Polyalkylene arylate resin composition

Abstract: Polyalkylene arylate resin compositions with improved crystallization rates, which give faster mold cycle times and increased manufacturing productivity, are provided by a crystalline polyalkylene arylate base resin (A) and a copolyester (B) having a polyalkylene arylate segment (a) which exhibits smectic liquid crystallinity and a polyalkylene arylate segment (b) which does not exhibit smectic liquid crystallinity.

Description: The present invention relates to a resin composition which exhibits improved crystallization rates during processing (resulting in higher productivity), and from which molded articles having excellent surface characteristics can be made. During the injection or extrusion molding of a crystalline thermoplastic polyalkylene arylate resin (e.g. as represented by a polyalkylene terephthalate), the rate of crystallization of the resin when cooled has a great influence on the molding time (molding cycle time), and thus influences the productivity (economic efficiency) relating to making molded articles from such resin. Known methods for accelerating the crystallization rate by raising the crystallization temperature include adding an inorganic filler, such as boron nitride or talc, to the polyalkylene arylate resin. However, when a crystalline thermoplastic polyalkylene arylate resin containing such a filler is extruded into a film, small spots (known in the art as "fish eyes") will be present in the film, possibly due to the non-uniform rate of crystallization that ensues. The resulting film is understandably of little commercial value. In order to solve this problem, the mixture of crystalline thermoplastic polyalkylene arylate resin and inorganic filler must be further processed (i.e. the mixture must be subjected to high shearing force in an extruder for prolonged time periods) thereby to convert the mixture into a homogeneous dispersion. Such further processing, however, lowers the molecular weight of the resin and in many cases yields molded articles having poor physical characteristics. The present invention is thus directed towards a solution to the above-described problems. More specifically, the present invention is based upon the discovery that by adding a specific copolymer comprised of a specific alkylene arylate segment exhibiting smectic liquid crystallinity and an ordinary polyalkylene arylate segment not exhibiting smectic liquid crystallinity, to a crystalline polyalkylene arylate base resin, significant improvements in the crystallization rate can be obtained. In addition, the problems associated with conventional techniques to improve crystallization rates (e.g. the so-called "fish eyes" in formed films) are overcome. Broadly, the present invention relates to a polyalkylene arylate resin composition comprising (A) 100 parts by weight of a crystalline polyalkylene arylate base resin, and (B) 1 to 100 parts by weight of a copolyester formed of (a) a polyalkylene arylate segment (referred to hereinafter as the "LC segment") which exhibits smectic liquid crystallinity and which is formed of repeating units represented by the general formula: wherein m is an integer from 4 to 10 inclusive and X represents either a single bond linking the arylene moieties or a constituent group selected from: -CH=CH-, -N=N(O)-, -CH=N-, and (b) a polyalkylene arylate segment (referred to hereinafter as the "non-LC segment") which does not exhibit smectic liquid crystallinity and which is formed of repeating units represented by the general formula: wherein Ar is and R is selected from an alkylene group, wherein the molar fraction of the segment (a) in the component (B) is between 10 and 90 mole %. The crystalline polyalkylene arylate base resin which is the main component of the composition according to the present invention is preferably a polyester prepared by the polycondensation of terephthalic acid and/or naphthalenedicarboxylic acid (or an ester-forming derivative thereof) with an alkylenediol (or an ester-forming derivative thereof). The alkylenediol may be not only HO-(CH₂) n' -OH (wherein n' is an integer between 2 and 10, inclusive) but also cyclohexanediol and diethylenecyclohexanediol. Representative examples of the polyalkylene arylate base resin formula include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalates, polyhexamethylene terephthalate, polycyclohexane terephthalates and polyesters of the diol components of the above polyesters with naphthalenedicarboxylic acid, isophthalic acid and mixtures thereof. The copolyester component (B) that may be used in the compositions of the present invention is a copolyester comprising both a LC segment (i.e represented by the general formula (1)) and a non-LC segment (i.e. represented by the general formula (2)). As described in, for example, Shigeo Iwayanagi, "Ekisho (Liquid Crystals)", (1984, Kyoritsu Shuppan), a smectic liquid crystal has a laminar structure wherein laminae are each comprised of molecules arranged in such a state that the axes of the molecules are parallel to each other, and the laminae are nearly perpendicular to the axes of the molecules, with the centers of gravity of the laminae being present on the same plane. Further, it is also known that a smectic liquid crystal exhibits a unique pattern such as batonets, mosaic or fan texture, when observed under a microscope with crossed nicols. A smectic liquid crystalline segment exhibiting such unique characteristics must contain in the same molecule both a mesogen having a high stiffness and a soft spacer which is a flexible group. That is, as represented by the general formula (1), the smectic liquid crystalline segment (a) must contain in its molecular skeleton both a mesogen containing at least two benzene rings, and a soft spacer composed of an alkyl group. A particularly preferred example of the LC segment (a) is a polyalkylene biphenylcarboxylate comprising repeating units represented by the general formula (1)-1: wherein m is an integer between 4 and 10 inclusive. If the number of carbon atoms, m, of the soft spacer is less than 4, the resulting polymer will neither exhibit smectic liqud crystallinity nor have a latent ability to become a smectic liquid crystal. On the contrary, as the number of carbon atoms increases, the melting point of the resulting polymer will serve to accelerate the crystallization in the crystalline polymer. The component (B) is a copolymer having in its molecular structure not only a LC segment (a) as described above (i.e. which exhibits smectic liquid crystallinity), but also another polyalkylene arylate segment (b) not exhibiting smectic liquid crystallinity. The non-LC segment (b) is represented by the general formula (2). Although any conventional polyalkylene arylate may be used as the non-LC segment (b), polyalkylene terephthalates and polyalkylene naphthoates are preferred. Particularly preferred are polyalkylene terephthalates and polyalkylene naphthoates having an alkyl group containing 2 to 10, particularly 2 to 4, carbon atoms. The relation between the structures of the non-LC segment (b) of the component (B) and the crystalline polyalkylene arylate (A) is not particularly limited. Thus, the structures of the non-LC segment (b) and the crystalline polyalkylene arylate (A) may be the same as, or different from, one another. However, in order to facilitate the homogeneous dispersion of the components (A) and (B) to obtain a molded article of high quality (e.g. free from the so-called "fish eye" defects), it is preferred that the non-LC segment (b) and the crystalline polyalkylene arylate (A) have the same structures. It is necessary from the standpoint of crystallization acceleration that the molar fraction of the smectic liquid crystalline segment (a) in the component (B) be between 10 and 90 mole %, and particularly between 30 and 90 mole %. The component (B) may or may not exhibit, smectic liquid crystallinity. That is, the benefits of the prsent invention can be achieved provided that the copolyester component (B) contains a segment in its molecular chain which exhibits smectic liquid crystallinity and provided that that liquid crystal segment is present in the molecular chain in an amount as described above. The copolyester component (B) can be prepared by melt-kneading a homopolyester solely composed of units represented by the general formula (1) with a homopolymer solely composed of units represented by the general formula (2) in the presence of a suitable ester interchange catalyst to obtain thereby a copolyester containing segments derived from each said homopolymer. Alternatively, the copolyester component (B) can be prepared by melt-kneading biphenylenedicarboxylic acid (or an ester-forming derivateve thereof), terephthalic acid and/or naphthalenedicarboxylic acid (or an ester-forming derivative thereof) and an alkylenediol in the presence of a suitable polycondensation catalyst under polycondensation reaction conditions. The amount of the copolyester component (B) to be added to 100 parts by weight of the polyalkylene arylate base resin (A) is between 1 to 100 parts by weight and preferably between 4 to 60 parts by weight. If the amount added is less than 1 part by weight, no beneficial effect on the crystallization will be obtained. On the other hand, if the amount exceeds 100 parts by weight, the resulting composition will be highly viscous in a molten state and thereby be more difficult to process. The resin composition of the present invention may also contain additives which are conventionally added to thermoplastic or thermosetting resins depending upon the performance characteristics that may be required. Examples of such additives include stabilizers such as antioxidants and ultra-violet light absorbers; antistatic agents; flame retardants; auxiliary flame retardants; coloring agents such as dyes and pigments; lubricants and fibrous, powdery, granular and/or flaky fillers. The resin compositions according to the present invention can be prepared by processes conventionally used to prepare synthetic resin compositions using conventional processing equipment. For example, the necessary components may be mixed and kneaded together and extruded with a single- or twin-screw extruder to obtain a molding pellet. During preparation, a part of the necessary components may be mixed, as a master batch, with a residual part thereof, followed by molding. Furthermore, in order to facilitate the dispersion and mixing of the necessary components, a part or the whole of the resins may be preliminarily ground, followed by mixing and melt extrusions. The resin compositions of the present invention exhibit enhanced rates of crystallization, thereby resulting in shorter molding cycle times and increased productivity. The compositions can moreover be crystallized at a uniform rate in the absence of high shear forces and/or long residence times during blending to give a molded article exhibiting excellent surface appearance. The compositions of the present invention having the above characteristics can be molded by injection or extrusion molding techniques into various film, sheet and fiber articles. Examples The present invention will be described in more detail by referring to the following non-limiting Examples. Example 1 Dimethyl terephthalate (DMT), dimethyl bibenzoate (DMDA) and 1,4-butanediol (1,4 BD) were fed into a hermetically closed reactor at a molar ratio of 0.4:0.6:1.5 and heated under a normal pressure in the presence of a tetrabutyl titanate catalyst to raise the temperature gradually from 140°C to 200°C so as to carry out ester interchange. The reaction mixture was melt-polymerized at 245°C under a reduced pressure of 67Pa (0.5 Torr) for one hour. The product was removed from the reactor and cut to obtain polymer chips (B). The obtained polymer was a copolymer comprising a segment and a segment The copolymer exhibited smectic liquid crystallinity at 218 to 255°C, when observed under a microscope using a DSC manufactured by Perkin Elmer and crossed nicols. 10 parts by weight of the above polymer chips as the component (B) were added to 100 parts by weight of polybutylene terephthalate (A) having an intrinsic viscosity of 1.0 and the obtained mixture was kneaded by the use of a conventional extruder. The resin composition thus prepared was cooled at a rate 10, 40 or 100°C/min to determine the value (temperature) of the endothermic peak indicative of the rate of crystallization, The resin composition was molded into a film by the use of an extruder fitted with a T-die and the surface appearance of the film was observed. The results are shown in Table 1. According to the present invention, a film having a uniform and smooth surface appearance was obtained. Example 2 Dimethyl terephthalate (DMT), dimethyl bibenzoate (DMDA) and 1,4-butanediol (1,4 BD) were fed into a hermetically closed reactor at a ratio of 0.3:0.7:1.5 and heated under a normal pressure in the presence of a tetrabutyl titanate catalyst to raise the temperature gradually from 140°C to 210°C. Thus, the ester interchange was carried out. The reaction mixture was melt-polymerized at 260°C under a reduced pressure of 67Pa (0.5 Torr) for 30 minutes. The product was taken out of the reactor and cut to obtain polymer chips (B). Although the polymer (B) thus obtained comprised the same segments as those of the polymer obtained in Example 1, the polymers are different from each other in the ratio between the segments. The polymer of the present Example exhibited smectic liquid crystallinity at 226 to 246°C. 15 parts by weight of this copolymer was added to 100 parts by weight of polybutylene terephthalate (A) having an intrinsic viscosity of 1.0. The obtained mixture was kneaded by the use of a conventional extruder. The obtained resin composition was examined for the value (temperature) of the endothermic peak indicating the rate of crystallization in a similar manner to that described in Example 1. The resin composition was molded into a film by the use of an extruder fitted with a T-die and the surface appearance of the film was observed. The results are shown in Table 1. Example 3 Dimethyl terephthalate (DMT), dimethyl bibenzoate (DMDA) and 1,4-butanediol (1,4 BD) were polymerized at a molar ratio of 0.6:0.4:1.5 in a similar manner to that described in Example 1 to obtain a copolymer (B). Although this copolymer was molten at 216°C, it did not exhibit smectic liquid crystallinity. The preparation of a resin composition and the evaluation thereof were carried out according to the same procedure as that described in Example 1 except that the copolymer prepared in this Example as the component (B) was added to 100 parts by weight of the polybutylene terephthalate (A). Example 4 Dimethyl terephthalate (DMT), dimethyl bibenzoate (DMDA) and 1,4-butanediol (1,4 BD) were fed into a hermetically closed reactor at a molar ratio of 0.2:0.8:1.5 and heated under a normal pressure in the presence of tetrabutyl titanate catalyst to raise the temperature gradually from 140°C to 210°. Thus, the ester interchange was carried out. The resulting reaction mixture was melt-polymerized at 270°C under a reduced pressure of 67Pa (0.5 Torr) for 20 minutes. The obtained product was taken out of the reactor and cut to obtain polymer chips. The polymer (8) thus prepared comprised the same segments as those of the polymer prepared in Example 1 or 2, though they are different from each other in the ratio between the segments. The polymer exhibited smectic liquid crystallinity at 242 to 259°C. 15 parts by weight of this copolymer was added to 100 parts by weight of polyethylene terephthalate (A) having an intrinsic viscosity of 1.2. The obtained mixture was kneaded by the use of a conventional extruder. The resin composition thus prepared was examined for the value of the endothermic peak indicating the rate of crystallization in a similar manner to that described in Examples 1 to 3. The resin composition was molded into a film by the use of an extruder fitted with a T-die and the appearance of the film was observed. The results are shown in Table 1. Comparative Example 1 The same polybutylene terephthalate as that used in Example 1 was alone examined for crystallization temperature in a similar manner to that described in Example 1. Further, the polybutylene terephthalate was molded into a film by the use of an extruder fitted with a T-die and the surface appearance of the film was observed. The results are shown in Table 1. Comparative Example 2 The same polybutylene terephthalate as that used in Example 1 was kneaded together with 0.01% by weight of powdered boron nitride (a product of Denki Kagaku Kogyo K.K.) by use of a conventional extruder to obtain a resin composition. This resin composition was examined for crystallization temperature in a similar manner to that described in Example 1. Further, the resin composition was molded into a film with an extruder fitted with a T-die and the surface appearance of the film was observed. The results are shown in Table 1. Comparative Example 3 Dimethyl bibenzoate (DMDA) and 1,4-butanediol were fed into a hermetically closed reactor at a molar ratio of 1.0:1.5 and polycondensed in a similar manner to that described in Example 1 to obtain a homopolymer solely composed of repeating units: 10 parts by weight of the homopolymer thus prepared was added to 100 parts by weight of PBT used instead of the component (B) of Example 1. The obtained mixture was kneaded and extruded to obtain a resin composition. This composition was evaluated in a similar manner to that described in Example 1. The results are shown in Table 1. Comparative Example 4 The same polyethylene terephthalate as that used in Example 4 was examined for crystallization temperature in a similar matter to that described in Example 1. Further, the polyethylene terephthalate was molded into a film with an extrusion molding machine fitted with a T-die and the surface appearance of the film was observed. The results are shown in Table 1. Comparative Example 5 The same polyethylene terephthalate as that used in Example 4 was kneaded together with 0.01% by weight of powdered boron nitride (a product of Denki Kagaku Kogyo K.K.) by the use of a conventional extruder to obtain a resin composition. This resin composition was examined for crystallization temperature in a similar manner to that described in Example 1. Further, the resin composition was molded into a film with an extrusion molding machine fitted with a T-die and the surface appearance of the film was observed. The results are shown in Table 1. As shown in Table 1, the composition of the present invention (of the Example) initiates crystallization at a higher temperature than that of the corresponding composition (of the Comparative Example), i.e. earlier than the corresponding composition. When the composition was cooled rapidly, the crystallization initiating temperature rose still remarkably. This rise in the crystallization initiating temperature means the enhancement of the rate of solidification (crystallization), thereby shortening the molding cycle.

Claims: A polyalkylene arylate resin composition comprising: (A) 100 parts by weight of a crystalline polyalkylene arylate base resin, and (B) 1 to 100 parts by weight of a copolyester formed of (a) a polyalkylene arylate segment (referred to herein as the"LC segment") which exhibits smectic liquid crystallinity and which is formed of repeating units represented by the general formula: wherein m is an integer from 4 to 10 inclusive and X represents either a single bond linking the arylene moieties or a constituent group selected from: -CH=CH-, -N=N(O)-, -CH=N-, and (b) a polyalkylene arylate segment (referred to herein as the "non-LC segment") which does not exhibit smectic liquid crystallinity and which is formed of repeating units represented by the general formula: wherein Ar is and R is selected from an alkylene group, wherein the molar fraction of the segment (a) in the component (B) is between 10 and 90%. A polyalkylene arylate resin composition as claimed in claim 1, wherein the crystalline polyalkylene arylate base resin (A) is a polyester prepared by the polycondensation of at least one acid (or ester-forming derivative thereof) selected from terephthalic acid and naphthalenedicarboxylic acid with at least one alkylenediol (or ester-forming derivative thereof) selected from those of the general formula HO-(CH₂) n′ -OH (wherein n′ is an integer from 2 to 10 inclusive), cyclohexanediol and diethylenecyclohexanediol. A polyalkylene arylate resin composition as claimed in claim 2, wherein the crystalline polyalkylene arylate base resin (A) is selected from polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalates, polyhexamethylene terephthalate, polycyclohexane terephthalates and polyesters of the diol components of these polyesters with naphthalenedicarboxylic acid, isophthalic acid and mixtures thereof. A polyalkylene arylate resin composition as claimed in any preceding claim, wherein the LC segment (a) of the copolyester (B) is a polyalkylene biphenylcarboxylate comprising repeating units represented by the general formula (1)-1: where m is an integer from 4 to 10, inclusive. A polyalkylene arylate resin composition as claimed in any preceding claim, wherein the non-LC segment (b) of the copolyester (B) is selected from polyalkylene terephthalates and polyalkylene naphthoates. A polyalkylene arylate resin composition as claimed in claim 5, wherein R in the general formula (2) of the non-LC segment (b) is at least one group selected from those of the formula -(CH₂) n -, wherein n is an integer from 2 to 10 inclusive. A polyalkylene arylate resin composition as claimed in any preceding claim, wherein the crystalline polyalkylene arylate (A) and the non-LC segment (b) of the copolyester (B) have the same structures. A polyalkylene arylate resin composition as claimed in any preceding claim, wherein the molar fraction of the LC segment (a) in the copolyester (B) is between 10 and 90 mole %. A polyalkylene arylate resin composition as claimed in claim 8, wherein the molar fraction of the LC segment (a) in the copolyester (B) is between 30 and 90 mole %. A polyalkylene arylate resin composition as claimed in any preceding claim, wherein the amount of the copolyester (B) is between 4 and 60 parts by weight per 100 parts by weight of the crystalline polyalkylene arylate (A).

Inventors: HIJIKATA KENJI, NAKANE TOSHIO, SAITO TATSUYA, WATANABE JUNJI, HIJIKATA, KENJI, NAKANE, TOSHIO, SAITO, TATSUYA, WATANABE, JUNJI
Applicants: POLYPLASTICS CO, POLYPLASTICS CO. LTD.
Application year: 1990
Main classification: C08L67
IPC codes: C08G63, C09K19, C08L67