanediol is contained in the above mixture, there is an advantage that the solvent resistance is improved, but when the proportion exceeds 30 mol%, the heat resistance may be lowered.

  Moreover, it is preferable that the molar fraction of ethylene glycol is 0-80 mol% in the said mixture. When ethylene glycol is contained in the above mixture, there is an advantage that the fluidity is improved, but when the proportion exceeds 80 mol%, the solvent resistance and heat resistance may be lowered.

  In addition, in the range which does not impair the effect of this invention, mix | blending other diol components other than the above is not restrict | limited in particular. Other diol components include aromatic diols such as ethylene oxide adducts of bisphenol A and bisphenol S.

  As raw materials for introducing a dicarboxylic acid residue having a naphthalene skeleton constituting the polyester resin, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5 -Naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,4-naphthalenedicarboxylic acid, 2,5-naphthalene Examples include dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 2,8-naphthalenedicarboxylic acid. Of these, 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid are preferred from the viewpoints of heat resistance and solvent resistance.

  Further, as long as the effects of the present invention are not impaired, a part of the dicarboxylic acid residue may be replaced with another dicarboxylic acid residue. As other components for introducing a dicarboxylic acid residue, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 4,4′-diphenyldicarboxylic acid, diphenyl ether dicarboxylic acid; oxalic acid, malonic acid, succinic acid, Examples thereof include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, maleic acid, and itaconic acid.

  In the present invention, from the viewpoint of chemical resistance, heat resistance, and versatility and economy, ethylene glycol as a raw material for introducing a diol residue, and a dicarboxylic acid residue having a naphthalene skeleton are introduced. A resin composed of 2,6-naphthalenedicarboxylic acid as a raw material, that is, polyethylene naphthalate is most preferable.

  In the polyester resin used in the present invention, a solution obtained by dissolving 1.0 g of a polyester resin in 100 ml of a mixture of phenol / 1,1,2,2-tetrachloroethane (mass ratio) = 60/40 at a temperature of 25 ° C. The intrinsic viscosity is preferably 0.40 to 1.00 dl / g, and more preferably 0.45 to 0.90 dl / g. The intrinsic viscosity is calculated by the above formula (1).

  When the intrinsic viscosity of the polyester resin is less than 0.40 dl / g, when the resin composition of the present invention is formed into a molded product, the mechanical properties may be inferior or heat resistance may be reduced. is there. Further, when the intrinsic viscosity of the polyester resin exceeds 0.70 dl / g, the melt viscosity becomes high and the fluidity becomes inferior. When the resin composition is produced or the obtained resin composition is used as a molded body. In some cases, it may not be practical.

  In the present invention, the polyester resin is preferably crystalline from the viewpoint of chemical resistance of the resulting resin composition. The definition of being crystalline will be described later.

  In the present invention, the mixing ratio of the polyarylate resin and the polyester resin needs to be (polyarylate resin) / (polyester resin) = 50/50 to 5/95 by mass ratio, preferably 55 / 45-8 / 92. When this mass ratio exceeds 50/50, the solvent resistance of the obtained resin composition is lowered, and as a result, transparency and mechanical properties are liable to be lowered. On the other hand, when the mass ratio is less than 5/95, the obtained resin composition becomes crystalline and may be crystallized to lower transparency when formed into a molded body.

  The resin composition of the present invention may contain an organic acid metal salt. The organic acid metal salt is a salt of an organic carboxylic acid and a metal ion. Polyarylate resin and polyester resin are not easily compatible with each other, but by containing organic acid metal salt, the compatibility of polyarylate resin and polyester resin is improved, and the resulting resin composition becomes more amorphous. There is an advantage that it becomes easy.

  Specific examples of organic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid Alkyl carboxylic acids such as arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, triacontanoic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid Alkyl dicarboxylic acids such as acids; acrylic acid, methacrylic acid, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, decenoic acid, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, oleic acid, icosenic acid, erucic acid, linol Alkenyl carboxylic acids such as acids; maleic acid, fumaric acid Glutaconic acid, aliphatic carboxylic acids, such as alkenyl dicarboxylic acid and isomers thereof, such as hexene diacid; benzoic acid, phthalic acid, naphthalene carboxylic acid, and aromatic carboxylic acids such as naphthalene dicarboxylic acid. Of these, alkylcarboxylic acids are preferably used from the viewpoint of improving compatibility.

  The metal ion is not particularly limited as long as it can react with the organic carboxylic acid to form a salt, but from the viewpoint of transparency and mechanical properties of the obtained resin composition, the group 1, group 2, group 12, Those selected from Group 13 metals are preferred. Examples of metal ions include lithium, sodium, potassium, magnesium, calcium, barium, zinc, and aluminum.

  As the organic acid metal salt, sodium acetate, potassium acetate, calcium stearate, and magnesium stearate are preferable from the viewpoint of the transparency and mechanical properties of the obtained resin composition.

  When the organic acid metal salt is contained in the resin composition of the present invention, the content thereof is preferably 0.001 to 0.1 parts by mass with respect to 100 parts by mass in total of the polyarylate resin and the polyester resin, More preferably from 005 to 0.08 parts by mass. If the content is less than 0.001 part by mass, the effect of the organic acid metal salt may not be exhibited and the resin composition may not be amorphous. Moreover, when content exceeds 0.1 mass part, when obtaining a resin composition, since resin will decompose | disassemble easily, mechanical characteristics will fall, and also the color tone of a resin composition may fall.

The resin composition of the present invention is excellent in transparency. In the present invention, the total light transmittance and haze can be used as an index of transparency.
When a molded product having a thickness of 3 mm is obtained from the resin composition of the present invention, the total light transmittance of the molded product is preferably 80% or more. More preferably, it is 83% or more. When the total light transmittance is less than 80%, the transparency is insufficient. In addition, since the polyarylate resin has a relatively high refractive index, the upper limit of the total light transmittance is usually about 90%. In the present invention, the total light transmittance is a value measured according to JIS K 7105.

Further, when a molded product having a thickness of 3 mm is obtained from the resin composition of the present invention, the haze of the molded product is preferably 10 or less, more preferably 8 or less, and further preferably 6 or less. In addition, when the obtained molded body is used in an application that requires visibility of the remaining amount of content such as a liquid container, the haze is preferably small, but if the haze is large, the mechanical properties are As long as the thickness of the molded body is not significantly impaired, the thickness of the molded body can be reduced to ensure transparency. The haze is a value calculated by the following formula (2).
Haze = (diffuse light transmittance) / (total light transmittance) × 100 (2)
In the above formula (2), the diffuse light transmittance and the total light transmittance are values measured according to JIS K 7105.

  Even if the total light transmittance is 80% or more, if the haze exceeds 10, it may become cloudy and the transparency may be insufficient. Further, even if the haze is 10 or less, if the total light transmittance is less than 80%, the transparency may be insufficient due to a markedly colored state. Therefore, in the present invention, it is preferable that both the total light transmittance and the haze satisfy the above preferable range.

The polyarylate resin used in the present invention and the resin composition of the present invention are preferably amorphous from the viewpoint of improving transparency. Here, the term “amorphous” means that it does not crystallize when cooled and solidified from a molten state. Using DSC, the resin composition is changed from a normal temperature (for example, 30 ° C.) to a molten state (for example, 300 ° C.) at a rate of temperature increase of 10 ° C./min, and then gradually cooled to a normal temperature at a rate of temperature decrease of 10 ° C./min. It can be defined by the fact that an exothermic peak derived from latent heat cannot be confirmed.
In general crystalline resins and resin compositions, when X-ray diffraction is performed in a solid state, a diffraction peak derived from crystals is observed, or a process of heating from normal temperature to a molten state by differential scanning calorimetry (DSC) In the process, an endothermic peak derived from the latent heat of melting of the crystal is observed, or an exothermic peak derived from the latent heat of crystallization is observed in the process of cooling from the molten state to room temperature.

  In the present invention, the polyarylate resin and the resulting resin composition do not show an exothermic peak derived from latent heat of crystallization in the process of cooling from the molten state to room temperature, and the resin composition before and after contact with chemicals This is important for suppressing changes in the appearance of objects. In molding methods such as injection molding and extrusion molding, generally, a molten resin is rapidly cooled and solidified. However, a resin having a low crystallization rate, such as polyethylene terephthalate, has a cooling rate that is too high. It becomes a molded body in an amorphous state. When such a molded product comes into contact with a chemical such as an organic solvent, the chemical penetrates from the surface of the molded product through the surface of the molded product, so that part of the resin crystallizes and the appearance of the molded product is transparent to opaque. It may change into something.

  On the other hand, if the resin composition comprising a polyarylate resin and a polyester resin does not crystallize even if it is slowly cooled from the molten state, crystallization hardly occurs even if chemicals penetrate into the molded body, and the molded body This is preferable because the appearance of the material does not change.

  Moreover, it is preferable that the polyester resin used in this invention is crystalline from a chemical-resistant viewpoint of the resin composition obtained. In the present invention, “crystallinity” means that the resin composition is heated from a normal temperature (for example, 30 ° C.) to a molten state (for example, 300 ° C.) at a temperature increase rate of 10 ° C./min using DSC. This can be confirmed by showing an exothermic peak derived from the latent heat of crystallization in either the temperature raising process or the temperature lowering process when the temperature is gradually lowered to room temperature at a temperature lowering rate of 10 ° C./min.

  The resin composition of the present invention can be produced by mixing a polyarylate resin, a polyarylate resin composition, and, if necessary, an organic acid metal salt. Examples of the mixing method include melt kneading. When melt-kneading, it is preferable to melt-knead under high shear conditions using a co-rotating twin screw extruder. The high shear condition is generally a method of increasing the number of kneading discs provided on the screw for melt-kneading the resin, or using a reverse screw type or neutral type kneading disc in combination. As another method, a method of using a specially shaped screw with good shear efficiency or increasing the screw rotation speed is exemplified. Among these methods, a method using a reverse screw type or neutral type kneading disk or a method using a specially shaped screw can suppress a decrease in the molecular weight of the resin composition during melt processing, and the resulting resin The composition is more preferable because it tends to be amorphous.

  When the resin composition is produced by melt kneading, the method for supplying the polyarylate resin and the polyester resin and, if necessary, the organic acid metal salt to the twin screw extruder is not particularly limited. For example, a method in which each raw material weighed at a predetermined blending ratio is uniformly dry blended using a mixer such as a tumbler or Henschel mixer, and then supplied to a twin-screw extruder from a quantitative feeder; For example, a method may be used in which each supply amount is set to a predetermined blending ratio from the supply machine and is supplied independently to the twin screw extruder.

  A melt-kneaded resin composition such as a twin screw extruder is cooled and solidified by a method such as a water bath or air cooling, and then pelletized. Pelletization is not particularly limited as long as granulation from a melt-kneaded product is achieved. For example, pelletization may be performed with a pelletizer or pulverized with a pulverizer. Alternatively, a hot cutter may be installed on the die of the twin-screw extruder, and the resin composition may be cooled and solidified after cutting. In addition, it is preferable to install a vacuum vent in the twin-screw extruder and evacuate the melt-kneading part and the subsequent parts because the molecular weight reduction of the resin composition can be suppressed.

  When the resin composition of the present invention is melt-kneaded, the kneading temperature is preferably in the range of 220 to 320 ° C. When the temperature is lower than 220 ° C., the melt viscosity of the resin composition to be melt-kneaded becomes too large, so that the power of the twin-screw extruder is insufficient and the kneading may be insufficient. On the other hand, when the kneading temperature exceeds 300 ° C., the resin is easily decomposed, so that the mechanical properties are lowered, and the color tone of the resin composition may be further lowered.

  In a device where raw materials are continuously supplied and the kneaded resin is continuously discharged from a discharge hole different from the supply hole, such as a twin-screw extruder, it is possible to set different temperatures for each part of the device From the viewpoint of the compatibility between the polyarylate resin and the polyester resin, and the color tone of the resulting resin composition, from 250 to 320 ° C. from the raw material supply section through the preheating section to the melt kneading section, from the melt kneading section onwards It is preferable to set the temperature to 220 to 270 ° C. until reaching the discharge hole.

  In addition, since the discharge amount of the resin discharged from the twin-screw extruder and the screw rotation speed are not generally determined, the power of the apparatus, the temperature at which the resulting resin composition is discharged, the degree of melt kneading, and It is preferable to adjust in consideration of the molecular weight.

  In the resin composition of the present invention, an organic phosphorus compound, an organic phosphorous compound, an organic phosphinic acid-based compound and the like may be added for the purpose of improving the initial color tone within a range not impairing the effects of the present invention. In addition, for the purpose of improving long-term durability, an antioxidant such as a hindered phenol or lactone, or a hindered amine light stabilizer may be added. Furthermore, various additives such as ultraviolet absorbers, bluing agents, flame retardants, mold release agents, antistatic agents, and lubricants may be added.

  The resin composition obtained by the above method is amorphous and excellent in transparency. Furthermore, it becomes excellent in tensile strength and solvent resistance.

  The 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, blow molding, extrusion molding method, compression molding method, melt casting method and the like are used.

  In the case of a container shape, injection molding and blow molding can be preferably used. In the case of a sheet shape, an extrusion molding method, a compression molding method, and a melt casting method can be preferably used. Depending on the shape, they can be appropriately selected and combined. The molding conditions are not particularly limited, but the cylinder temperature is preferably 220 to 300 ° C., more preferably 220 to 290 ° C. from the viewpoint of residence stability and fluidity during melt processing. Moreover, it is preferable that mold temperature is 20-100 degreeC from a viewpoint of the thermal deformation temperature of a molded object, and a residual stress reduction. Furthermore, the residence time from when the resin composition enters the cylinder through the hopper until it is injected or discharged from the nozzle is preferably 20 to 400 seconds, and more preferably 20 to 300 seconds. In the case of injection molding, the mold temperature is preferably 20 to 100 ° C., the back pressure during measurement is 5 to 15 MPa, and the injection speed is preferably 20 to 200 mm / second.

  Specific examples of molded articles formed by molding the resin composition of the present invention include resin parts for electrical appliances such as peripherals of displays such as flat-screen TVs, personal computers, mobile phones, mobile devices, and housings, headlight covers, and lamp covers. In addition to automotive exterior resin parts such as reflectors, 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.
<Evaluation method>
(1) Intrinsic viscosity (unit: dl / g)
Measurement was performed at a concentration of 1 g / l and a temperature of 25 ° C. using a mixed solution of phenol / 1,1,2,2-tetrachloroethane (mass ratio) = 60/40 as a solvent.
(2) DSC measurement Using a DSC apparatus (trade name “Diamond DSC”, manufactured by Perkin Elmer Co., Ltd.), the temperature was raised from 30 ° C. to 300 ° C. at a heating rate of 10 ° C./min, and then to 30 ° C. The presence or absence of a peak corresponding to the latent heat of crystallization in the process of gradually decreasing the temperature at a temperature decrease rate of 10 ° C./min was confirmed.
(3) Transparency (total light transmittance)
A plate-type test piece having a thickness of 3 mm was prepared from the resin compositions obtained in Examples and Comparative Examples, and a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name “NDH-2000”) was used according to JIS K7105. The total light transmittance was measured. Evaluation was made according to the following criteria.
A: Total light transmittance is 83% or more.
A: The total light transmittance is 80% or more and less than 83%.
X: Total light transmittance is less than 80%.
(4) Transparency (haze)
A plate-type test piece having a thickness of 3 mm was prepared from the resin compositions obtained in Examples and Comparative Examples, and a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name “NDH-2000”) was used according to JIS K7105. The haze was measured. Evaluation was made according to the following criteria.
A: Haze is 6 or less.
○: Haze exceeds 6 and is 10 or less.
X: Haze exceeds 10.
(5) Tensile strength ASTM No. 1 dumbbell-shaped test pieces having a thickness of 3.2 mm were prepared from the resin compositions obtained in the examples and comparative examples, and the tensile strength was measured according to ASTM D-638. Evaluation was made according to the following criteria. In the present invention, those having a value of ◯ or more are considered to be practically usable.
A: 70 MPa or more.
○: It was 60 MPa or more and less than 70 MPa.
X: It was less than 60 MPa.
(6) Solvent resistance (appearance)
From the resin compositions obtained in Examples and Comparative Examples, plate-type test pieces having a thickness of 3 mm were prepared and visually observed. The test piece is immersed in methanol (special grade reagent) at 50 ° C. for 30 days. When the test piece is taken out from methanol, the methanol adhering to the surface of the test piece is wiped off, and further, the temperature is 23 ° C. and the relative humidity is 50% RH. After exposure, the appearance of the test piece was visually observed after 1 hour and 2 days. Evaluation was performed according to the following criteria. In the present invention, those having a value of ◯ or more are considered to be practically usable.
A: There was no change in the test piece before and after the immersion treatment.
○: Compared with the test piece before the immersion treatment, whitening occurred in a part of the surface layer of the test piece after the immersion treatment.
(Triangle | delta): Compared with the test piece before immersion treatment, the test piece showed whitening on the whole after immersion treatment.
X: Compared with the test piece before the immersion treatment, the test piece was entirely whitened after the immersion treatment, and micro cracks having a depth of 1 mm or less occurred in the test piece.
XX: Compared with the test piece before the immersion treatment, the entire test piece became opaque after the immersion treatment, and cracks exceeding 1 mm in depth occurred in the test piece.
(7) Solvent resistance (total light transmittance)
A plate-type test piece having a thickness of 3 mm was prepared from the resin compositions obtained in Examples and Comparative Examples, and immersed in methanol (special grade reagent) at 50 ° C. for 30 days. When the test piece was taken out of methanol, the methanol adhering to the surface of the test piece was wiped off, and further exposed to an environment at a temperature of 23 ° C. and a relative humidity of 50% RH. After 3 days, the total light transmittance was the same as in (3) above. Was measured. The difference between the total light transmittance obtained and the total light transmittance obtained in (3) above was calculated. Evaluation was made according to the following criteria. In the present invention, those having a value of ◯ or more are considered to be practically usable.
A: The difference in total light transmittance is 2 or less.
A: The difference in total light transmittance is more than 2 and 5 or less.
X: The difference in the total light transmittance exceeds 5.
(8) Solvent resistance (haze)
A plate-type test piece having a thickness of 3 mm was prepared from the resin compositions obtained in Examples and Comparative Examples, and immersed in methanol (special grade reagent) at 50 ° C. for 30 days. When the test piece was taken out of methanol, the methanol adhering to the surface of the test piece was wiped off, and further exposed to an environment of a temperature of 23 ° C. and a relative humidity of 50% RH, and the haze was measured in the same manner as in the above (4) after 3 days. . The difference between the obtained haze and the haze obtained in the above (4) was calculated. Evaluation was made according to the following criteria. In the present invention, those having a value of ◯ or more are considered to be practically usable.
A: The difference in haze is zero.
○: Haze difference is 1 or less.
X: The difference in haze exceeds 1.
(9) Solvent resistance (tensile strength)
An ASTM No. 1 dumbbell-shaped test piece having a thickness of 3.2 mm was prepared from the resin compositions obtained in Examples and Comparative Examples, and immersed in methanol (special grade reagent) at 50 ° C. for 30 days. When the test piece is taken out of methanol, the methanol adhering to the surface of the test piece is wiped off, and further exposed to an environment of a temperature of 23 ° C. and a relative humidity of 50% RH, and the tensile strength is measured in the same manner as (5) after 3 days. did. The ratio [(tensile strength after immersion treatment) / (tensile strength before immersion treatment)] between the obtained tensile strength and the tensile strength obtained in (5) above was calculated. Evaluation was made according to the following criteria. In the present invention, those having a value of ◯ or more are considered to be practically usable.
A: (Tensile strength after immersion treatment) / (Tensile strength before immersion treatment) is 0.900 or more.
○: (Tensile strength after immersion treatment) / (Tensile strength before immersion treatment) 0.600 or more and less than 0.900.
X: (Tensile strength after immersion treatment) / (Tensile strength before immersion treatment) is less than 0.600.

<Raw material>
The raw materials used in Examples and Comparative Examples are shown below.
(A) Preparation of polyarylate resin / polyarylate resin (A-1) 3 kg of sodium hydroxide was dissolved in 250 L of ion-exchanged water in a 500 L reaction vessel equipped with a water cooling jacket and a stirring device, 8.3 kg (36.4 mol) of bisphenol A (hereinafter sometimes referred to as BPA), 0.18 kg (1.2 mol) of p-tert-butylphenol (DIC) as a molecular weight regulator, It was set as the water phase.

  Furthermore, in another reaction vessel, 130 L of dichloromethane (manufactured by Tokuyama Corporation, “methylene chloride”) was mixed with phthalic acid chloride (molar ratio = 50) which is an equimolar mixture of 3.75 kg of isophthalic acid dichloride and 3.75 kg of terephthalic acid dichloride. : 50) was dissolved to obtain an organic phase.

  0.075 kg of a 50% by weight aqueous solution of benzyltrimethylammonium chloride was added to the aqueous phase where the temperature was kept at 20 ° C., and the organic phase was further added. After stirring for 6 hours, the stirring was stopped. did. The aqueous and organic phases were separated by decantation. After adding 0.25 g of acetic acid to the organic phase from which the aqueous phase had been removed, 130 L of ion-exchanged water was added. The mixture was further stirred at 20 ° C. for 20 minutes, and the aqueous phase was removed again by decantation. This washing operation is repeated until the aqueous phase becomes neutral, and then the organic phase is poured into 50 L, 100 L of warm water in a 200 L container equipped with a homomixer, and the dichloromethane is evaporated to form a powder. Of polyarylate resin was obtained. This powdery polyarylate resin was dehydrated and dried under reduced pressure at 120 ° C. for 24 hours using a vacuum dryer to obtain a polyarylate resin (A-1). The intrinsic viscosity of this resin was 0.72 dl / g. As a result of DSC measurement, no crystal melting peak was observed.

-Preparation of polyarylate resin (A-2) In a reaction vessel having an internal volume of 500 L equipped with a water cooling jacket and a stirrer, 3 kg of sodium hydroxide was dissolved in 250 L of ion-exchanged water, and then 10.56 kg of bisphenol AP. (36.4 mol), 0.18 kg (1.2 mol) of p-tert-butylphenol (manufactured by DIC) as a molecular weight modifier was dissolved to obtain an aqueous phase.

  Furthermore, in another reaction vessel, 130 L of dichloromethane (manufactured by Tokuyama Corporation, “methylene chloride”) was mixed with phthalic acid chloride (molar ratio = 50) which is an equimolar mixture of 3.75 kg of isophthalic acid dichloride and 3.75 kg of terephthalic acid dichloride. : 50) was dissolved to obtain an organic phase.

  0.075 kg of a 50% by weight aqueous solution of benzyltrimethylammonium chloride was added to the aqueous phase where the temperature was kept at 20 ° C., and the organic phase was further added. After stirring for 6 hours, the stirring was stopped. did. The aqueous and organic phases were separated by decantation. After adding 0.25 g of acetic acid to the organic phase from which the aqueous phase had been removed, 130 L of ion-exchanged water was added. The mixture was further stirred at 20 ° C. for 20 minutes, and the aqueous phase was removed again by decantation. This washing operation is repeated until the aqueous phase becomes neutral, and then the organic phase is poured into 50 L, 100 L of warm water in a 200 L container equipped with a homomixer, and the dichloromethane is evaporated to form a powder. Of polyarylate resin was obtained. This powdery polyarylate resin was dehydrated and dried under reduced pressure at 120 ° C. for 24 hours using a vacuum dryer to obtain a polyarylate resin (A-2). The intrinsic viscosity of this resin was 0.73 dl / g. As a result of DSC measurement, no crystal melting peak was observed.

-Preparation of polyarylate resin (A-3) 3 kg of sodium hydroxide was dissolved in 250 L of ion exchange water in a 500 L internal reaction vessel equipped with a water cooling jacket and a stirrer, and then 5.8 kg of BPA ( 25.4 mol), 3.4 kg (11.0 mol) of bisphenol TMC, and 0.18 kg (1.2 mol) of p-tert-butylphenol (manufactured by DIC) as a molecular weight regulator were dissolved to obtain an aqueous phase.

  Furthermore, in another reaction vessel, 130 L of dichloromethane (manufactured by Tokuyama Corporation, “methylene chloride”) was mixed with phthalic acid chloride (molar ratio = 50) which is an equimolar mixture of 3.75 kg of isophthalic acid dichloride and 3.75 kg of terephthalic acid dichloride. : 50) was dissolved to obtain an organic phase.

  0.075 kg of a 50% by weight aqueous solution of benzyltrimethylammonium chloride was added to the aqueous phase where the temperature was kept at 20 ° C., and the organic phase was further added. After stirring for 6 hours, the stirring was stopped. did. The aqueous and organic phases were separated by decantation. After adding 0.25 g of acetic acid to the organic phase from which the aqueous phase had been removed, 130 L of ion-exchanged water was added. The mixture was further stirred at 20 ° C. for 20 minutes, and the aqueous phase was removed again by decantation. This washing operation is repeated until the aqueous phase becomes neutral, and then the organic phase is poured into 50 L, 100 L of warm water in a 200 L container equipped with a homomixer, and the dichloromethane is evaporated to form a powder. Of polyarylate resin was obtained. This powdery polyarylate resin was dehydrated and dried under reduced pressure at 120 ° C. for 24 hours using a vacuum dryer to obtain a polyarylate resin (A-3). The intrinsic viscosity of this resin was 0.73 dl / g. As a result of DSC measurement, no crystal melting peak was observed.

-Preparation of polyarylate resin (A-4) 3 kg of sodium hydroxide was dissolved in 250 L of ion-exchanged water in a 500 L internal reaction vessel equipped with a water cooling jacket and a stirrer, and then 9.76 kg of bisphenol Z. (36.4 mol), 0.18 kg (1.2 mol) of p-tert-butylphenol (manufactured by DIC) as a molecular weight modifier was dissolved to obtain an aqueous phase.

  Furthermore, in another reaction vessel, 130 L of dichloromethane (manufactured by Tokuyama Corporation, “methylene chloride”) was mixed with phthalic acid chloride (molar ratio = 50) which is an equimolar mixture of 3.75 kg of isophthalic acid dichloride and 3.75 kg of terephthalic acid dichloride. : 50) was dissolved to obtain an organic phase.

  0.075 kg of a 50% by weight aqueous solution of benzyltrimethylammonium chloride was added to the aqueous phase where the temperature was kept at 20 ° C., and the organic phase was further added. After stirring for 6 hours, the stirring was stopped. did. The aqueous and organic phases were separated by decantation. After adding 0.25 g of acetic acid to the organic phase from which the aqueous phase had been removed, 130 L of ion-exchanged water was added. The mixture was further stirred at 20 ° C. for 20 minutes, and the aqueous phase was removed again by decantation. This washing operation is repeated until the aqueous phase becomes neutral, and then the organic phase is poured into 50 L, 100 L of warm water in a 200 L container equipped with a homomixer, and the dichloromethane is evaporated to form a powder. Of polyarylate resin was obtained. This powdery polyarylate resin was dehydrated and dried under reduced pressure at 120 ° C. for 24 hours using a vacuum dryer to obtain a polyarylate resin (A-3). The intrinsic viscosity of this resin was 0.56 dl / g. As a result of DSC measurement, no crystal melting peak was observed.

Preparation of polyarylate resin (A-5) 3 kg of sodium hydroxide was dissolved in 250 L of ion exchange water in a 500 L reaction vessel equipped with a water cooling jacket and a stirrer, and then bisphenol A (hereinafter referred to as BPA). 8.3 kg (36.4 mol) and 0.18 kg (1.2 mol) of p-tert-butylphenol (DIC) as a molecular weight regulator were dissolved to obtain an aqueous phase.

  Further, in another reaction vessel, 130 L of dichloromethane (manufactured by Tokuyama Corporation, “methylene chloride”) is mixed with 3.0 kg of isophthalic acid dichloride and 4.5 kg of terephthalic acid dichloride (isophthalic acid / terephthalic acid molar ratio = 40:60) was dissolved to obtain an organic phase.

  0.075 kg of a 50% by weight aqueous solution of benzyltrimethylammonium chloride was added to the aqueous phase where the temperature was kept at 20 ° C., and the organic phase was further added. After stirring for 6 hours, the stirring was stopped. did. The aqueous and organic phases were separated by decantation. After adding 0.25 g of acetic acid to the organic phase from which the aqueous phase had been removed, 130 L of ion-exchanged water was added. The mixture was further stirred at 20 ° C. for 20 minutes, and the aqueous phase was removed again by decantation. This washing operation is repeated until the aqueous phase becomes neutral, and then the organic phase is poured into 50 L, 100 L of warm water in a 200 L container equipped with a homomixer, and the dichloromethane is evaporated to form a powder. Of polyarylate resin was obtained. This powdery polyarylate resin was dehydrated and dried under reduced pressure at 120 ° C. for 24 hours using a vacuum dryer to obtain a polyarylate resin (A-5). The intrinsic viscosity of this resin was 0.67 dl / g. As a result of DSC measurement, no crystal melting peak was observed.

-Preparation of polyarylate resin (A-6) 3 kg of sodium hydroxide was dissolved in 250 L of ion exchange water in a 500 L internal reaction vessel equipped with a water cooling jacket and a stirrer, and then bisphenol A (hereinafter referred to as BPA). 8.3 kg (36.4 mol) and 0.18 kg (1.2 mol) of p-tert-butylphenol (DIC) as a molecular weight regulator were dissolved to obtain an aqueous phase.

  Further, in another reaction vessel, 130 L of dichloromethane (manufactured by Tokuyama, “methylene chloride”) was mixed with 5.25 kg of isophthalic acid dichloride and 2.25 kg of terephthalic acid dichloride (isophthalic acid / terephthalic acid molar ratio = 70:30) was dissolved to obtain an organic phase.

  0.075 kg of a 50% by weight aqueous solution of benzyltrimethylammonium chloride was added to the aqueous phase where the temperature was kept at 20 ° C., and the organic phase was further added. After stirring for 6 hours, the stirring was stopped. did. The aqueous and organic phases were separated by decantation. After adding 0.25 g of acetic acid to the organic phase from which the aqueous phase had been removed, 130 L of ion-exchanged water was added. The mixture was further stirred at 20 ° C. for 20 minutes, and the aqueous phase was removed again by decantation. This washing operation is repeated until the aqueous phase becomes neutral, and then the organic phase is poured into 50 L, 100 L of warm water in a 200 L container equipped with a homomixer, and the dichloromethane is evaporated to form a powder. Of polyarylate resin was obtained. This powdery polyarylate resin was dehydrated and dried under reduced pressure at 120 ° C. for 24 hours using a vacuum dryer to obtain a polyarylate resin (A-6). The intrinsic viscosity of this resin was 0.65 dl / g. As a result of DSC measurement, no crystal melting peak was observed.

(B) Preparation of polyester resin / polyester resin (B-1) 40 kg of dimethyl 2,6-naphthalenedicarboxylate, 20 kg of ethylene glycol and 0.024 kg of calcium acetate monohydrate are supplied to a transesterification reaction tank under a nitrogen gas atmosphere. The temperature was raised from 140 ° C. to 230 ° C. over 4 hours, and the transesterification reaction was carried out while distilling the produced methanol out of the reaction system. To the obtained reaction product, 0.02 kg of sodium phosphate and 0.012 kg of germanium dioxide were added and transferred to a polymerization tank. Subsequently, the pressure in the polymerization tank was gradually reduced from 1013 hPa to 1.3 hPa after 1 hour, and at the same time, the temperature in the polymerization tank was raised from 230 ° C. to 285 ° C. over 1.5 hours. Furthermore, the polymerization reaction was performed at a temperature of 285 ° C. for 2 hours under a reduced pressure of 1.3 hPa or less.

  Thereafter, the inside of the reactor is pressurized with nitrogen, discharged as a strand from a base provided at the bottom of the reactor, cooled and solidified in a water bath, cut with a pelletizer, and pelletized polycondensate, so-called polyethylene A naphthalate resin was obtained. The polycondensate pellets were dried at 110 ° C. for 48 hours under reduced pressure using a vacuum dryer to obtain a polyester resin (B-1). The intrinsic viscosity of this resin was 0.64 dl / g. As a result of DSC measurement, a crystal melting peak was observed at 265 ° C. during the temperature rising process, and a crystallization peak was observed at 190 ° C. during the temperature lowering process.

・ Polyester resin (B-2)
Polyethylene terephthalate resin (trade name “NEH-2070” manufactured by Unitika Ltd.) was used as (B-2). In this resin, the dicarboxylic acid residue was a terephthalic acid unit, and the diol residue was an ethylene glycol unit. The intrinsic viscosity was 0.88 dl / g. As a result of DSC measurement, a crystal melting peak was observed at 252 ° C. during the temperature rising process, and a crystallization peak was observed at 166 ° C. during the temperature lowering process.

・ Polyester resin (B-3)
A copolymerized polyester resin (trade name “Thermix 6761” manufactured by Eastman Chemical Co., Ltd.) was used as (B-3). In this resin, 95 mol% of dicarboxylic acid residues were TPA units, 5 mol% was isophthalic acid units, and diol residues were 1,4-cyclohexanedimethanol units. The intrinsic viscosity was 0.9 dl / g. As a result of DSC measurement, a crystal melting peak was observed at 279 ° C. during the temperature rising process, and a crystallization peak was observed at 210 ° C. during the temperature decreasing process.
(C) Organic acid metal salt sodium acetate (made by Wako Pure Chemical Industries, special grade reagent)

<Example 1>
After mixing 50 parts by mass of dry (A-1), 50 parts by mass of (B-1) and 0.01 parts by mass of (C-1) with a total charge of 3 kg, a loss-in-weight continuous quantitative supply device ( Using a Kubota product name “CE-W-1”), a screw diameter 37 mm, L / D38 twin screw extruder having two vent portions (manufactured by Toshiba Machine Co., Ltd., product name “TEM-37BS”) To the supply port. The barrel set temperature from the extruder feed section to the kneading section is 290 ° C., the barrel set temperature after the kneading section of the extruder is 260 ° C., the vent pressure reduction is 0.099 MPa (gauge pressure), the screw rotation speed is 200 rpm, and the discharge amount Melt kneading was performed at 20 kg / h. The melt-kneaded product taken up in the form of a strand from the nozzle was cooled and solidified in a water bath, cut with a pelletizer, and then dried with hot air at 100 ° C. for 8 hours to obtain a pellet-shaped resin composition. The intrinsic viscosity and DSC of this resin composition were measured. Next, the obtained resin composition was used using a 32 mmφ injection molding machine (trade name “EC100NII” manufactured by Toshiba Machine Co., Ltd.), a cylinder temperature of 280 ° C., a residence time in the cylinder of 120 seconds, a mold temperature of 40 ° C., A plate type test piece having a thickness of 3 mm and an ASTM No. 1 dumbbell type test piece having a thickness of 3.2 mm were produced by injection molding under the conditions of a back pressure of 10 MPa during measurement and an injection speed of 100 mm / second. The obtained test piece was subjected to evaluation. The evaluation results are shown in Table 1.

<Examples 2 to 11>
Resin composition and test in the same manner as in Example 1 except that the type and blending ratio of the polyarylate resin, the blending ratio of (B-1), and the blending ratio of the organic acid metal salt were changed as shown in Table 1. Pieces were obtained and submitted for evaluation. The evaluation results are shown in Table 1.
<Comparative Examples 1-6>
The resin composition and the test piece were the same as in Example 1 except that the blending ratio of (A-1), the type and blending ratio of the polyester resin, and the blending ratio of the organic acid metal salt were changed as shown in Table 2. And submitted for evaluation. The evaluation results are shown in Table 2.

  The resin compositions obtained in Examples 1 to 11 were excellent in transparency and excellent in tensile strength. Further, even after immersion in methanol, there was no change in appearance, transparency and tensile strength were maintained, and the solvent resistance was excellent.

  The resin composition obtained in Comparative Example 1 reached a certain level in transparency and tensile strength. However, since no polyester resin was blended in the resin composition, a clear change in appearance was observed after methanol immersion, and transparency and tensile strength were also reduced.

  The resin composition obtained in Comparative Example 2 reached a certain level in transparency and tensile strength. However, since the compounding amount of the polyarylate resin in the resin composition was excessive, a clear change in appearance was observed after immersion in methanol, and transparency and tensile strength were also reduced.

  The resin composition obtained in Comparative Example 3 reached a certain level in transparency and tensile strength. However, since no polyarylate resin was blended in the resin composition, crystallization was facilitated, a clear appearance change was observed after immersion in methanol, and transparency was lowered.

  In the resin composition obtained in Comparative Example 4, the ratio of the organic acid metal salt in the resin composition was too high, so that the intrinsic viscosity of the resin composition was low, and a clear appearance change was observed after methanol immersion, and the transparency And the tensile strength was lowered.

  The resin composition obtained in Comparative Example 5 had a low tensile strength because the structure of the polyester resin was not specified in the present application. In addition, a clear appearance change was observed after immersion in methanol, and transparency was lowered.

  The resin composition obtained in Comparative Example 6 had a low tensile strength because the structure of the polyester resin was not specified in the present application. In addition, a clear change in appearance was observed after methanol immersion, and transparency and tensile strength were reduced.

Claims (8)

The polyarylate resin represented by the following formula (I) and the polyester resin represented by the following formula (II) are in a mass ratio of (polyarylate resin) / (polyester resin) = 50/50 to 5/95. A resin composition comprising:

In the above formula (I), g represents a positive integer. R ^a is an alkylene group having 1 to 10 carbon atoms, an alkylidene group having 1 to 10 carbon atoms, an allylalkylidene group having 1 to 10 carbon atoms, or a cyclohexane having 1 to 10 carbon atoms. Selected from an alkylene group, a divalent saturated or unsaturated aliphatic hydrocarbon group selected from a cycloalkylidene group having 1 to 10 carbon atoms, an oxy group, a thio group, a sulfonyl group, and an N-phenylphthalimidine group Represents at least one kind. R ¹ , R ² and R ³ are chlorine, bromine, fluorine, nitro group, cyano group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 10 carbon atoms, and the number of carbon atoms. It is at least 1 sort (s) of substituent selected from the allyl group which is 1-10, Comprising: You may mutually be same or different. d, e, and f are integers of 0 to 4, and may be the same or different from each other.

In the above formula (II), j represents a positive integer. R ^b is a divalent saturated or unsaturated group selected from an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, and a cycloalkylidene group having 1 to 10 carbon atoms. It represents at least one selected from aliphatic hydrocarbon groups. R ⁴ and R ⁵ are chlorine, bromine, fluorine, nitro group, cyano group, alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 1 to 10 carbon atoms, or 1 to 1 carbon atoms. And at least one substituent selected from an allyl group of 10, which may be the same as or different from each other. h and i are integers of 0 to 3, and may be the same or different from each other.   The organic acid metal salt is contained in an amount of 0.001 to 0.1 parts by mass with respect to a total of 100 parts by mass of the polyarylate resin and the polyester resin.   The resin composition according to claim 1 or 2, wherein a total light transmittance in a molded product having a thickness of 3 mm obtained by molding the resin composition is 80 to 90%, and the resin composition is A resin composition characterized by having a haze of 1 to 10 in a molded product having a thickness of 3 mm obtained by molding.   The resin composition according to any one of claims 1 to 3, wherein the resin composition is heated by a differential scanning calorimeter from 30 ° C to 300 ° C at a temperature rising rate of 10 ° C / min, and then the temperature is lowered. A resin composition characterized by exhibiting no exothermic peak due to latent heat of crystallization in any of the temperature raising process and the temperature lowering process when the temperature is lowered to 30 ° C. at a rate of 10 ° C./min.   The dicarboxylic acid residue constituting the polyarylate resin contains at least a terephthalic acid residue and an isophthalic acid residue, and the molar ratio of the terephthalic acid residue to the isophthalic acid residue is (terephthalic acid residue) / (isophthalic acid residue) Residue) = 60/40 to 25/75, The resin composition according to any one of claims 1 to 4.   The dihydric phenol residue constituting the polyarylate resin is 2,2-bis (4-hydroxyphenyl) propane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4 6. The composition according to claim 1, wherein the compound is at least one selected from -hydroxyphenyl) cyclohexane and 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane. The resin composition described in 1.   The dicarboxylic acid residue constituting the polyester resin is at least one selected from 1,5-naphthalenedicarboxylic acid residue and 2,6-naphthalenedicarboxylic acid residue, and the diol residue constituting the polyester resin Is at least one selected from ethylene glycol and 1,4-butanediol. The resin composition according to any one of claims 1 to 6, wherein   The molded object formed by shape | molding the resin composition in any one of Claims 1-7.