JP5302014B2 - Resin composition for forming a deposited film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition improving flowability without impairing heat resistance of a conventional resin composition including polyarylate resin and polycarbonate resin, and causing little change in appearance when exposed to a high temperature. <P>SOLUTION: A resin composition includes (A) polyarylate, (B) polycarbonate, and (C) polystyrene, and satisfies formulas (I) and (II): (A)/(B)=50/50 to 95/5 (I); (C)/ä(A)+(B)+(C)}=0.5/100 to 20/100 (II). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a resin composition having a polyarylate resin as a main component and excellent in heat resistance and fluidity.

  Polyaryrex resin consisting of dihydric phenols such as bisphenol compounds and terephthalic acid and isophthalic acid is an amorphous polymer and is already well known as an engineering plastic with excellent transparency, mechanical properties and heat resistance. ing. Such polyarylate resins are used in various fields because of their characteristics. From the viewpoint of improving molding processability and impact resistance, it is known that a resin composition in which polycarbonate is mixed with polyarylate is useful. (Patent Document 1, Patent Document 2).

  In general, improvement of polymer fluidity includes a method of dispersing a low molecular compound as a plasticizer (Patent Document 3) and a method of adding a polyester having a flexible structure such as an alkylene group (Patent Document 4). In either case, the heat resistance is reduced. In addition, a method of lowering the molecular weight of the polymer is conceivable. However, although the fluidity is improved by a decrease in melt viscosity, the physical properties represented by impact resistance are often lowered, which is not preferable.

  A technique has been found for improving the molding processability of polyarylate resin by adding a different polymer other than the polyester. For example, in Patent Document 5, it has been found that blending a polystyrene resin with a polyarylate resin improves molding processability without significant deterioration in physical properties.

  In recent years, automobiles and electrical products have been reduced in weight and size, and component parts have also been reduced in size, particularly in thickness. Therefore, when manufacturing parts by injection molding, improvement of the fluidity of the resin material is strongly demanded. Therefore, it is also considered to use polyarylate resin with improved fluidity by the above-mentioned method, but in the case of parts exposed to high temperature during use, in addition to insufficient heat resistance of the resin material, heat deformation temperature However, there are cases where the appearance of the molded article deteriorates due to changes in the surface condition of the molded article when the high temperature condition continues, and the request may not be met. For example, in a reflector of a lamp manufactured by vapor-depositing a metal such as aluminum on a resin molded product, there may be a problem that the vapor deposition surface of the reflector changes due to the heat of the lamp and the mirror surface is disturbed. .

Japanese Patent Publication No. 50-27061 JP 58-83050 A JP-A-49-90343 JP-A-50-34342 JP 48-51049

  The problem to be solved by the present invention is that the heat resistance of a conventional resin composition comprising a polyarylate resin and a polycarbonate resin is not impaired, the flowability is improved, and the appearance changes when exposed to high temperatures, particularly It is an object of the present invention to provide a resin composition which is produced by metal deposition on a molded article and hardly deteriorates in a mirror surface state.

  As a result of intensive studies to solve such problems, the present inventor has further improved flowability and stable appearance by blending a specific polystyrene resin with a mixture of polyarylate resin and polycarbonate resin. The present invention has been found out.

  That is, the gist of the present invention is as follows.

It consists of (A) polyarylate having an inherent viscosity of 0.40 to 0.60 dl / g , (B) polycarbonate, and (C) polystyrene, and the mass ratio of each component is represented by the following formulas (I) and (II). A resin composition for forming a deposited film, which is a satisfactory resin composition, wherein the (C) polystyrene is syndiotactic polystyrene having a melting point of 200 ° C or higher .
(A) / (B) = 50/50 to 95/5 (I)
(C) / {(A) + (B) + (C)} = 0.5 / 100 to 20/100 (II)

  The resin composition of the present invention can improve the fluidity without impairing the excellent physical properties of a composition comprising a polyarylate resin and a polycarbonate resin, and further change in appearance or vapor deposition even when used for a long time at a high temperature. Since there are few surface fluctuations, it can be used for thin-walled molded products that are required to have heat resistance and good appearance, in particular, to maintain a mirror surface state at high temperatures, and is very useful.

  Hereinafter, the present invention will be described in detail.

  The polyarylate resin used in the present invention is a polyester comprising an aromatic dicarboxylic acid or a derivative thereof and a dihydric phenol or a derivative thereof, and is produced by a method such as solution polymerization, melt polymerization, or interfacial polymerization.

  Preferred examples of the raw material for introducing the aromatic dicarboxylic acid residue include terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2 , 7-Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, methyl terephthalic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-diphenylether 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, etc. However, terephthalic acid and isophthalic acid are preferred, and they should be used in combination from the viewpoint of melt processability and mechanical properties. Particularly preferred. In that case, the mixing molar ratio (terephthalic acid / isophthalic acid) is arbitrarily in the range of 100/0 to 0/100, preferably 80/20 to 10/90, more preferably 60/40 to 25/75. If it is within the range, the resulting polyarylate becomes amorphous and has excellent transparency.

  The raw material for introducing the bisphenol residue is bisphenol. Specific examples thereof include resorcinol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5- Dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy -3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxy Examples include diphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane, and the like. Polyarylate resins made of these compounds tend to be amorphous and excellent in transparency. These compounds may be used alone or in combination of two or more. Of these compounds, 2,2-bis (4-hydroxyphenyl) propane is preferably used, and optimally used alone.

The polyarylate resin composed of these raw materials has an inherent viscosity of 0.40 to 0.60 dl / g at a temperature of 25 ° C. of a solution obtained by dissolving 1.0 g of a sample in 100 ml of 1,1,2,2-tetrachloroethane. it is necessary, it is good preferable is 0.45 to 0.55. If the inherent viscosity is less than 0.40, the mechanical properties of the resulting resin composition are inferior or the heat distortion temperature is lowered, which is not preferable. Conversely, if the inherent viscosity exceeds 0.60, the melt viscosity is high. Therefore, the fluidity of the resulting resin composition may be inferior, which is not preferable.

  The polycarbonate resin used in the present invention is a polycarbonate formed by repeating a bisphenol residue unit and a carbonate residue unit. Since the polycarbonate resin has bisphenol residue units similar to those of the polyarylate resin, it exhibits good compatibility with polyarylate.

  Examples of bisphenols as polycarbonate raw materials for introducing bisphenol residue units include 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (3,5-dibromo-4-hydroxyphenyl). Propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) ) Cyclohexane, 1,1-bis (4-hydroxyphenyl) decane, 1,3- or 1,2-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'-dihydroxy-2,5-dihydroxydiphenyl ether, and the like. In addition, diphenols described in US Pat. Nos. 2,999,835, 3,028,365, 3,334,154, and 4,131,575 can be used. These may be used alone or in combination of two or more. Among these compounds, it is preferable to use at least 2,2-bis (4-hydroxyphenyl) propane, more preferably the compound is used alone.

  Examples of the polycarbonate raw material for introducing the carbonate residue unit include phosgene and diphenyl carbonate.

The polycarbonate resin composed of these raw materials has an inherent viscosity at a temperature of 25 ° C. of 0.40 to 0.003 of a solution (concentration 1 g / dl) obtained by dissolving 1.0 g of a sample in 100 ml of 1,1,2,2-tetrachloroethane. It is preferably 70 dl / g, more preferably 0.42 to 0.65. If the inherent viscosity is less than 0.40, the mechanical properties of the resin composition obtained are inferior or the heat distortion temperature is lowered, which is not preferable. Conversely, if the inherent viscosity exceeds 0.70, the melt viscosity is high. Therefore, the fluidity of the resulting resin composition may be inferior, which is not preferable.

  In the present invention, the blending ratio of the polyarylate resin and the polycarbonate resin is such that the mass ratio of (A) polyarylate resin / (B) polycarbonate resin is 50 from the viewpoint of molding processability of the resin composition and heat distortion resistance of the molded product. The range of / 50 to 95/5 is preferable, and 60/40 to 90/10 is more preferable. If the ratio of the polyarylate resin in the mass ratio is less than 50, sufficient heat resistance cannot be obtained, and conversely if it exceeds 95, the fluidity during melt processing becomes insufficient.

  The polystyrene resin used in the present invention is a polymer comprising a styrene compound as a monomer, and is a polymer of unsubstituted styrene, a monomer having a substituent on the phenyl group, or a copolymer thereof. In the present invention, a crystalline polystyrene resin having a high degree of stereoregularity in the arrangement of monomers is preferable to an amorphous material generally called GP-PS. The stereoregularity of the monomer is roughly divided into three types, which are isotactic in which all side chains (phenyl groups in the case of polystyrene resin) are on the same side of the molecular chain when the polymer molecular chain is stretched in a straight line. , Syndiotactic in which the side chains are located completely alternately on both sides of the molecular chain, and atactic in which the side chains are randomly arranged on both sides of the molecular chain.

  In general vinyl polymers, atactic polymer is amorphous, but isotactic and syndiotactic polymers are often crystalline. Also in the case of polystyrene, isotactic polymer and syndiotactic polymer are crystalline polymers, but when comparing crystallization speed, isotactic polymer is slow, but syndiotactic polymer is relatively fast. In the present invention, the use of syndiotactic polystyrene tends to be a resin composition from which a molded product can be obtained with little change in appearance and deterioration of the mirror state of the vapor deposition surface even when used at high temperatures.

  The higher the stereoregularity of the polystyrene resin used in the present invention, the better. The higher the stereoregularity, the higher the degree of crystallinity of the polystyrene resin, and the higher the degree of crystallinity of the polystyrene used in the resin composition of the present application, This is suitable because a molded product with less deterioration of the mirror surface state can be easily obtained. The judgment as to whether or not the polystyrene resin is crystalline can be confirmed by X-ray diffraction, IR measurement, and thermal analysis. Specifically, in the case of X-ray diffraction or IR measurement, the presence or absence of a peak derived from the crystal structure, in thermal analysis, for example, in the differential scanning calorimeter (DSC), when the temperature is raised from the low temperature to the melting point or higher Whether it is crystalline or amorphous can be determined by the presence or absence of an endothermic peak derived from. The crystallinity can be determined by the magnitude of the peak intensity as the crystallinity increases. Among the analysis methods described above, the DSC method can be easily measured, and the results are easily judged.

In the present invention, the melting point measured by the DSC method is 200 ° C. or higher, and by using a polystyrene resin having an endotherm calculated from the melting peak of 15 J / g or more, the appearance change when used at high temperature, vapor deposition It becomes the suitable resin composition from which the molded article with little deterioration of the mirror surface state of a surface is obtained. Among them, syndiotactic polystyrene having a high tacticity is most preferable because it has a melting point of 270 ° C. or higher and a melting endotherm of 30 J / g or higher. A method for producing such syndiotactic polystyrene is disclosed in Japanese Patent Application Laid-Open No. 62-104818. Note that the melting point changes when a monomer having a substituent in the phenyl group is used. In the case of methyl-substituted styrene, if it is a homopolymer, the melting point may be lowered to 200 ° C. or less even if it is a syndiotactic polymer. Therefore, it is preferable to use a copolymer with unsubstituted styrene. Although isotactic polystyrene is also crystalline, it is generally said that the crystallization rate is slow, but it can be used in the present invention because it has a melting point of 230 ° C. Whether the crystalline polystyrene resin is isotactic or syndiotactic can be determined by X-ray diffraction or ¹³ C-NMR.

In the present invention, the mass ratio of (C) polystyrene resin needs to be in the relationship of the following formula with the mass ratio of (A) polyarylate resin and (B) polycarbonate resin.
(C) / {(A) + (B) + (C)} = 0.5 / 100 to 20/100 (2)
The said formula represents the compounding ratio of the polystyrene resin when the whole resin composition is 100 parts by mass, the polystyrene needs to be 0.5 to 20 parts by mass, and 1 to 15 parts by mass is preferable. When the blending ratio of the polystyrene resin is less than 0.5 parts by mass, the effect of improving the fluidity of the resin composition is not so much seen. On the other hand, when it exceeds 20 parts by mass, the impact resistance of the resin composition is remarkably lowered and the molded product is In the case of depositing a metal, the adhesion deteriorates, which is not preferable.

  The resin composition of the present invention has an inherent viscosity at a temperature of 25 ° C. of 0.40 to 0.65 of a solution obtained by dissolving 1.0 g of a sample in 100 ml of a mixture of phenol / 1,1,2,2-tetrachloroethane having a mass ratio of 60/40. It is preferably dl / g, more preferably 0.45 to 0.60 dl / g. If the inherent viscosity is less than 0.40 dl / g, the mechanical properties are inferior. On the other hand, if the inherent viscosity exceeds 0.65 dl / g, the melt viscosity is high and the fluidity during injection molding may be deteriorated.

  In addition to the above components, the resin composition of the present invention contains a hindered phenol-based or lactone-based antioxidant or a hindered amine-based light stabilizer from the viewpoint of further improving the heat discoloration resistance of the molded product. Also good. Further, the resin composition of the present invention contains various additives such as an ultraviolet absorber, a bluing agent, a flame retardant, a mold release agent, an antistatic agent and a lubricant, as long as the heat discoloration of the molded product is not lowered. Also good.

  In the present invention, the method of blending the polyarylate resin, polycarbonate resin, and polystyrene resin is not particularly limited as long as each component is uniformly dispersed. Specifically, polyarylate resin, polycarbonate resin, and liquid crystal polymer resin may be uniformly dry blended using a tumbler or Henschel mixer, and then melt-kneaded and extruded to form pellets.

  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 usually, an injection molding method, an extrusion molding method, and a compression molding method are preferably used.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited only to these Examples.

1. Evaluation method
(1) Inherent viscosity (dl / g): Using an Ubbelohde viscometer, phenol / 1,1,2,2-tetrachloroethane in a mass ratio of 60/40 as a solvent, concentration 1 g / dl, temperature Measurements were taken at 25 ° C.
(2) Deflection temperature under load (° C.): Based on ISO75, the deflection temperature under load at 1.8 MPa was measured using a test piece having a thickness of 4 mm.
(3) Charpy impact value (kJ / m ² ): Based on ISO-179-1eA, a Charpy impact value with a notch was measured using a test piece having a thickness of 4 mm.
(4) Bar flow flow length (mm): After pellet-shaped resin composition is dried with hot air at 120 ° C for 8 hours or more, it is placed on a 32mmφ injection molding machine (trade name EC100NII manufactured by Toshiba Machine) with a thickness of 2mm and a width of 20mm. A flow test mold was attached, the cylinder temperature was set to 340 ° C., the mold temperature was set to 100 ° C., and the flow length at an injection pressure of 120 MPa and an injection time of 4 seconds was measured.
(5) Appearance change: 2mm-thick plate mold molded with a 8000 mirror finish mold was heat-treated at 150 ° C for 2 hours, and the deposited surface was observed. A sample in which no disturbance was observed on the mirror surface was indicated as ◯, and a sample in which disturbance was observed was indicated as ×.

2． Raw materials The raw materials used in the examples and comparative examples are as follows.
(A) Polyarylate resin Polyarylate (A-1) to (A-2) synthesized by the following method was used.

Production Example 1
Sodium hydroxide 0.62 kg (15.5 mol) was dissolved in 50 L of ion-exchanged water in a 100-L reaction vessel equipped with a water-cooling jacket and a stirring device, and then 2,2-bis (4- 1.64 kg (7.2 mol) of hydroxyphenyl) propane (hereinafter referred to as BPA) and 0.062 kg (0.41 mol) of p-tertbutylphenol (hereinafter referred to as PTBP) were dissolved. In another container, terephthalic acid dichloride (hereinafter referred to as TPC) and isophthalic acid dichloride (hereinafter referred to as IPC) were dissolved in 20 L of dichloromethane having a water content of 20 ppm in an amount of 0.75 kg (3.7 mol). After adjusting each solution to 20 ° C., all of the dichloromethane solution was added to the place where the aqueous solution was stirred in a reaction vessel. Immediately after the addition, the rotation speed of the stirrer was adjusted so that the required power for stirring per unit volume was 10 kW / m 3, and stirring was continued for 6 hours. After standing separation, the aqueous phase was extracted, and 120 g (2 mol) of acetic acid was added to the remaining dichloromethane phase. Thereafter, 25 L of ion-exchanged water was added, stirred for 20 minutes, and allowed to stand again to extract the aqueous phase. After repeating this washing operation until the aqueous phase becomes neutral, the dichloromethane phase is poured into 50 ° C. warm water in a container equipped with a homomixer to evaporate the methylene chloride to obtain a powdered polyarylate. It was. This powdery polyarylate was dehydrated and then dried at 120 ° C. under reduced pressure for 24 hours using a vacuum dryer to obtain polyarylate (A-1). The inherent viscosity was measured and found to be 0.53 dl / g. The composition and inherent viscosity are shown in Table 1.

Production Example 2
Polyarylate (A-2) was obtained in the same manner as in Production Example 1 except that the blending amounts of sodium hydroxide, BPA, PTBP, TPC and IPC were changed to the values shown in Table 1. Table 1 shows the inherent viscosity measured for these.

(B) Polycarbonate resin
(B-1) Polycarbonate having a concentration of 1 g / dl using 1,1,2,2-tetrachloroethane as a solvent and an inherent viscosity of 0.64 at a temperature of 25 ° C. (trade name Caliber 200-3, manufactured by Sumitomo Dow)
(B-2) Polycarbonate having an inherent viscosity of 0.49 (trade name Caliber 200-13, manufactured by Sumitomo Dow)

(C) Polystyrene resin
(C-1) Syndiotactic polystyrene resin with a melting point of 272 ° C and a heat of fusion of 34 J / g (made by Idemitsu Kosan Co., Ltd., Zalek 300ZC)
(C-2) Syndiotactic polystyrene resin with a melting point of 247 ° C and a heat of fusion of 24 J / g (made by Idemitsu Kosan Co., Ltd., Zalek 142AE)
(C-3) Amorphous polystyrene resin (Toyostyrene G210C manufactured by Toyo Styrene Co., Ltd.)

Examples 1-8
Table 2 shows (A) polyarylate resin and (B) carbonate resin that were dried at 120 ° C for 8 hours or more using a hot air circulation dryer, and (C) polystyrene resin that was dried at 70 ° C for 6 hours or more. After mixing at the indicated blending ratio with a total charge of 3 kg, Kubota's loss-in-weight continuous quantitative feeder CE-W-1 has a screw diameter of 37 mm and L / D40 twin screw extrusion with two vents. Machine (TEM37BS manufactured by Toshiba Machine Co., Ltd.) was supplied to the main supply port. Then, the barrel temperature of the extruder is set to 300 ° C, the degree of vent vacuum is -0.099 MPa (gauge pressure), the discharge rate is 20 kg / h, the screw speed is 300 rpm, and the resin composition taken into a strand from the die is bathed in water. The mixture was cooled and solidified, cut with a pelletizer, and then dried with hot air at 120 ° C. for 8 hours to obtain pellets of a resin composition.

  The inherent viscosity of the resulting resin composition pellets was measured, and using a 32mmφ injection molding machine (EC100NII manufactured by Toshiba Machine Co., Ltd.), at a cylinder temperature of 340 ° C and a mold temperature of 100 ° C, 80mm x 10mm x 4mm Measure the deflection temperature under load (DTUL) and Charpy impact value by injection molding a strip-shaped molded product, and deposit aluminum on a 2mm-thick plate molded product molded with a 8000th mirror finish mold This was heat-treated at 150 ° C. for 2 hours, and the vapor deposition surface was observed. Furthermore, the bar flow flow length was measured. The results are shown in Table 2.

Comparative Examples 1-5, 6-12
Resin composition pellets were prepared and evaluated in the same manner as in the Examples except that the formulations shown in Table 3 and Table 4 were used. The results are shown in Table 3 and Table 4.

  In Examples, resin compositions having good heat resistance, impact resistance, and fluidity were obtained at each blending ratio.

  In Comparative Examples 1 to 5, since no polystyrene resin was blended, the fluidity was inferior compared to Examples 1 to 5.

  In Comparative Examples 6 and 7, since the blending ratio of the polystyrene resin was large, the fluidity was excellent but the impact resistance was inferior.

  In Comparative Examples 8 to 10, since an amorphous polystyrene resin was blended, an appearance change occurred due to thermal aging.

  In Comparative Example 11, since the polyarylate resin having a large inherent viscosity was blended, the inherent viscosity of the resin composition was large, and the fluidity was inferior.

In Comparative Example 12, since the ratio of polyarylate resin / polycarbonate resin was 30/70, the deflection temperature under load was less than 150 ° C.

Claims (1)

It consists of (A) polyarylate having an inherent viscosity of 0.40 to 0.60 dl / g , (B) polycarbonate, and (C) polystyrene, and the mass ratio of each component is represented by the following formulas (I) and (II). A resin composition for forming a deposited film, which is a satisfactory resin composition, wherein the (C) polystyrene is syndiotactic polystyrene having a melting point of 200 ° C or higher .
(A) / (B) = 50/50 to 95/5 (I)
(C) / {(A) + (B) + (C)} = 0.5 / 100 to 20/100 (II)