JP2014058322A - Resin composition for biodiesel fuel container and molded body using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylate resin composition that has sufficient flowability and moldability, while maintaining heat resistance and mechanical physical properties of conventional polyarylate resin, and has sufficient resistance to biodiesel fuel.SOLUTION: This invention provides a resin composition for biodiesel fuel containers. In the composition, with respect to 100 pts.mass of the total of polyarylate resin (A) and polycarbonate resin (B), 0.1-5 pts.mass of carbodiimide compound (C), 0.01-0.5 pts.mass of antioxidant (D), and 0.01-0.5 pts.mass of fatty acid amide (E) are contained.

Description

  The present invention relates to a highly durable polyarylate resin composition for biodiesel fuel.

Conventionally, polyarylate resins are widely used in fields such as electric / electronics, automobiles, and machines because they are excellent in heat resistance, mechanical strength, and transparency. However, chemical resistance and hydrolysis resistance were not always sufficient.
For example, in the field of various containers such as pharmaceuticals and food and beverage containers and on-vehicle fragrance containers, when the above polyarylate resin is used, the durability is insufficient and the heat resistance, mechanical strength, and transparency are reduced. There was a problem to do.

  In contrast to such a polyarylate resin, in Patent Document 1, a polyester resin composed of 1,4-cyclohexanedimethanol is melt-mixed with respect to the polyarylate resin and used for a solvent such as alcohol without impairing transparency. Chemical resistance is sufficiently improved. Such a polyarylate resin composition was sufficiently resistant to diesel fuel. However, the durability against biodiesel fuel was poor.

  On the other hand, with respect to the durability of polyarylate resin, in particular, deterioration of mechanical properties accompanying a decrease in molecular weight, attempts have been made to increase hydrolysis resistance and durability by end-capping polyarylate resin. In Patent Document 2, by using an acylated product of bisphenol that is a monomer component of a polyarylate resin (a product obtained by extracting OH from a carboxylic acid), the terminal carboxyl group is sealed in a form that does not show a hydrolysis catalytic effect, The hydrolysis resistance of polyarylate resin is greatly improved. However, even such polyarylate resins with improved hydrolysis resistance have not been sufficiently durable against biodiesel fuel.

  There was also a need to further improve moldability using polyarylate resins. In particular, in a thin molded body, improvement in fluidity of the polyarylate resin to be used has been demanded. Conventionally, attempts have been made to alloy a polyarylate resin and a polycarbonate resin to improve fluidity, but there is also a problem that durability against biodiesel fuel decreases due to alloying.

JP 2002-302596 A Japanese Patent Laid-Open No. 3-131623

  In recent years, diesel fuel has been reviewed from the expectation for the reduction of carbon dioxide emissions, and the use of biodiesel fuel has been actively studied. The biodiesel fuel is a fuel composed of vegetable oils such as rapeseed oil, sunflower oil, soybean oil, corn oil, and the like, and fatty acid methyl esters obtained by separating and removing glycerin from methanol by converting the waste edible oil into crude oil using methanol. Such biodiesel fuel is used in a certain ratio in the fatty acid methyl ester alone or in light oil.

  However, since biodiesel fuel has a completely different chemical structure from diesel fuel, a material that is resistant to diesel fuel is not necessarily resistant to biodiesel fuel, and it has been necessary to provide special resistance. Biodiesel fuel has a wide range of raw material options, and material resistance may change depending on the raw material. As a result, it is necessary to review the materials used in the diesel system, which is a problem in the spread of biodiesel fuel.

  Furthermore, since biodiesel fuel contains many contaminant components, it must be filtered once using a filter in order to be used as automobile fuel. Conventionally, amorphous polyamide has been used as such a filter member. The filtration filter member is required to be transparent so that the fuel filtration state and the filter clogging state can be visually recognized. Moreover, durability which can maintain mechanical strength over a long period of time as an automobile member is also required. However, even the above amorphous polyamide has insufficient durability against biodiesel fuel.

The present invention provides a polyarylate resin composition having sufficient fluidity and moldability and sufficient resistance to biodiesel fuel while maintaining the heat resistance and mechanical properties of conventional polyarylate resins. For the purpose.
A molded product obtained from such a polyarylate resin composition can be suitably used in a member that comes into direct contact with biodiesel fuel, particularly in a fuel tank or a filter container of a fuel filter unit for commercial vehicles.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.

That is, the gist of the present invention is as follows.
(1) 0.1-5 mass parts of carbodiimide compound (C) and 0.01-0.5 mass of antioxidant (D) with respect to 100 mass parts of the total of polyarylate resin (A) and polycarbonate resin (B). Part, Fatty acid amide (E) The resin composition for biodiesel fuel containers formed by containing 0.01-0.5 mass part.
(2) The resin composition for a biodiesel fuel container according to (1), wherein a polyarylate resin (A) having a carboxyl value of 20 mol / ton or less is used.
(3) The inherent viscosity (η ₀ ) and the inherent viscosity (η ₁ ) measured under the following conditions (i) and (ii) are (η ₁ ) / (η ₀ ) = 0.9 to 1.1. The resin composition for a biodiesel fuel container according to (1) or (2), wherein the polyarylate resin (A) to be filled is used.
(I) Inherent viscosity (η ₁ ) measured with a mixed solvent of phenol / tetrachloroethane = 6/4 (mass ratio) containing 0.01 mol / L of sodium acetate
(Ii) Inherent viscosity (η ₀ ) measured with tetrachloroethane solution in the absence of sodium acetate
(4) The resin composition for a biodiesel fuel container according to (1) to (3), wherein the carbodiimide compound (C) is poly (1,3,5-triisopropylbenzene) carbodiimide.
(5) The resin composition for a biodiesel fuel container according to (1) to (4), wherein the antioxidant (D) is a hindered phenol-based antioxidant.
(6) The resin composition for a biodiesel fuel container according to (1) to (5), further comprising a release agent (F).
(7) The resin composition for a biodiesel fuel container according to (1) to (6), wherein the release agent (F) is a pentaerythritol compound.
(8) A molded article formed by molding the biodiesel fuel container resin composition of (1) to (7).
(9) The molded article according to (8), which is used as a filter container for biodiesel fuel.

  According to the present invention, there is provided a polyarylate resin composition having sufficient fluidity and moldability and sufficient resistance to biodiesel fuel while maintaining the heat resistance and mechanical properties of a conventional polyarylate resin. can get.

  Hereinafter, the present invention will be described in detail.

  The polyarylate resin (A) in the present invention is a polyester composed of an aromatic dicarboxylic acid residue and a bisphenol residue. The polyarylate resin (A) can be produced by a known and common method such as melt polymerization or interfacial polymerization.

  Examples of the polyarylate raw material for introducing an aromatic dicarboxylic acid residue include terephthalic acid, isophthalic acid, phthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. Acid, 1,5-naphthalenedicarboxylic acid, methyl terephthalic acid, 4,4'-biphenyl dicarboxylic acid, 2,2'-biphenyl dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid 4,4′-diphenylsulfone dicarboxylic acid, 4,4′-diphenylisopropylidenedicarboxylic acid, 1,2-bis (4-carboxyphenoxy) ethane, 5-sodium sulfoisophthalic acid and the like. . These aromatic dicarboxylic acids can be used in combination of two or more.

  Among the aromatic dicarboxylic acids, terephthalic acid and isophthalic acid are preferable, and terephthalic acid and isophthalic acid are used in a mixture in that the melt processability and mechanical properties of the resulting polyarylate resin can be easily improved. More preferably. In that case, the mixing molar ratio of terephthalic acid and isophthalic acid (terephthalic acid / isophthalic acid) can be selected arbitrarily, but from the viewpoint of polymerizability and melt processability of the resulting polyarylate resin, and improvement of mechanical properties , 90/10 to 10/90, preferably 70/30 to 30/70, more preferably 55/45 to 45/55.

  Examples of polyarylate raw materials for introducing bisphenol residues include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 2,2-bis (4-hydroxy-3,5-dimethylphenyl). Propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4′-dihydroxydiphenylsulfone, 4, Bisphenols such as 4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane It is done.

  Among the bisphenols, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferable from the viewpoints of the polymerizability of the polyarylate resin and the improvement of the mechanical properties of the resulting polyarylate resin. Further, when 2,2-bis (4-hydroxyphenyl) propane is used, it can be mixed with other bisphenols, but there are two types in that the chemical resistance of the resulting polyarylate resin is remarkably improved. Hereinafter, it is particularly preferable to use it alone.

In the present invention, the inherent viscosity (η ₁ ) measured under condition (i) of the polyarylate resin (A) and the inherent viscosity (η ₀ ) measured under condition (ii) are (η ₁ ) / (η ₀ ) = 0.9 or more, and more preferably 0.95 or more. When (η ₁ ) / (η ₀ ) is less than 0.9, the molecular weight tends to decrease when contacting with polyarylate biodiesel fuel, particularly the tensile elongation tends to decrease, and the amount of carbodiimide compound necessary for blending increases. There is a tendency and is not preferable.
In the measurement of the inherent viscosity, the inherent viscosity in the condition (i) is measured at a temperature of 25 ° C. using a phenol / tetrachloroethane = 6/4 (mass ratio) solution in the presence of a predetermined amount of sodium acetate. It is an inherent viscosity (η ₁ ), and the inherent viscosity in condition (ii) is an inherent viscosity (η ₀ ) measured at a temperature of 25 ° C. using a tetrachloroethane solution in the absence of sodium acetate. The inherent viscosity (η ₁ ) has an effect of decomposing an acid anhydride bond existing in a polyarylate molecular chain, and sodium acetate has an effect of accelerating the decomposition, so that the acid in the polyarylate resin to be measured It is an indicator of the molecular weight of the remaining fragment that has broken the anhydride bond. An acid anhydride bond is formed by a reaction that occurs as a secondary reaction during the polymerization of polyarylate.

As a method for controlling the ratio of (η ₁ ) / (η ₀ ), there may be mentioned reduction of acid anhydride bonds contained in the polyarylate molecular main chain. In order to reduce the acid anhydride bond, it is effective to increase the polymerization reaction rate of polyarylate. Specifically, the polymerization reaction rate can be adjusted by selecting the type of polymerization catalyst to be used, the blending amount, the stirring speed during polymerization, and the like.

The inherent viscosity (η ₀ ) of the polyarylate resin (A) is preferably 0.45 to 1.0, more preferably 0.50 to 0.9, and 0.52 to 0.8. More preferably it is. When the inherent viscosity (η ₀ ) is less than 0.45, the resulting resin composition has a low molecular weight, so that the mechanical properties, heat resistance, and chemical resistance may be inferior, and the inherent viscosity (η ₀ ) is 1. If it exceeds 0, the melt viscosity becomes high, which may cause discoloration during melt processing or decrease in fluidity. The inherent viscosity (η ₀ ) is an index of the molecular weight of the polyarylate resin (A), and can be appropriately adjusted by adjusting, for example, the raw material monomer charge ratio or using a molecular weight regulator.

  The carboxyl value contained in the polyarylate resin (A) is preferably 20 mol / ton or less, more preferably 18 mol / ton or less, and further preferably 15 mol / ton or less. When the carboxyl number exceeds 20 mol / ton, the biodiesel fuel resistance of the resin composition is greatly reduced.

  The polycarbonate resin (B) in the present invention is a resin composed of a bisphenol residue and a carbonate residue. Since the polycarbonate resin (B) has a bisphenol residue similar to the polyarylate resin (A), the polycarbonate resin (B) exhibits good compatibility with the polyarylate resin (A). The resulting resin composition becomes transparent. Furthermore, in the present invention, the polycarbonate resin (B) has an effect of improving the fluidity of the polyarylate resin (A), and further has the advantage that the impact resistance of the resulting resin composition can be improved.

  Examples of the polycarbonate raw material for introducing the bisphenol residue include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, and 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, 1,4-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 4,4′-dihydroxydiphenyl ether, 4,4 ′ -Dithiodiphenol, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4,4 - such as dihydroxy-2,5-dihydroxydiphenyl ether and the like. Other examples of bisphenols include U.S. Pat. No. 2,999,835, U.S. Pat. No. 3,028,365, U.S. Pat. No. 3,334,154, U.S. Pat. Diphenols described in 131,575 can be used. These may be used alone or in combination of two or more. Among these compounds, it is preferable to use 2,2-bis (4-hydroxyphenyl) propane from the viewpoint of cost performance, and it is preferable to use 2,2-bis (4-hydroxyphenyl) propane alone. Most preferred.

  Examples of the precursor for introducing the carbonate residue include phosgene and diphenyl carbonate.

  In the present invention, the inherent viscosity of the polycarbonate resin (B) is preferably 0.3 to 0.7 dl / g, and more preferably 0.35 to 0.65 dl / g. When the inherent viscosity of the polycarbonate resin (B) is less than 0.3 dl / g, the resulting resin composition may have poor mechanical properties, heat resistance, and biodiesel fuel resistance. On the other hand, when it exceeds 0.7 dl / g, since the melt viscosity of the polycarbonate resin (B) becomes high, discoloration or a decrease in fluidity may occur during melt processing.

  The blending ratio of the polyarylate resin (A) and the polycarbonate resin (B) is not particularly limited, but mechanical properties, heat resistance, biodiesel fuel resistance, fluidity, and processability of the resin composition of the present invention are improved. (A) / (B) = 90 / 10-50 / 50 (mass ratio) is preferable, 85 / 15-55 / 45 (mass ratio) is more preferable, and 80/20 More preferably, it is -60/40 (mass ratio). If the polyarylate resin (A) exceeds 90% by mass, fluidity and processability may be inferior. If the polyarylate resin (A) is less than 50% by mass, mechanical properties, heat resistance and biodiesel fuel resistance are inferior. The trend increases.

  The carbodiimide compound (C) in the present invention refers to a compound having a carbodiimide group represented by (—N═C═N—) in the molecule. A compound having one carbodiimide group in the molecule is referred to as a monocarbodiimide compound, and a compound having two or more carbodiimide groups in the molecule is referred to as a polycarbodiimide compound. These carbodiimide compounds may be used alone or in combination of two or more. It is also possible to use a mixture of monocarbodiimide and polycarbodiimide.

  Examples of the monocarbodiimide having one carbodiimide group in the same molecule include N, N′-di-2,6-diisopropylphenylcarbodiimide, N, N′-diphenylcarbodiimide, N, N′-di-2, 6-dimethylphenylcarbodiimide, N, N′-di-2,6-di-tert-butylphenylcarbodiimide, N-tolyl-N′-phenylcarbodiimide, N, N′-di-p-nitrophenylcarbodiimide, N, N′-di-p-aminophenylcarbodiimide, N, N′-di-p-hydroxyphenylcarbodiimide, p-phenylene-bis-di-o-tolylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, ethylene-bis- Diphenylcarbodiimide, N-octadecyl-N'-phenylcarb Bodiimide, N-benzyl-N'-phenylcarbodiimide, N-phenyl-N'-tolylcarbodiimide, N, N'-di-o-ethylphenylcarbodiimide, N, N'-di-p-ethylphenylcarbodiimide, N, N'-di-o-isopropylphenyl carbodiimide, N, N'-di-p-isopropylphenyl carbodiimide, N, N'-di-o-isobutylphenyl carbodiimide, N, N'-di-p-isobutylphenyl carbodiimide, N, N′-di-2,6-diethylphenylcarbodiimide, N, N′-di-2-ethyl-6-isopropylphenylcarbodiimide, N, N′-di-2-isobutyl-6-isopropylphenylcarbodiimide, N , N'-di-2,4,6-trimethylphenylcarbodiimide, N, N'- Aromatic monocarbodiimides such as -2,4,6-triisopropylphenylcarbodiimide, N, N'-di-2,4,6-triisobutylphenylcarbodiimide, di-β-naphthylcarbodiimide, N, N'-di- o-Tolylcarbodiimide, N, N'-dioctyldecylcarbodiimide, N-tolyl-N'-cyclohexylcarbodiimide, N, N'-di-cyclohexylcarbodiimide, N, N'-di-p-tolylcarbodiimide, hexamethylene-bis -Dicyclohexylcarbodiimide, N, N'-benzylcarbodiimide, N-octadecyl-N'-tolylcarbodiimide, N-cyclohexyl-N'-tolylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimi It can include diisobutyl carbodiimide, dioctyl carbodiimide, t- butyl isopropyl carbodiimide, an aliphatic / or alicyclic mono carbodiimides such as di -t- butyl carbodiimide. Among these, aromatic monocarbodiimide is preferably used from the viewpoint of biodiesel fuel resistance and transparency of the obtained molded body, and N, N′-di-2,6-diisopropylphenylcarbodiimide is more preferable.

  Various commercially available products can be used as the polycarbodiimide having two or more carbodiimide groups in the same molecule. For example, Rheinhemy's Stabuzol P, Rheinhemy's Stabuzol P-100, Rheinhemi's Examples thereof include aromatic polycarbodiimides such as Stavacsol P-400 and aliphatic / or alicyclic polycarbodiimides such as LA-1 manufactured by Nisshinbo. Among them, from the viewpoint of biodiesel fuel resistance and fluidity, aromatic polycarbodiimide is preferable, and among aromatic polycarbodiimides, those having a number average molecular weight of 300 to 8000 are preferable, and considering fluidity, 300 to 5000, More preferably, those having 300 to 2000 can be suitably used. The degree of polymerization is preferably 20 or less, more preferably 10 or less. Rheinhemy's Stavacsol P is known as an oligomer-type aromatic polycarbodiimide having a number average molecular weight of about 700, and can be particularly preferably used.

The number of carbodiimide groups in the polycarbodiimide molecule of the present invention is preferably 2 to 50, more preferably 3 to 40, and even more preferably 4 to 30. The number of carbodiimide groups is the number of carbodiimides in the polycarbodiimide molecule, and corresponds to the degree of polymerization if it is a polycarbodiimide obtained from a diisocyanate compound. For example, the polymerization degree of polycarbodiimide obtained by connecting 21 diisocyanate compounds in a chain form is 20, and the number of carbodiimide groups in the molecular chain is 20. Usually, polycarbodiimide is a mixture of molecules of various lengths, and the number of carbodiimide groups is represented by an average value. The number of carbodiimide groups can be measured by ¹³ C-NMR, IR, GPC, titration method or a combination thereof, and can be grasped as the number of carbodiimide groups. It is possible to observe a peak at 130 to 142 ppm in ¹³ C-NMR and 2130 to 2140 cm −1 in IR.

  The compounding quantity of a carbodiimide compound (C) needs to be 0.1-5 mass parts with respect to a total of 100 mass parts of polyarylate resin (A) and polycarbonate resin (B), and is 0.1-3.0. The amount is preferably mass parts, more preferably 0.2 to 2.5 parts by mass, and particularly preferably 0.3 to 2.0 parts by mass. When the blending amount of the carbodiimide compound (C) is less than 0.1 parts by mass, the resulting resin composition tends to have carboxylic acid terminals, acid anhydride bonds, hydroxyl groups, etc., and has sufficient biodiesel fuel. Can not be obtained. When the blending amount of the carbodiimide compound (C) exceeds 5 parts by mass, a solvent relaxation phenomenon due to biodiesel fuel of the resin composition to be obtained occurs, or thermal decomposition of the resin composition is induced, and biodiesel fuel resistance is rather lowered.

  The antioxidant (D) in the present invention is a phosphite compound, a phosphate compound, a hindered phenol compound, a benzotriazole compound, a triazine compound, a binderd amine compound, a thioether compound, a copper compound, or an alkali metal. A halide or the like can be used. Among them, phosphite compounds, hindered phenol compounds, and thioether compounds are preferable, and hindered phenol compounds are particularly preferable in terms of high effects of suppressing thermal decomposition during melt processing and enhancing biodiesel fuel resistance. preferable.

  As the phosphite compound that can be used as the antioxidant (D), various commercially available products can be used, for example, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphos. Phyto (ADEKA stab PEP-36, molecular weight 633), bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (ADEKA ADEKA STAB PEP-24G, molecular weight 604), Tris (2, 4 -Di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite (ADEKA ADEKA STAB PEP-8, molecular weight 733), bis (nonylphenyl) pentaerythritol diphosphite (ADEKA ADEKA STAB PEP-4C, Molecular weight 633 It can be mentioned.

  As the hindered phenol compound that can be used as the antioxidant (D), various commercially available products can be used, for example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-hydroxyphenyl) propionate. (IRGANOX 1010 manufactured by BASF), thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (IRGANOX 1035 manufactured by BASF), octadecyl-3- (3,5-di-) tert-Butyl-4-hydroxyphenyl) propionate (IRGANOX1076, manufactured by BASF, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] (IRGANOX made by BASF 098), benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester (IRGANOX 1135 manufactured by BASF), 2,4-dimethyl-6- (1- Methylpentadecyl) phenol (IRGANOX1141), diethyl [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] phosphonate (IRGANOX1222 manufactured by BASF), 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol (IRGANOX 1330 manufactured by BASF), calcium diethylbis [[[3,5-Bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phospho And a mixture of polyethylene wax (IRGANOX1425WL manufactured by BASF), 4,6-bis (octylthiomethyl) -o-cresol (IRGANOX1520L manufactured by BASF), ethylenebis (oxyethylene) bis [3- (tert-butyl -4-hydroxy-m-tolyl) propionate] (IRGANOX245 manufactured by BASF), 1,6-hexanediol-bis [3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF) IRGANOX259), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (IRGANOX3114 manufactured by BASF), 1,3,5-tris [(4-tert-butyl- 3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (IRGANOX3790, manufactured by BASF), reaction product of N-phenylbenzenamine and 2,4,4-trimethylpentene ( IRGANOX5057 manufactured by BASF), 6- (4-hydroxy-3-5-di-t-butylanilino) -2,4-bisoctylthio-1,3,5-triazine (IRGANOX565 manufactured by BASF), 1,3,5 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (ADEKA STAB AO-20 manufactured by ADEKA), 1,1,3-tris (2-methyl-4-hydroxy-5-tert- Butylphenyl) butane (ADEKA STAB AO-30 manufactured by ADEKA), 4,4′-butylidenebis (6-tert-butyl-3) Methylphenol) (ADEKA STAB AO-40 manufactured by ADEKA), 3- (4′-hydroxy-3 ′, 5′-di-tert-butylphenyl) propionic acid-n-octadecyl (ADEKA STAB AO-50 manufactured by ADEKA), Pentaerythritol tetrakis [3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] (ADEKA STAB AO-60 manufactured by ADEKA), triethylene glycol bis [3- (3-t-butyl -4-hydroxy-5-methylphenyl) propionate] (ADEKA STAB AO-70 manufactured by ADEKA), 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-) 5-methylphenylpropionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] -Undecane (Adeka Adeka Stub AO-80), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (Adeka Adeka Stub AO) -330), 2,2-oxamidobis- [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Naugard XL-1 manufactured by Crompton-Uniroyal Chemical), and the like. In particular, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-hydroxyphenyl) propionate] (IRGANOX1010) can be used. Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-hydroxyphenyl) propionate] is effective in suppressing the thermal decomposition during melt processing and enhancing the biodiesel fuel resistance. Most preferred. These may be used alone or in combination of two or more.

  Various commercially available products can be used as the thioether compound that can be used as the antioxidant (D). For example, pentaerythritol tetrakis (3-dodecylthiopropionate) (SEENOX 412S manufactured by Cypro Kasei Co., Ltd., Sumitomo Chemical Co., Ltd.) Sumilizer TP-D, Adeka AO-412S), didodecyl thiodipropionate (Cypro Kasei SEENOX DL, BASF IRGANOX PS 800 FL, Sumitomo Chemical Sumilizer TPL-R), ditridecylthiodipro Pionate (ADEKA AO-503), ditetradecyl thiodipropionate (Cipro Kasei SEENOX DM, Sumitomo Chemical Sumilizer TPM), dioctadecyl thiodipropionate (Cipro Kasei S ENOX DS, BASF Corp. IRGANOX PS 802 FL, manufactured by Sumitomo Chemical Co., Ltd. Sumilizer TPS), 2-mercaptobenzimidazole (manufactured by Sumitomo Chemical Co., Ltd. Sumilizer MB) can be exemplified. These may be used alone or in combination of two or more.

  The compounding quantity of antioxidant (D) needs to be 0.01-0.5 mass part with respect to a total of 100 mass parts of polyarylate resin (A) and polycarbonate resin (B), 0.01- The amount is preferably 0.4 parts by mass, more preferably 0.02 to 0.3 parts by mass, and particularly preferably 0.03 to 0.2 parts by mass. When the blending amount of the antioxidant (D) is less than 0.01 parts by mass, the resulting resin composition has insufficient antioxidant effect, resulting in insufficient residence stability and biodiesel fuel resistance. When the blending amount of the antioxidant (D) exceeds 0.5 parts by mass, the decomposition of the antioxidant (D) itself is promoted, the residence stability is inferior, coloring and yellowing become remarkable, and biodiesel fuel resistance Inferior to that. Moreover, even if it has biodiesel fuel resistance, coloring and yellowing may become remarkable, and the quality of the molded object which may be obtained may worsen.

  Biodiesel fuel, as described above, is a fuel composed of vegetable oils such as rapeseed oil, sunflower oil, soybean oil and corn oil, and fatty acid methyl esters obtained by separating and removing glycerin from methanol by converting the waste edible oil into crude oil. is there. The biodiesel fuel is used in a certain ratio in the fatty acid methyl ester alone or in light oil, and the name changes depending on the blending ratio, and B100 (biodiesel fuel 100%), B05 (biodiesel fuel 5%) ) Etc. It is within the range of B05-B20 that the spread degree is high also in this mixed fuel. Among them, biodiesel fuel derived from waste cooking oil has a lot of unsaturated hydrocarbons contained in impurities and fatty acid methyl esters, and thermal deterioration due to generation of radicals is remarkable. That is, the resin composition is likely to be oxidized and deteriorated. Moreover, since biodiesel fuel has high ester polarity and high affinity with water, biodiesel fuel is likely to contain a lot of water. This moisture content tends to promote hydrolysis of the resin composition. Furthermore, in a specific resin composition, solvent relaxation may be caused, and the tendency is more remarkable as the temperature is higher.

  On the other hand, the current diesel fuel, that is, light oil, is mainly composed of hydrocarbons, and unlike the biodiesel fuel, it contains less water. Diesel fuels have less unsaturated hydrocarbons than biodiesel fuels and are less prone to oxidative degradation of resin compositions, but certain resin compositions, like biodiesel fuels, may cause solvent relaxation. . In addition, since the main component is different from biodiesel fuel, the resin composition causing solvent relaxation also has a different tendency from biodiesel fuel.

The solvent relaxation phenomenon is the following phenomenon.
A general thermoplastic resin exists in a state where molecular chains are entangled, and this entanglement brings toughness to the resin. In order to destroy a resin in which molecular chains are entangled in this way, it is necessary to pull out the molecular chains from the entanglement of molecular chains, which requires a large amount of energy. However, when a solvent or chemical that is compatible with the resin comes into contact with the resin, the chemical enters the gap between the entanglement of the molecular chains, and the molecular chains move easily, so that the molecular chains can be easily pulled out, which is much lower than usual. Resin is destroyed by stress. Such a deterioration mechanism by chemicals is called a solvent relaxation phenomenon, and in such a system, even if the molecular weight is maintained, embrittlement is promoted.

  As described above, it was possible to take measures by paying attention to the resin composition that is in contact via the solvent as a main cause of deterioration of the resin composition, but in biodiesel fuel, in addition to the solvent relaxation phenomenon, oxidation deterioration, There is concern about hydrolysis, and the factor of concern will increase. Furthermore, in a resin composition that comes into contact with a mixed fuel of light oil and biodiesel fuel, it is necessary to prevent relaxation of the solvent for both fuels in addition to oxidative degradation and hydrolysis. Therefore, it can be said that the resin composition that has been resistant to light oil so far has a case where the mixed fuel is insufficient in resistance, and the performance required for the resin composition to be used is also increasing.

As a requirement for efficiently improving the biodiesel fuel resistance of the resin composition of the present invention,
(B) To suppress a decrease in molecular weight upon contact with biodiesel fuel, and (b) to suppress solvent relaxation. For (A), a polyarylate resin having a low carboxyl value is used, the above (η ₁ ) / (η ₀ ) is set within a predetermined range, and a predetermined amount of carbodiimide and antioxidant are used in combination. That is. For (b), it is possible to suppress the polyarylate resin by using a specific carbodiimide, and it is particularly effective to use polycarbodiimide.

  The fatty acid amide (E) in the present invention includes, for example, saturated fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide and behenic acid amide, oleic acid amide and erucic acid amide. And alkylene bis fatty acid amides such as methylene bis stearic acid amide and ethylene bis stearic acid amide. These higher fatty acid amides may be used alone or in combination of two or more. Among these fatty acid amides, stearic acid amide is particularly preferable.

  The compounding quantity of fatty acid amide (E) needs to be 0.01-0.5 mass part with respect to a total of 100 mass parts of polyarylate resin (A) and polycarbonate resin (B), 0.01-0 Is preferably 4 parts by mass, more preferably 0.02 to 0.3 parts by mass, and particularly preferably 0.03 to 0.2 parts by mass. When the blending amount of the fatty acid amide (E) is less than 0.01 parts by mass, the fluidity of the polyarylate resin (A) and the polycarbonate resin (B) becomes insufficient. When the compounding quantity of fatty acid amide (E) exceeds 0.5 mass part, not only biodiesel fuel resistance will fall, but the visibility of the resin composition obtained may fall. The fatty acid amide can improve the fluidity of the resin composition without inducing solvent relaxation, hydrolysis, and oxidative deterioration of the resin composition comprising the polyarylate resin (A) and the polycarbonate resin composition (B). In addition, there is an effect of improving the releasability.

  The polyarylate resin composition of the present invention may further contain a release agent (F). As a mold release agent which can be mix | blended with a polyarylate resin composition, aliphatic carboxylic acid, ester of aliphatic carboxylic acid and alcohol, an aliphatic hydrocarbon compound etc. can be mentioned, for example. Among these, an ester of an aliphatic carboxylic acid and an alcohol is preferable in that the solvent relaxation by the biodiesel fuel does not occur and the mechanical properties do not deteriorate.

  Examples of the ester of an aliphatic carboxylic acid and an alcohol that can be used as the release agent (F) include stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, and glycerin diester. Stearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, dipentaerythritol tetrastearate, dipentaerythritol tetramilli State, dipentaerythritol tetrapalmitate, dipentaerythritol tetraoleate and the like. Among them, there are dipentaerythritol partial esters in which four molecules of stearic acid are reacted with one molecule of dipentaerythritol, such as dipentaerythritol tetrastearate, dipentaerythritol tetramyristate, dipentaerythritol tetrapalmitate, dipentaerythritol tetraoleate. Dipentaerythritol tetrastearate is preferred, and particularly preferred.

  When using a mold release agent (F), it is preferable that the compounding quantity is 0.01-1.0 mass part with respect to 100 mass parts of polyarylate resin (A), and 0.03-0.8. It is more preferably part by mass, more preferably 0.05 to 0.6 part by mass, and particularly preferably 0.1 to 0.5 part by mass.

  It is preferable that the resin composition of the present invention is not accompanied by large discoloration and deterioration of mechanical properties even by various light rays in an outdoor environment such as ultraviolet rays. In general, a highly transparent material is often used for the fuel filter case to ensure visibility. When such a material is used over a long period of time in an outdoor environment, discoloration and deterioration of mechanical properties are remarkable, which causes a problem in the market. On the other hand, the polyarylate resin hardly deteriorates in mechanical properties, but fleece transitions due to ultraviolet irradiation and turns yellow or browns. The fleece transition phenomenon is a phenomenon in which the molecular structure of the polyarylate resin is chemically changed by ultraviolet rays, and ultraviolet rays having a wavelength of 380 nm or less are blocked with the structural change. This phenomenon occurs only on the resin surface layer. As a result, since ultraviolet rays are absorbed on the surface of the molded body in the thickness direction of the molded body, the deterioration of the mechanical properties due to the ultraviolet rays of the polyarylate resin molded body is suppressed, that is, the weather resistance is significantly improved.

  The resin composition of the present invention reduces yellowing due to the fleece transition unique to the polyarylate resin to a range that does not affect practical visibility, and has improved durability against biodiesel fuel. is there. That is, by using a predetermined amount of a carbodiimide compound and an antioxidant for the polyarylate resin, the resin composition becomes transparent and yellowish. The fact that the resin composition is yellowish from the beginning means that even if the fleece transition occurs afterwards in the outdoor environment, the color change due to yellowing is reduced to the extent that no significant color change appears. . In the present invention, the color tone change due to ultraviolet irradiation is, for example, based on JIS Z8722 after a 1000 hour irradiation test using a sunshine weather meter using a carbon arc as a light source, using a resin composition plate having a thickness of 3 mm, The color difference (ΔE * ab) before and after the irradiation test is preferably 10 or less, and more preferably 5 or less.

  Moreover, the resin composition of this invention can also reduce choking in addition to the reduction of the visibility change by an ultraviolet-ray. Choking is a state in which the surface of the resin composition is deteriorated mainly by the influence of ultraviolet rays and is covered with a powdery resin. Choking not only impairs the mechanical strength of a molded article made of a resin composition, but also greatly reduces visibility.

  As for the deflection temperature under load of the resin composition of the present invention, the value measured under a load of 5.0 MPa using a test piece having a thickness of 4 mm is preferably 120 ° C. or more, and preferably 130 ° C. or more. Is more preferable. For example, when a container part for automobile fuel is exposed to high temperature conditions, positive pressure or negative pressure is applied to the container part according to the flow of fuel. In such a condition where temperature and load are applied, it is particularly important that the deflection temperature under load is high.

  The resin composition of the present invention includes the polyarylate resin (A), polycarbonate resin (B), carbodiimide compound (C), antioxidant (D), fatty acid amide (within a range not impairing the effects of the present invention. In addition to E), an antioxidant, an ultraviolet absorber, a bluing agent, a pigment, a flame retardant, a release agent, an antistatic agent, a lubricant, an organic filler, an inorganic substance, and the like within the range not impairing the effects of the present invention A system filler or the like may also be included.

  Moreover, in the resin composition of this invention, resin other than prescribed | regulated by this invention may be added in the range which does not impair the effect of this invention. Examples of the resin include polyamide (nylon), polyester amide, polyurethane, polyether, polyolefin, polystyrene, AS resin, ABS resin, polyacrylic acid, polyacrylic ester, polymethacrylic acid, polymethacrylic ester, polyethylene terephthalate, polytrileate. Examples include methylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. These components may be used alone or in combination of two or more, may be simply mixed, or may be copolymerized.

  However, as described above, there are concerns that various alloys lose their transparency, there is a concern that restrictions may arise in applications that require transparency, and there is a concern that the need to refrain from blending amounts in order to maintain transparency. is there. In addition, as described above, even in the case of a compatible alloy that can maintain the transparency even if the blending amount is large, in the case of blending a large amount of the crystalline resin, there is a problem such as white turbidity due to crystallization of the resin composition, There is also a concern that application restrictions will occur. Furthermore, as described above, it is necessary to suppress the solvent relaxation phenomenon in order to impart chemical resistance. However, in the case where polymer alloy is excellent in compatibility, polymer molecules that are alloyed or copolymerized compared to a single polymer. The affinity between them is likely to be low, and there is a concern that the resistance to biodiesel fuel will decrease.

  In the present invention, the method of blending the polyarylate resin (A) with the polycarbonate resin (B), the carbodiimide compound (C), the antioxidant (D), and the fatty acid amide (E) is not particularly limited. Should be in a state of being uniformly dispersed. Specifically, for example, it may be uniformly dry blended using a tumbler or Henschel mixer, then melt-kneaded and extruded, and subjected to a cooling, cutting, and drying step, and pelletized. In melt kneading, a general kneader such as a single screw extruder, a twin screw extruder, a roll kneader, or a Brabender can be used, but from the viewpoint of improving dispersibility, a twin screw extruder should be used. Is preferred.

  The resin composition of the present invention can be molded into various molded products by any method. The molding method is not particularly limited, and an injection molding method, an extrusion molding method, a compression molding method, a blow molding method, or the like can be applied.

The resin composition of the present invention has high durability against biodiesel fuel, and can be used as an automobile part, in particular, as a molded body part in contact with biodiesel fuel. In particular, since it is excellent in fluidity and workability, it can be suitably used in a thin-walled molded body or a thick-walled molded body that easily causes sink marks. Moreover, it can use suitably also for the mixed fuel which mixes and uses biodiesel fuel and light oil, suppressing the oxidative degradation of a resin composition and a solvent relaxation. In addition to durability against biodiesel fuel, it does not change color tone with time even when used outdoors, and choking is also suppressed. For example, a filter that can visually check the fuel filtration state. It can be suitably used as a fuel filter container.
A sedimentator filter is a part attached to the engine system of a diesel vehicle or the like, and is a device that separates moisture and impurities mixed in the fuel. The removed moisture and impurities remain in the sedimentator filter. Will be.
Also, since it is not deteriorated by a cleaning agent mainly composed of alcohol used for maintenance and cleaning of automobile parts, so-called parts cleaner, for example, to the surface of the fuel filter container when the automobile is used for a long time. Even when dust and oil are washed away, the parts cleaner does not cause deterioration of the fuel filter container or deterioration of visibility.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to only these examples.

1. Evaluation method (1) Inherent viscosity (η ₀ )
The resin composition was dissolved in 1,1,2,2-tetrachloroethane to prepare a sample solution having a concentration of 1 g / dl. Subsequently, the drop time of the sample solution and the solvent was measured at a temperature of 25 ° C. using an Ubbelohde viscometer, and the inherent viscosity was determined using the following equation.
Inherent viscosity = ln [(sample solution drop time / solvent only drop time) / resin concentration (g / dl)]

(2) Inherent viscosity (η ₁ )
Inherent viscosity (η ₀ ) except that the solvent used was a mixed solvent in which 0.01 mol / L of sodium acetate was blended with respect to a phenol / 1,1,2,2-tetrachloroethane = 6/4 (mass ratio) solution. ), The inherent viscosity (η ₁ ) was measured.

_{(3) (η 1) /} (η 0) of calculating inherent viscosity (eta ₀₎ and inherent viscosity (eta ₁₎ than (η ₁₎ / was obtained (η _0). (Η ₁ ) / (η ₀ ) is an index indicating the degree of acid anhydride bond abundance in the polyarylate molecular chain. The smaller (η ₁ ) / (η ₀ ), the greater the amount of acid anhydride bonds, and the closer (η ₁ ) / (η ₀ ) is to 1, the less acid anhydride bonds are present. In the present invention, (η ₁ ) / (η ₀ ) is preferably 0.9 or more.

(4) Carboxyl value (mol / ton)
The resin composition was dissolved in methylene chloride, phenol red was added as a pH indicator, and titration was performed with a benzyl alcohol solution of 0.1 N potassium hydroxide to obtain a carboxyl value.

(5) Deflection temperature under load (℃)
Based on ISO 75-1, it measured with the load of 5.0 MPa using the test piece of thickness 4mm. However, the test piece shall not be subjected to pre-annealing for the purpose of removing residual strain or the like.

(6) Immersion test in biodiesel fuel (6-1) Preparation of immersion solution Biodiesel fuel B100 (manufactured by Revo International Co., Ltd., C-FUEL, derived from waste cooking oil) and JIS No. 2 diesel oil were mixed at a mass ratio of 3/7. . Further, this mixed fuel (hereinafter referred to as B30) and water were mixed at a volume ratio of 9/1 to obtain an immersion solution.
In the immersion solution, B30 and water are phase-separated. Since B30 has a smaller specific gravity than water, when the immersion solution is allowed to stand, water becomes B30 in the lower phase and B30 in the upper phase.

(6-2) Dipping method of test piece A dumbbell test piece having a thickness of 4 mm was obtained by injection molding using each resin composition. Next, a stainless steel container having a volume of 2 L was filled with the immersion solution adjusted in (7-1). Moreover, the raising bottom was given so that the dumbbell test piece might not touch water directly but to contact B30, and the wire mesh was installed on it. A dumbbell specimen was placed on a wire mesh and a stainless steel container was capped with a gap. The stainless steel container was allowed to stand at a temperature of 90 ° C. for 1000 hours in a hot air dryer (with explosion-proof function). After 1000 hours, the dumbbell test piece was taken out, and the inherent viscosity before and after the immersion test, tensile yield strength, tensile breaking elongation, and mass were compared.

(6-3) Inherent viscosity retention rate Using the resin slice cut out from the dumbbell piece, (1) Perform the same operation as the inherent viscosity, measure the inherent viscosity before and after the immersion test, and calculate the inherent viscosity retention rate according to the following formula: Calculated.
Inherent viscosity retention (%) = {(Inherent viscosity after immersion test) / (Inherent viscosity before immersion test)} × 100

(6-4) Tensile yield strength retention rate Based on ISO 527-1 and 2, the tensile yield strength before and after the immersion test was measured, and the tensile yield strength retention rate was calculated by the following formula.
The dumbbell test piece used was subjected to an annealing treatment for 3 hours under a temperature condition controlled at each (deflection temperature of load −10 ° C.) obtained in (5).
Tensile yield strength retention rate (%) = {(Tensile yield strength after immersion test) / (Tensile yield strength before immersion test)} × 100
The tensile yield strength retention is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. If it is less than 70% in this test, there is a concern that cracks due to insufficient strength will occur over time during actual use, and it is judged that there is no practicality.

(6-5) Tensile rupture elongation retention rate (6-4) The tensile rupture elongation was measured in the same manner as when the tensile yield strength retention rate was obtained, and the tensile yield strength retention rate was calculated by the following equation. .
Tensile elongation at break (%) = {(tensile elongation at break after immersion test) / (tensile elongation at break before fuel immersion test)} × 100
The tensile elongation at break retention is preferably 40% or more, and more preferably 50% or more. When it is less than 40% in this test, there is a concern that cracks due to insufficient toughness may occur over time during actual use, and it is determined that there is no practicality.

(6-6) Mass change rate Using an electronic balance, the mass of one dumbbell piece before and after the immersion test was measured, and the mass change rate was calculated according to the following equation.
Mass change rate (%) = [1-{(mass after immersion test) / (mass before immersion test)}] × 100
The mass change rate is preferably 1.0% or less, more preferably 0.7% or less, and more preferably 0.5% or less. In this test, when the mass change rate exceeds 1.0%, in actual use, there is a concern about leakage due to looseness of the fitting portion, cracking due to tightening, etc. due to dimensional change accompanying mass change, and it is judged that there is no practicality.

(6-7) Appearance change Dumbbell pieces were visually confirmed and evaluated according to the following criteria by comparison before and after the immersion test. Those with Δ and X were judged not to be practical. The visibility mentioned below means having transparency to the extent that the presence or absence of contents can be confirmed when used as a filter container, for example.
A: No change in transparency. It is completely transparent and has visibility.
○: No change in transparency. It has visibility.
Δ: Choking occurs or fine cracks occur on the surface of the test piece. Visibility is reduced.
X: The surface of the test piece is smooth, but the whole including the inside of the test piece is whitened and loses visibility.

(7) Flowability evaluation Using each resin composition, an injection molding machine (“S2000i-100B” manufactured by FANUC) has a mold temperature of 120 ° C., an injection pressure of 160 MPa, an injection time of 4 seconds, and a set injection speed of 100 mm / second. Under the fixed conditions, the cylinder temperature was appropriately changed, and the flow length of the test piece when molded was measured. The mold used was a bar flow test mold having a thickness of 2 mm, a width of 20 mm, and a length of 980 mm. In this test, the temperature at which the bar flow flow length exceeded 200 mm was defined as the flowable temperature.
However, the cylinder temperature was set to increase from 300 ° C. in increments of 10 ° C. When it was predicted that flow was impossible, the test was conducted assuming that a temperature of 300 ° C. or higher could be set as the test start temperature. In this test, when the bar flow flow length was less than 200 mm at 350 ° C., the flowability was insufficient, and the shape that could be molded was limited.

(8) Weather resistance test A plate-shaped test piece having a thickness of 3 mm was obtained by injection molding using each resin composition. A plate-shaped test piece was placed in a sunshine weather meter (Suga Test Instruments Co., Ltd., S80HB type, light source: carbon arc lamp), set to a black panel temperature of 63 ° C., a precipitation cycle of 18 min / 120 min, and processed for 1000 hours. Thereafter, visibility evaluation and color difference measurement were performed.

(8-1) Visibility evaluation The plate-like test piece was visually confirmed and evaluated according to the following criteria. Those with x were judged not to be practical. The visibility mentioned below means having transparency to the extent that the presence or absence of contents can be confirmed when used as a filter container, for example. Practically, ◎ and ○ are preferable.
A: No change in transparency. It is completely transparent and has visibility.
○: No change in transparency. It has visibility.
(Triangle | delta): Although choking generate | occur | produces in a part of test piece surface, it has visibility.
X: Choking occurs on the entire surface of the test piece or fine cracks occur.
As a result, visibility is totally lost.

(8-2) Color difference (ΔE * ab)
Based on JIS Z8722, △ E * ab is measured under transmission conditions using a spectrophotometric colorimeter (Nippon Denshoku Co., Ltd. SE-6000 type, light source: D-65, viewing angle: 2 °). did. In addition, only the thing which was evaluation of (double-circle) and (circle) in said (7-1) visibility evaluation was implemented. The color difference (ΔE * ab) is preferably 10 or less, and more preferably 5 or less.

(9) Alcohol resistance A plate-shaped test piece having a length of 127 mm, a width of 13 mm, and a thickness of 3.2 mm was obtained by injection molding using each resin composition. The obtained plate-shaped test piece was subjected to an annealing treatment for 3 hours under the temperature condition controlled at each (deflection temperature of load −10 ° C.) obtained in (5). The obtained plate-shaped test piece was attached to a three-point support type iron jig while applying strain to the center in the length direction so that the strain rate was 1.5%. Absorbent cotton impregnated with isopropanol (reagent) was left in contact with the strained part. In order to suppress the volatilization of isopropanol, the whole was covered and sealed with a polyethylene bag. After leaving at room temperature for 24 hours, the plate-shaped test piece was removed from the iron jig and the absorbent cotton was removed. Then, the distorted portion was observed and evaluated according to the following criteria.
○: No abnormality.
Δ: Cracks or crazes occur or break within 24 hours after standing at room temperature.
X: Dissolve or swell.

(10) Releasability Using each resin composition, a cup-shaped test piece having an outer diameter of 30 mmφ, an inner diameter of 28 mmφ, a depth of 20 mm, and a bottom wall thickness of 1 mm was obtained with an injection molding machine (S-2000i-100B type manufactured by FANUC). Obtained. For injection molding, a die having a pinpoint gate of 200 μmφ with a draft of 4/100 was used. The cylinder temperature was set to (7) the temperature obtained as a result of fluidity evaluation, and the mold temperature was set to (5) deflection temperature under load −20 ° C. The rate at which 200 non-defective products were obtained with injection pressure of 100 MPa, injection speed of 100 cc / sec, cooling time of 25 seconds and 1 cycle of 3 seconds (deformers of the ejector part were generated, and those that could not be removed) The product was judged as defective.

2. Raw material (1) Polyarylate resin (a-1): Bisphenol A / terephthalic acid / isophthalic acid = 50/25/25 (mol%), inherent viscosity (η ₀ ) 0.72 dl / g, Tg Polyarylate resin having a temperature of 197 ° C. (Η ₁ ) / (η ₀ ) is 1.00, and the carboxyl value is 10 mol / t.
(A-2): Polyarylate having bisphenol A / terephthalic acid / isophthalic acid = 50/25/25 (mol%), inherent viscosity (η ₀ ) of 0.54 dl / g, and Tg of 195 ° C. resin. (Η ₁ ) / (η ₀ ) is 1.00, and the carboxyl value is 10 mol / t.
(A-3): Polyarylate having bisphenol A / terephthalic acid / isophthalic acid = 50/25/25 (mol%), inherent viscosity (η ₀ ) of 0.65 dl / g, and Tg of 195 ° C. resin. (Η ₁ ) / (η ₀ ) was 0.85, and the carboxyl value was 10 mol / t.
(A-4): Polyarylate resin having bisphenol A / terephthalic acid / isophthalic acid = 50/25/25 (mol%), inherent viscosity (η0) of 0.55 dl / g, and Tg of 194 ° C. . (Η1) / (η0) is 0.99, carboxyl value 30 mol / t. (A-4) was obtained by treating (a-3) according to the procedure of Production Example 1 below.

(2) Polycarbonate resin (b-1): Polycarbonate resin composed of bisphenol and phosgene (“Caliver 200-3” manufactured by Sumitomo Dow), inherent viscosity 0.645 dl / g.
(B-2): Polycarbonate resin composed of bisphenol and phosgene (“Caliber 200-30” manufactured by Sumitomo Dow), inherent viscosity of 0.435 dl / g.

(3) Carbodiimide compound (c-1): Aromatic polycarbodiimide (oligomer type)
(Poly (1,3,5-triisopropylbenzene) carbodiimide) (Rhein Chemie's “Stavacsol P”, number average molecular weight of about 700)
(C-2): Aromatic polycarbodiimide (Poly (1,3,5-triisopropylbenzene) carbodiimide) (Rhein Chemie's “Stabaczol P-400”, number average molecular weight of about 6400)
(C-3): Aromatic monopolycarbodiimide N, N′-di-2,6-diisopropylphenylcarbodiimide (Rhein Chemie “Stabaczol I”)
(C-4): Alicyclic polycarbodiimide poly (4,4′-dicyclohexylmethanecarbodiimide) (“LA-1” manufactured by Nisshinbo Co., Ltd.)
(C-5): Aliphatic monocarbodiimide diisopropylcarbodiimide (reagent)
-(C-6): Alicyclic monocarbodiimide dicyclohexylcarbodiimide (reagent)

(4) Antioxidant / (d-1): Hindered phenol antioxidant pentaerythritol tetrakis [3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] (BASF Japan) "Irganox 1010")
(D-2): Phosphite antioxidant bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (“ADEKA STAB PEP-36” manufactured by ADEKA)
-(D-3): Thioether-based antioxidant pentaerythritol tetrakis (3-dodecylthiopropionate) ("SEENOX412S" manufactured by Cypro Kasei Co., Ltd.)

(5) Fatty acid amide (e-1): Saturated fatty acid amide Stearic acid amide ("LOXAMID S" manufactured by Emery Oleo Chemicals)
(E-2): alkylene bis fatty acid amide ethylene bis stearic acid amide ("LOXAMID EBS" manufactured by Emery Oleo Chemicals)
(E-3): unsaturated fatty acid amide erucic acid amide ("LOXAMID E" manufactured by Emery Oleo Chemicals)
(E-4): unsaturated fatty acid amide oleic acid amide ("LOXAMID VPN205" manufactured by Emery Oleo Chemicals)

(6) Mold release agent (f-1): Dipentaerythritol compound dipentaerythritol hexastearate (“VPG-2571” manufactured by Emery Oleochemicals)
(F-2): Glycerin compound Glycerin monostearate (“G129” manufactured by Emery Oleochemicals)

(7) Other resin components (g-1): Amorphous nylon resin (TR55 manufactured by EMS)
(G-2): polyetherimide resin (“ULTEM # 1010” manufactured by SABIC Innovative Plastics)
-(G-3): Polyester resin ("NEH-2070" manufactured by Unitika Ltd.)
-(G-4): Copolyester resin ("COPOLYESTER # 13319" manufactured by Eastman Chemical Company)
-(G-5): Copolyester resin ("DRYSTAR # 0601" manufactured by Eastman Chemical Company)

Production Example 1
The polyarylate resin of (a-3) was dissolved in a solvent in which 0.01 mol / L of sodium acetate was mixed with a phenol / 1,1,2,2-tetrachloroethane = 6/4 (mass ratio) mixed solvent. And allowed to stand for 3 hours. Thereafter, the polymer was reprecipitated in methanol, and the obtained polymer was washed by being immersed in methanol for 2 days.

Example 1
70 parts by mass of polyarylate resin (a-1), 30 parts by mass of polycarbonate resin (b-1), 1 part by mass of carbodiimide compound (c-5), 0.05 part by mass of antioxidant (d-1), fatty acid amide (E-1) After 0.2 parts by mass are uniformly mixed, a total charge of 3 kg is biaxial with a screw diameter of 26 mm using a loss-in-weight continuous quantitative supply device (CE-W-1 type manufactured by Kubota). It was supplied to the main supply port of an extruder (TEM 26SS type manufactured by Toshiba Machine Co., Ltd.) and melt kneaded. On the way, deaeration was performed at a vent pressure reduction of -0.099 MPa (gauge pressure), and the resin composition pellets were obtained after taking a strand from the die and cooling and solidifying in a hot tub and cutting with a pelletizer. Melt kneading was performed under the conditions of an extruder barrel temperature setting of 340 ° C., a discharge rate of 20 kg / h, and a screw rotation speed of 300 rpm. The obtained resin composition pellets were sufficiently dried by drying with hot air at 100 ° C. for 12 hours.
After using the obtained dry resin composition pellets and performing injection molding at a cylinder temperature of 350 ° C. and a mold temperature of 140 ° C. using an injection molding machine (EC-100 type manufactured by Toshiba Machine Co., Ltd.) to obtain various test pieces Various evaluations were performed. The results are shown in Table 1.

Examples 2-11
Various evaluations were performed after obtaining various test pieces in the same manner as in Example 1 except that the composition shown in Table 1 was followed. The results are shown in Table 1.

Examples 12-18
Various evaluations were performed after obtaining various test pieces in the same manner as in Example 1 except that the composition shown in Table 2 was followed. The results are shown in Table 2.

Examples 19-31
Various evaluations were performed after obtaining various test pieces in the same manner as in Example 1 except that the composition shown in Table 3 was followed. In addition, about Example 33, the mixing | blending of 0.2 mass part of mold release agents (f-1) was further performed at the time of the uniform mixing of a raw material. For Example 34, the release agent (f-2) was blended in the same manner as in Example 33. The results are shown in Table 3.

Comparative Examples 1-15
Various evaluations were performed after obtaining various test pieces in the same manner as in Example 1 except that the composition shown in Table 4 was followed. The results are shown in Table 4.

Comparative Example 16
Using amorphous polyamide resin (g-1), injection molding is performed using an injection molding machine (EC-100 type manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. to obtain various test pieces. After that, various evaluations were performed. The results are shown in Table 5.

Comparative Example 17
Using polyetherimide resin (g-2), injection molding was performed using an injection molding machine (EC-100 model manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 380 ° C. and a mold temperature of 140 ° C. to obtain various test pieces. Various evaluations were made afterwards. The results are shown in Table 5.

Comparative Examples 18-20
Instead of the polycarbonate resin, any one of the polyester resin (g-3), the copolyester resin (g-4), and the copolyester resin (g-5) is used, and the barrel temperature setting of the twin-screw extruder is 290 ° C., Various evaluations were performed after obtaining various test pieces in the same manner as in Example 1 except that the cylinder temperature of the injection molding machine was 300 ° C. and the mold temperature was 80 ° C. The results are shown in Table 5.

  Since Examples 1 to 30 were in accordance with the prescribed composition of the present application, it was possible to obtain a resin composition excellent in heat resistance, mechanical properties, fluidity, and moldability. It also had biodiesel fuel resistance, weather resistance, and alcohol resistance.

  Since Comparative Examples 1-6 did not mix any of the carbodiimide compound, antioxidant, and fatty acid amide, the biodiesel fuel resistance and weather resistance were inferior.

  Since the comparative example 7 did not mix | blend polycarbonate resin, its fluidity | liquidity was inferior.

  In Comparative Example 8, since the polyarylate resin was not blended, the biodiesel fuel resistance and weather resistance were inferior.

  Since the comparative example 9 did not mix | blend the carbodiimide compound, biodiesel fuel tolerance and a weather resistance were inferior.

  Since the compound of the carbodiimide compound was less than the lower limit value in Comparative Example 10, the biodiesel fuel resistance was inferior.

  In Comparative Example 11, the biodiesel fuel resistance was inferior because the compounding of the carbodiimide compound exceeded the upper limit.

  Since the comparative example 12 did not mix | blend antioxidant, biodiesel fuel tolerance was inferior.

  In Comparative Example 13, the blending of the antioxidant was less than the lower limit value, so the biodiesel fuel resistance was inferior.

  Comparative Example 14 was inferior in biodiesel fuel resistance because the blending of the antioxidant exceeded the upper limit.

Since the comparative example 15 did not mix | blend fatty acid amide, its fluidity | liquidity was inferior.

  Since the predetermined resin was not used in Comparative Example 16, biodiesel fuel resistance, weather resistance, and alcohol resistance were inferior.

  Since Comparative Example 17 did not use a predetermined resin, the biodiesel fuel resistance was poor.

Since Comparative Examples 18-20 used polyester resin or copolymer polyester resin instead of polycarbonate resin, biodiesel fuel resistance was inferior.

Claims (9)

  Carbodiimide compound (C) 0.1-5 parts by mass, antioxidant (D) 0.01-0.5 parts by mass, fatty acid with respect to 100 parts by mass in total of polyarylate resin (A) and polycarbonate resin (B) A resin composition for a biodiesel fuel container, comprising 0.01 to 0.5 parts by mass of amide (E).   The resin composition for a biodiesel fuel container according to claim 1, wherein a polyarylate resin (A) having a carboxyl value of 20 mol / ton or less is used. Inherent viscosity (η ₀ ) and inherent viscosity (η ₁ ) measured under the following conditions (i) and (ii) satisfy the relationship of (η ₁ ) / (η ₀ ) = 0.9 to 1.1 Resin (A) is used, The resin composition for biodiesel fuel containers according to claim 1 or 2.
(I) Inherent viscosity (η ₁ ) measured with a mixed solvent of phenol / tetrachloroethane = 6/4 (mass ratio) containing 0.01 mol / L of sodium acetate
(Ii) Inherent viscosity (η ₀ ) measured with tetrachloroethane solution in the absence of sodium acetate   The resin composition for a biodiesel fuel container according to any one of claims 1 to 3, wherein the carbodiimide compound (C) is poly (1,3,5-triisopropylbenzene) carbodiimide.   The resin composition for a biodiesel fuel container according to any one of claims 1 to 4, wherein the antioxidant (D) is a hindered phenol-based antioxidant.   Furthermore, the resin composition for biodiesel fuel containers in any one of Claims 1-5 formed by containing a mold release agent (F).   The resin composition for a biodiesel fuel container according to any one of claims 1 to 6, wherein the release agent (F) is a pentaerythritol compound.   The molded object formed by shape | molding the resin composition for biodiesel fuel containers in any one of Claims 1-7. The molded article according to claim 8, which is used as a filter container for biodiesel fuel.