JP2015021068A - Polyarylate resin composition, and blow-molded article obtained from the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylate resin composition which hardly occurs drawdown during direct blow molding while keeping heat resistance, transparency, mechanical properties that the polyarylate resin originally has, and an excellent blow-molded article which is suitable for not only a small-sized container but also a large-sized container packaging material having a height of higher than 300 mm, because of having excellent blow moldability.SOLUTION: A polyarylate resin composition contains 0.5-3 pts.mass of a glycidoxy group-containing silane compound (B) with respect to 100 pts.mass of a polyarylate resin (A).

Description

  The present invention relates to a polyarylate resin composition that is difficult to draw down and is suitable for direct blow molding.

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. In addition, because of its excellent UV barrier properties, it also has the effect of protecting the contents from UV deterioration, so as a packaging container, for example, a container body of a medicine or a beverage, or a hollow container such as an on-vehicle fragrance container (Patent Documents 1 and 2).
As a method for producing a hollow molded body, an injection molding method in which a molten resin is directly injected into a mold to directly form a molded body, or a molten parison is injected into a mold to form a bottomed parison (preform) once. An injection blow molding method in which it is inserted into a blow mold and air is blown later. A parison is formed by extruding molten resin into a cylindrical shape, and this is sandwiched between molds to blow air into the interior (extrusion blow). Molding) is employed.
The injection molding method and the injection blow molding method require high technology for producing and molding a mold, and it is difficult to manufacture a container having a complicated shape having fine, deep, large, and handles. Has the disadvantages. In addition, these molding methods are suitable for mass-produced containers due to high equipment costs such as molds and molding equipment, but have a problem that they are not suitable for multi-product / small-volume production. In contrast, direct blow molding (extrusion blow molding) has features such as ease of molding, high productivity, and relatively low equipment costs such as molding machines and molds. For the molding, an extrusion blow molding method (direct blow molding method) is employed.
In the case of the direct blow molding method, it is necessary to avoid the drawdown phenomenon in which the parison extruded in the molten state hangs down by its own weight in order to perform the molding smoothly. For this reason, a high melt viscosity is required for the resin used. Therefore, it is generally considered that a vinyl chloride resin or polyolefin having a high melt viscosity is suitable for this direct blow molding. In particular, when a large container is molded, the problem of drawdown is remarkable, and it is difficult to mold with high accuracy.

Japanese Patent Laid-Open No. 11-43132 JP-A-11-70627

The present inventor has found that there are the following problems when a container made of polyarylate resin is obtained using the direct blow molding method.
Normally, polyarylate resin is known as a resin having a high melt viscosity, but in the case of a small container, it could be molded relatively well. On the other hand, in the case of a large container, even if a polyarylate resin having a high melt viscosity is used, drawdown occurs and it is difficult to obtain a molded product having a uniform thickness.
This is because the weight of the container increases as the size of the container increases, and deformation due to its own weight during blow molding tends to occur.
In addition, containers made of alloy materials of polyarylate resin and polyethylene terephthalate (PET) resin, and multilayer containers using polyarylate resin as one of the constituent layers have improved the blowability of polyarylate resin and improved processability. However, the original heat resistance, transparency and mechanical properties of the polyarylate resin were impaired.
The present invention provides a polyarylate resin composition that is difficult to draw down during direct blow molding while maintaining the heat resistance, transparency, and mechanical properties inherent to the polyarylate resin, and also provides an excellent blow molded article. For the purpose.

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) A polyarylate resin composition containing 0.5 to 3 parts by mass of a glycidoxy group-containing silane compound (B) with respect to 100 parts by mass of the polyarylate resin (A).
(2) The polyarylate resin composition according to (1), wherein the glycidoxy group-containing silane compound (B) is represented by the following structural formula (I):
(Wherein R ¹ and R ² are each independently hydrogen or an alkyl group, k is an integer of 0 or more, and n is an integer of 1 to 3)
(3) The polyarylate resin composition of (1) to (2), wherein R ¹ and R ^{2 in the} structural formula (I) are a methyl group or an ethyl group.
(4) The polyarylate resin composition according to any one of (1) to (3), wherein k is 3 in the structural formula (I).
(5) The polyarylate resin composition of (1) to (4), wherein the polyarylate resin (A) has a carboxyl value of 15 mol / ton or more.
(6) The inherent viscosity (η ₁ ) and the inherent viscosity (η ₀ ) measured under the following conditions (i) and (ii) are (η ₁ ) / (η ₀ ) = 0.95 or less. The polyarylate resin composition according to any one of (1) to (5).
(I) Inherent viscosity (η ₁ ) measured using a mixed solution having a mass ratio of phenol / 1,1,2,2-tetrachloroethane / sodium acetate = 6/4 / 0.006 as a solvent.
(Ii) Inherent viscosity (η ₀ ) measured using 1,1,2,2-tetrachloroethane as a solvent
(7) A blow molded article obtained from the polyarylate resin composition of (1) to (6).

  ADVANTAGE OF THE INVENTION According to this invention, the polyarylate resin composition which has the heat resistance of the conventional polyarylate resin, transparency, and the drawdown property improved is obtained. When this resin composition is directly blow-molded, a hollow molded body having less uneven thickness and having the original characteristics of polyarylate resin can be obtained.

  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 method such as melt polymerization, solution 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′-biphenyldicarboxylic acid, 2,2′-biphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, Aromatic dicarboxylic acids such as 4,4′-diphenylsulfone dicarboxylic acid, 4,4′-diphenylisopropylidenedicarboxylic acid, 1,2-bis (4-carboxyphenoxy) ethane, 5-sodium sulfoisophthalic acid and the like can be mentioned. 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 (mol%), preferably 75/25 to 25/75 (mol%), more preferably 65/35 to 35/65 (mol%). More preferably.

Examples of the polyarylate raw material for introducing a bisphenol residue include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 2,2-bis (4-hydroxy-3,5- Dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4 , 4′-dihydroxydiphenyl ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 4-methyl-2,2-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 4,4 '-Dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 2-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine, 4 , 4 '-(3,3,5-trimethylcyclohexylidenediphenol, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene Is mentioned.
Among the bisphenols, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferable from the viewpoints of the polymerizability of the polyarylate resin, the economical efficiency of the resulting polyarylate resin, and the improvement of mechanical properties. 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.

  The carboxyl value of the polyarylate resin (A) is preferably 15 mol / ton or more, more preferably 20 mol / ton or more, and further preferably 30 mol / ton or more. The carboxyl value in the polyarylate resin (A) represents the content ratio of the carboxylic acid terminal in the polyarylate resin, but the polyarylate resin composition of the present invention is drawn down by reacting with the glycidoxy group. It becomes possible to improve. When the carboxyl value is less than 15 mol / ton, the draw-down resistance of the resulting polyarylate resin composition cannot be sufficiently improved.

  Examples of the method of introducing a carboxylic acid terminal into the polyarylate resin (A) include a method of stopping the polymerization reaction before the reaction is completed, a method of hydrolyzing an ester bond with an alkali or the like.

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 ) = 0.95 or less, more preferably 0.90 or less. When (η ₁ ) / (η ₀ ) exceeds 0.95, the molecular weight tends to decrease when contacting with the polyarylate resin, particularly the tensile elongation tends to decrease, and the amount of carbodiimide compound necessary for blending tends to increase. It is not preferable.

In the measurement of the inherent viscosity, the inherent viscosity in the condition (i) is a mixed solution having a mass ratio of phenol / 1,1,2,2-tetrachloroethane / sodium acetate = 6/4 / 0.006. Is the inherent viscosity (η ₁ ) measured at a temperature of 25 ° C., and the inherent viscosity in the condition (ii) is measured at a temperature of 25 ° C. using 1,1,2,2-tetrachloroethane as a solvent. Is the inherent viscosity (η ₀ ). 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 increasing acid anhydride bonds contained in the polyarylate molecular main chain. In order to increase the acid anhydride bond, it is effective to make the dicarboxylic acid component slightly larger than the bisphenol component and reduce the polymerization reaction rate of the polyarylate during the interfacial polymerization. As a specific operation for reducing the polymerization reaction rate, the polymerization reaction rate can be adjusted by selecting the type of polymerization catalyst to be used, the blending amount, the stirring speed during the 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 molecular weight of the resulting polyarylate resin composition becomes low, so the mechanical properties, heat resistance, and chemical resistance may be inferior, and the inherent viscosity (η ₀ ) is low. If it exceeds 1.0, the melt viscosity becomes too high, and discoloration during melt processing or decrease in fluidity may occur. 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 glycidoxy group-containing silane compound (B) in the present invention is preferably a compound represented by the following general formula (I). The silane compound used in the present invention must have a glycidoxy group, and the polyarylate resin and the silane compound can be obtained by reacting the carboxylic acid at the terminal of the polyarylate resin or an acid anhydride bond present in the molecular chain with the glycidoxy group. Can be combined. Further, it is necessary to have at least one alkoxy group or hydroxyl group. Since an alkoxy group or a hydroxyl group is condensed and bonded to an alkoxy group or a hydroxyl group of another silane molecule, by reacting with the glycidoxy group, polyarylate molecules can be bonded to each other to extend the molecular chain length. Furthermore, when n in the formula is 2 or more, it is preferable that 3 or more molecules of polyarylate are bonded to form a branched structure, so that the spinnability in the melted state is improved and it is difficult to draw down during direct blow molding. . Specific examples of the following general formula (I) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylethyldi And ethoxysilane. Among these, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane are particularly preferable because they can make the resulting polyarylate resin composition difficult to draw down.

(Wherein R ¹ and R ² are each independently hydrogen or an alkyl group, k is an integer of 0 or more, and n is an integer of 1 to 3)

  The compounding quantity of a glycidoxy group containing silane compound (B) needs to be 0.5-3 mass parts with respect to 100 mass parts of polyarylate resin (A), and should be 0.7-2.5 mass parts. Is preferable, and it is more preferable that it is 1-2 mass parts. When the blending amount of the glycidoxy group-containing silane compound (B) is less than 0.5 parts by mass, the resulting polyarylate resin composition has a poor effect of improving the drawdown property, and when it exceeds 3 parts by mass, the glycidoxy group is contained. Since the silane compounds (B) are bonded to each other and a large amount of gel is generated, the appearance of the resulting blow molded article is impaired.

  The polyarylate resin composition of the present invention can contain various additives within a range not impairing the effects of the present invention. Examples of additives that can be used include antioxidants, ultraviolet absorbers, bluing agents, pigments, flame retardants, mold release agents, antistatic agents, lubricants, organic fillers, and inorganic fillers. .

  In the polyarylate resin composition of the present invention, a resin other than that defined in the present invention may be added within a range not impairing the effects of the present invention. Examples of such resins include polyamide (nylon), polyester amide, polyurethane, polyether, polyolefin, polystyrene, AS resin, ABS resin, polyacrylic acid, polyacrylic acid ester, polymethacrylic acid, polymethacrylic acid ester, Examples include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyetherimide, polysulfone, and polyethersulfone. These resin components may be used singly or in combination of two or more, may be simply mixed, or may be copolymerized.

  In the present invention, the method of blending the polyarylate resin (A) and the glycidoxy group-containing silane compound (B) is not particularly limited as long as each component can be uniformly dispersed. As a specific method, for example, after uniformly blending using a tumbler or a Henschel mixer, melt-kneading extrusion may be performed, followed by cooling, cutting, and drying steps to form pellets. 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 polyarylate 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, and the like can be applied. As the injection molding method, a general injection molding method can be used, and further, a gas injection molding method, an injection molding press molding method, or the like can be employed. Examples of the extrusion molding method include a T-die method and a round die method. Examples of the compression molding method include stamping molding and high pressure press molding. Examples of the blow molding method include a direct blow method in which molding is performed directly from raw material chips, an injection blow molding method in which blow molding is performed after a preformed body (bottom parison) is first molded by injection molding, and a stretch blow molding method. Etc. In addition, any of a hot parison method in which blow molding is continuously performed after forming the preform, and a cold parison method in which the preform is cooled and taken out and then heated again to perform blow molding can be employed. In particular, when a hollow container is molded by the direct blow molding method, it is possible to obtain a molded body having a constant thickness that is difficult for the extruded molten resin to be drawn down.

  The thickness of the blow molded article of the present invention is not particularly limited, but is usually 0.1 to 7 mm, preferably 0.2 to 5 mm, more preferably 0.3 to 3 mm from the viewpoint of strength and shape retention of the hollow container. It is.

The polyarylate resin composition of the present invention can be blow-molded in a wide range from a small container to a large container, but can be well blow-molded even in a large container having a height exceeding 300 mm. For example, when blow molding is performed on a large container having a height of 300 mm and an average wall thickness of 2 mm under conditions of a blow air pressure of 8 kgf / cm ² from a parison, it depends on the size and thickness of the target blow molded body. The time until the bottom of the molded body comes into contact with the mold bottom is preferably 8 seconds or longer, more preferably 10 seconds or longer, and further preferably 12 seconds or longer. When the time until the bottom of the blow molded body contacts the mold bottom is less than 8 seconds, it is easy to draw down, and even if a blow molded body is obtained, the wall thickness is different from the predetermined thickness, There may be many thick spots, or it may be deformed by its own weight.

  Furthermore, various surface treatments can be performed on the molded body made of the polyarylate resin composition of the present invention. The surface treatment here is to form vapor deposition, plating, painting, coating, printing, etc. as a new layer on the surface layer of the molded body, and a method used for ordinary resins can be applied. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing.

Since the polyarylate resin composition of the present invention is excellent in heat resistance, transparency and mechanical properties, various parts materials, foods, toiletries, cosmetics, pharmaceuticals, agricultural chemicals in the automotive field, electrical / electronic field It can be suitably used as a container for industrial oils and fats and industrial chemicals.
As automobile parts, for example, lamp sockets, lamp reflectors, lamp housings, instrument panels, center console panels, deflector parts, car navigation parts, car audio visual parts, auto mobile computer parts, etc. can be used.
Electrical / electronic components include, for example, personal computers, notebook computers, printers, copiers, scanners, fax machines and other office automation equipment, game machines, display devices, personal digital assistants, mobile phones, mobile books, mobile TVs, recording media drives It can be used in a recording medium reader, an optical camera, a digital camera, and the like.
Various containers include, for example, food bottles such as dairy bottles, soft drink bottles, water bottles, containers for toiletries such as fragrances, toothpastes and detergents, cosmetic containers such as various powders, creams and sprays, Since it can be used in pharmaceutical containers such as eye drops and eye drops and is excellent in blow moldability, it is suitable not only for the small containers but also for large container packaging materials having a height exceeding 300 mm.

  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 polyarylate resin composition was dissolved in 1,1,2,2-tetrachloroethane to prepare a sample solution having a concentration of 1 g / dl. Subsequently, the flow time T of the sample solution and the drop time T _{0 of the} solvent were measured at a temperature of 25 ° C. using an Ubbelohde viscometer, and the inherent viscosity (η ₀ ) was determined using the following equation.
Inherent viscosity (η ₀ ) = Ln (η _rel ) / c
However, η _rel is a relative viscosity and is calculated by the following equation. C = 1 g / dl.
η _rel = T / T ₀

(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. _{(Η 1) / (η 0} ) as the decreases, it indicated that often abundance of anhydride bonds, _{(η 1) / (η 0} ) is larger, anhydride bonds is reduced. In the present invention, (η ₁ ) / (η ₀ ) is preferably 0.95 or less.

(4) Carboxyl value (mol / ton)
After the polyarylate 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) Drawdown (seconds)
Using a twin screw extruder (PCM30 manufactured by Ikegai Co., Ltd.) with a screw diameter of 30 mm equipped with a T die (width 50 mm, lip spacing 0.5 mm), polyarylate resin composition under conditions of barrel temperature 360 ° C. and discharge rate 3 kg / h The product was extruded into a sheet. Then, after cutting once at the die base, the arrival time until the sheet length reached 300 mm was measured. In the case of a material that is easy to draw down, the arrival time is shortened because the sheet hangs down by its own weight.

(6) Sheet appearance A sheet piece was cut out from the sheet prepared in (5) so that the width was 50 x the sheet length was 100 mm. About the said sheet piece, the presence or absence of the gel-like thing was confirmed. In the sheet piece, when the number of gel-like substances was 5 or less, it was judged as “low”, when it exceeded 5, “high”, and when it was 0, “none”.

(7) Blow moldability Using a blow molding machine ("IPB-10" manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.), the parison is extruded at a cylinder temperature of 365 ° C, a discharge rate of 15 kg / h, a die outer diameter of 80 mm, and a wall thickness of 2 mm, Evaluation was performed according to the following criteria using a test piece blow-molded at 130 ° C. and a blow air pressure of 8 kgf / cm ² .
A: Blow molding is possible, the wall thickness is uniform, and no drawdown occurs. Moreover, there is no generation of a gel-like material on the surface of the molded body, and the appearance is good.
◯: Can be blow molded and does not draw down. However, a gel-like material is generated on the surface of the molded body, and the appearance is inferior.
Δ: Blow molding is possible, but drawdown is performed.
X: Blow moldability is inferior.

2. Raw material (1) Polyarylate resin (a-1): bisphenol component is bisphenol A, dicarboxylic acid component is terephthalic acid / isophthalic acid = 5/5 (molar ratio), and inherent viscosities η ₀ and η ₁ are 0.68 dl / G, 0.53 dl / g (η ₁ / η ₀ is 0.78), and a polyarylate resin having a carboxyl number of 38 mol / t.
(A-2): The bisphenol component is bisphenol A, the dicarboxylic acid component is terephthalic acid / isophthalic acid = 5/5 (molar ratio), and the inherent viscosities η ₀ and η ₁ are 0.78 dl / g, 0.68 dl / A polyarylate resin having g (η ₁ / η ₀ of 0.87) and a carboxyl number of 35 mol / t.
(A-3): The bisphenol component is bisphenol A, the dicarboxylic acid component is terephthalic acid / isophthalic acid = 5/5 (molar ratio), and the inherent viscosities η ₀ and η ₁ are 0.54 dl / g, 0.48 dl / A polyarylate resin having g (η ₁ / η ₀ of 0.89) and a carboxyl number of 30 mol / t.
(A-4): The bisphenol component is bisphenol A, the dicarboxylic acid component is terephthalic acid / isophthalic acid = 5/5 (molar ratio), the inherent viscosities η ₀ and η ₁ are 0.72 dl / g, 0.69 dl / A polyarylate resin having g (η ₁ / η ₀ is 0.69) and a carboxyl number of 16 mol / t.
(A-5): The bisphenol component is bisphenol A, the dicarboxylic acid component is terephthalic acid / isophthalic acid = 5/5 (molar ratio), and the inherent viscosities η ₀ and η ₁ are 0.72 dl / g, 0.72 dl / A polyarylate resin having g (η ₁ / η ₀ is 1.00) and a carboxyl number of 8 mol / t.

(2) Silane compound (b-1): Glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Silicone)
(B-2): Glycidoxypropyltriethoxysilane (KBE-403 manufactured by Shin-Etsu Silicone)
(B-3): Glycidoxypropylmethyldiethoxysilane (KBE-402 manufactured by Shin-Etsu Silicone)
(B-4): Methyltriethoxysilane (Shin-Etsu Silicone KBE-13)

(3) Epoxy compound (c-1): bisphenol A type epoxy resin (jER828 manufactured by Japan Epoxy Resin Co., Ltd.)

Example 1
After 100 parts by mass of the polyarylate resin (a-1) and 1 part by mass of the glycidoxy group-containing silane compound (b-1) were uniformly mixed, a total charge amount of 3 kg was added to a loss-in-weight continuous quantitative supply device (CE-BOTA manufactured by Kubota Corporation). W-1 type) was supplied to the main supply port of a twin screw extruder having a screw diameter of 26 mm (TEM26SS type manufactured by Toshiba Machine Co., Ltd.), and melt kneading was performed. On the way, deaeration was performed at a vent pressure reduction of -0.099 MPa (gauge pressure), the strand was taken out from the die into a strand shape, cooled and solidified in a water tank, and cut with a pelletizer to obtain a polyarylate resin composition pellet. The melt kneading was performed under the conditions of an extruder barrel temperature setting of 330 ° C., a discharge rate of 20 kg / h, and a screw rotation speed of 300 rpm.
The obtained polyarylate resin composition pellets were sufficiently dried by hot air drying at 120 ° C. for 12 hours, and then evaluated for drawdown property and sheet appearance. The results are shown in Table 1.

Examples 2-8
A polyarylate resin composition pellet was produced in the same manner as in Example 1 except that the formulation was as shown in Table 1, and various evaluations were performed. The results are shown in Table 1.

Comparative Examples 1-4
A polyarylate resin composition pellet was prepared in the same manner as in Example 1 except that the formulation was as described in Table 2, and various evaluations were performed. The results are shown in Table 2.

  In the polyarylate resin compositions of Examples 1 to 8, the polyarylate resin and the glycidoxy group-containing silane compound were used, and each blending ratio was set to a specific range, so that it was difficult to draw down and the gel-like product was small. It was.

  In Comparative Example 1, since a glycidoxy group-containing silane compound was not blended, it was easy to draw down.

In Comparative Example 2, since the polyarylate resin used had a small carboxyl number and η ₁ / η ₀ exceeded 0.9, it was easy to draw down.

  In Comparative Example 3, since the blending amount of the glycidoxy group-containing silane compound was too large, the drawdown property was good, but there were many gels and the appearance was not good.

  In Comparative Example 4, since a silane compound having no glycidoxy group was used, it was easy to draw down and a lot of gel-like substances were obtained.

In Comparative Example 5, a compound having a glycidoxy group different from the silane compound was used, but it was easy to draw down and had many gels.

Claims (7)

  The polyarylate resin composition which contains 0.5-3 mass parts of glycidoxy group containing silane compounds (B) with respect to 100 mass parts of polyarylate resin (A). The polyarylate resin composition according to claim 1, wherein the glycidoxy group-containing silane compound (B) is represented by the following structural formula (I).
(Wherein R ¹ and R ² are each independently hydrogen or an alkyl group, k is an integer of 0 or more, and n is an integer of 1 to 3) The polyarylate resin composition according to claim 1 or 2, wherein R ¹ and R ² in the structural formula (I) are a methyl group or an ethyl group.   The polyarylate resin composition according to claim 1, wherein k is 3 in the structural formula (I).   The polyarylate resin composition according to any one of claims 1 to 4, wherein the carboxyl value of the polyarylate resin (A) is 15 mol / ton or more. The inherent viscosity (η ₁ ) and the inherent viscosity (η ₀ ) measured under the following conditions (i) and (ii) are (η ₁ ) / (η ₀ ) = 0.95 or less. ~ 5 polyarylate resin composition.
(I) Inherent viscosity (η ₁ ) measured using a mixed solution having a mass ratio of phenol / 1,1,2,2-tetrachloroethane / sodium acetate = 6/4 / 0.006 as a solvent.
(Ii) Inherent viscosity (η ₀ ) measured using 1,1,2,2-tetrachloroethane as a solvent A blow molded article obtained from the polyarylate resin composition according to claim 1.