Document daB3X43DJyVqr2M1Yq8yw5bKR

United States Patent [19] Ogawa et al. [ii] Patent Number: 4,536,531 [45] Date of Patent: Aug. 20, 1985 [54] POLYESTER RESIN COMPOSITION [75] Inventors: Yoshinari Ogawa; Noriyuki Akagi, both of Sagamihara, Japan [73] Assignee: Teijin Limited,Osaka, Japan [21] Appl. No.: 496,059 [22] Filed: May 19, 1983 Related U.S. Application Data [63] Continuation-in-part ofSer. No. 343,456, Jan. 28, 1982, abandoned. [30] Foreign Application Priority Data Jan. 30, 1981 May 8, 1981 Jul. 17, 1981 [JP] Japan ................................. 56-11549 [JP] Japan ................................. 56-68106 [JP] Japan ............................... 56-110804 [51] Int. Cl/ ...................... C08L 67/02; C08L 67/04 [52] U.S. Cl..................................... 524/135; 524/133; 524/417; 524/145; 524/147; 524/152; 524/153; 524/394; 524/400; 524/425; 524/445; 524/451; 524/452; 524/456; 524/513; 524/539; 524/414; 525/411; 525/437; 525/438 [58] Field of Search .............. 525/411, 415, 166, 437; 524/539, 513, 605, 394, 400, 451, 425, 452, 445, 456, 133, 135, 417, 145, 147, 152, 153, 414 [56] References Cited U.S. PATENT DOCUMENTS 3,583,935 6/1971 Weissermel ........................ 523/440 3,835,089 9/1974 Fox .................................... 525/411 3,892,821 7/1975 Koleske............................. 525/411 4,212,791 4,222,928 4,223,113 7/1980 Avery ............................ 524/539 9/1980 Kawamura....................... 523/451 9/1980 Bier ................................. 525/444 FOREIGN PATENT DOCUMENTS 47-45820 11/1972 Japan............................... 525/411 49-27091 7/1974 Japan............................... 525/411 2015014 9/1979 UnitedKingdom . Primary Examiner--John C. Bleutge Assistant Examiner--Patricia Short Attorney, Agent, or Firm--Burgess, Ryan & Wayne [57] ABSTRACT A polyester resin composition having excellent molding mobility and crystallizing property, comprises (A) at least one thermoplastic polyester resin selected from polyethylene terephthalate resins and polybutylene terephthalate resins; (B) a polycaprolactone having a number average molecular weight of from 200 to 2,000 in an amount of 0.1 to 30 parts by weight per 100 parts by weight of the polyester resin, in which polycaprolac tone molecules, at least 50% of the terminal radicals thereof, are modified to be non-reactive, (C) 0.01 to 10 parts by weight of a crystal nucleating agent per 100 parts of the polyester resin, and optionally, (D) at least one additive selected from fillers and specific phospho rous compounds which may be in combination with a specific epoxy compound, the polyester resin composi tion being useful for producing a molded product hav ing an excellent dimensional stability and mechanical strength. 9 Claims, No Drawings 4,536,531 12 accelerating the crystallization of the polyester resin by POLYESTER RESIN COMPOSITION adding thereto a crystal nucleating agent comprising an inorganic solid substance, such as talc, carbon black or This, application is a continuation-in-part of applica graphite, or an organic solid substance, such as metal tion Ser. No. 343,456, filed January 28, 1982, now aban 5 salts of organic monocarboxylic acids. doned. Although the addition of the crystal nucleating agent BACKGROUND OF THE INVENTION is effective for shortening the molding cycle time to a certain extent, there is still room for improvement. For 1. Field of the Invention example, even in the case where a crystal nucleating The present invention relates to a polyester resin 10 agent is added to a polyester resin and the resultant composition. More particularly, the present invention mixture is injected into a mold while the temperature of relates to a thermoplastic polyester resin composition the mold is maintained at a level of 85 C. to 110 C., having a high crystallinity and excellent moldability, since the velocity of crystallization of the polyester mechanical strength and dimensional stability. resin in the mold is unsatisfactorily low, the separation 2. Description of the Prior Art 15 of the resultant molded product from the mold becomes It is known that polyester resins, for example, poly unsatisfactory and a long time period of the cooling ethylene terephthalate resins, have excellent mechani procedure must be applied to the molded product. Also, cal properties, chemical resistance, heat resistance and since the crystallization of the molded polyester resin electrical properties and, therefore, are widely utilized product is not completed in the mold, the resultant in the production of electrical insulating materials, auto 20 product exhibits an unsatisfactory resistance to heat mobile parts and the like. The above-mentioned proper when the product has a small thickness. If this type of ties can be enhanced by the addition of various addi product is exposed to a high temperature atmosphere, tives, for example, fiber reinforcement, e.g. glass fibers an additional crystallization of the polyester resin takes or carbon fibers, function-imparting materials, e.g. place, which results in changes in the dimensions of the flame retarder, antistatic agent or antioxidant, and the 25 product. like. Due to the enhancement, the use of polyester resins Polybutylene terephthalate resin exhibits such an has increasingly been broadened. advantageous property that, even if the temperature of It is also known that generally, the properties of a the injection mold is 100 C. or less, the injected resin is crystalline polymer resins, such as polyethylene tere easily crystallized uniformly in the mold, and, therefore, phthalate resins, are variable, largely depending on the 30 the molded product has a uniform crystallinity from the degree of crystallinity thereof. center portion to the surface layer of the molded prod Therefore, it is possible to increase various proper uct. That is, polybutylene terephthalate resin has an ties, such as dimensional stability and resistances to excellent moldability, similar to that of nylon resins and chemicals and heat (heat deflection temperature) of the polyacetal resins. However, polybutylene terephthalate polyester resin, by enhancing the degree of crystallinity 35 resins are disadvantageous in that the shrinkage thereof of the polyester resin. in the molding procedure is undesirable large-and the There have been various attempts to increase the heat resistance thereof is unsatisfactory. degree of crystallinity of the polyester resins. For exam Various attempts were carried out to obtain a mixture ple, U.S. Pat. No. 3,368,995 discloses a method in which of polyethylene terephthalate resin with polybutylene a molded polymer resin article is prepared in a partially 40 terephthalate, having a reduced shrinkage and en crystallized state and, then, subjected to a post-heat hanced heat resistance. These attempts are disclosed, treatment to complete the crystallization of the article. for example, in Japanese Unexamined Patent Publica In another known method, the molded polyester resin tion (Kokai) Nos. 50-33832 (1975), 53-92862 (1978), and article in the partially crystallized state is immersed in a 54-94556 (1979). However, the improved properties of treating liquid capable of promoting the crystallization 45 the above-mentioned mixtures are still unsatisfactory. of the polyester resin. Recently, there has been a tendency whereby some However, the above-mentioned known methods are molded materials are required to have an enhanced disadvantageous in that, after the molding procedure, it function, a reduced weight and a reduction in the is necessary to apply a certain post-treatment to the amount of raw materials consumed. In order to meet molded article, and, therefore, such methods are not 50 with the above-mentioned requirements, polyester ma always satisfactory. terials are molded into a complicated shape with a small British Pat. No. 1,111,012 discloses still another thickness or size and a compact structure. In this case, it method in which the molding procedure is carried out is indispensable that the melt of a polyester material to by injecting a polyester resin melt into a mold which has be molded exhibits excellent mobility in a mold during been heated to a temperature of approximately 140 C. 55 the molding procedure. and then, solidifying the molded polymer resin in the The mobility of the melted thermosplastic polyester mold so as to accelerate the crystallization of the poly resin largely depends on the molecular weight of the mer resin. However, this method is disadvantageous in polyester resin. It is well known that the higher the that the use of a beating medium is necessary to main molecular weight of the polyester resin, the lower the tain the temperature of the mold at the desired high 60 mobility of the melt of the polyester resin. Therefore, a level, which is undesirable from the point of view of polyester resin having a low molecular weight may be safety and of saving energy in the molding procedure, used as a molding thermoplastic polyester resin having and in that the molding cycle time becomes long. a satisfactory mobility. In order to eliminate the above-mentioned disadvan However, it is also well known that the mechanical tages of the prior art, attempts were made to utilize 65 strength, for example, tensile strength and toughness, various crystal nucleus-forming agents so as to acceler such as flexural strength, of the molded material de ate the crystallization of the polyester resin. For exam pends on the molecular weight of the polyester resin. ple, British Pat. No. 1,111,012 also discloses a method of That is, the lower the molecular weight of the polyester 4,536,531 34 resin, the poorer the mechanical strength of the molded The polyester resin composition of the present inven product from the polyester resin. When a thermoplastic tion contains a crystal nucleating agent and optionally polyester resin having a low molecular weight is an additive selected from inorganic fillers. The crystal molded, the resultant product exhibits a poor mechani nucleating agent is effective for promoting the start of cal strength. If the polyester resin having a low molecu- 5 crystallization of the polyester resin. lar weight and, therefore, exhibiting a high mobility, is The inorganic filler is effective for enhancing the used for producing a molded product having a small mechanical strength, the surface property, electric thickness, the resultant molded product naturally exhib properties and/or thermal properties of the polyester its very poor mechanical strength and, therefore, is resin compound. useless for actual use. 10 Also, the polyester resin composition of the present Various attempts were made to provide molded invention may additionally contain at least one phos products having enhanced mechanical strength. For phorus compound selected from those of the formulae example, U.S. Pat. No. 3,578,729 discloses a mixture of (II) and (III) a thermoplastic polyester resin with an acrylic type ester-ethylene copolymer; U.S. Pat. No. 3,591,659 dis- 15 closes a mixture of a thermoplastic polyester resin with Y (II) a polyacrylic aliphatic ester; Japanese Examined Patent Publication (Kokoku) No. 46-5224 discloses a mixture of a thermoplastic polyester resin with a rubber-like Z--P--z II 0 polymer such as butyl rubber; U.S. Pat. No. 3,368,995 20 and discloses a mixture of a thermoplastic polyester resin with glass fibers; Japanese Examined Patent Publication Y (III) (Kokoku) No. 48-32948 discloses a mixture of a thermo X--P--Z plastic polyester resin with aromatic polyamine fibers; and Japanese Examined Patent Publication (Kokoku) 25 wherein X, Y and Z respectively represent, indepen No. 48-6175, U.S. Pat. No. 3,553,157, and U.S. Pat. No. dently from each other, a member selected from the 3,583,935 disclose mixtures of polyester resins with group consisting of a hydrogen atom, radicals of the epoxy compounds. formula -OR3 in which R3 represents a member selected However, the above-mentioned attempts resulted in from a hydrogen atom and monovalent hydrocarbon decreased mobilities of the resultant polymer mixtures. 30 radicals. Therefore, the polymer mixtures were not suitable for The above-mentioned phosphorus compounds are molding a product having a small thickness. effective for enhancing moldability and crystallinity of . SUMMARY OF THE INVENTION the polyester resin composition at a relatively low molded temperature. An object of the present invention is to provide a 35 Furthermore, the polyester resin composition of the polyester resin composition which is capable of provid present invention may additionally contain, together ing a molded product having excellent dimensional with the above-mentioned phosphorus compound, at stability and heat resistance at low cost, even when the least one epoxy compound selected from those of the molding procedure is carried out at a relatively low formula (IV): temperature of the mold of 110 C. or less. 40 Another object of the present invention is to provide a polyester resin composition which has enhanced mo bility when melted and which is capable of providing a (CH2------ CH--CHjO.C^R4 molded product having excellent toughness. o The above-mentioned objects can be attained by the 45 wherein n represents an integer of 2 or more and R4 polyester resin composition of the present invention represents a hydrocarbon radical having the number of which comprises: valences corresponding to n. (A) at least one thermoplastic polyester resin selected The combination of the phosphorus compound with from the group consisting of polyethylene terephthalate the epoxy compound is effective for increasing the heat resins and polybutylene terephthalate resins; and 50 resistance of the polyester resin composition. (B) per 100 parts by weight of the polyester resin, 0.1 to 30 parts by weight of a polycaprolactone having a number average molecular weight of from 200 to 2,000, DESCRIPTION OF THE PREFERRED EMBODIMENTS which polycaprolactone molecules have terminal radi The polyester resin composition of the present inven cals thereof modified to be nonreactive and in the num- 55 tion comprises a component (A) consisting of at least ber corresponding to 50% or more of the entire number one thermoplastic polyester resin selected from poly of the terminal radicals in the polycaprolactone mole ethylene terephthalate resins and polybutylene tere cules; and phthalate resins, 0.1 to 30 parts by weight of a compo (C) 0.01 to 10 parts by weight of a crystal nucleating nent (B) consisting of a polycaprolactone having a num agent for the polyester resin, per 100 parts by weight of 60 ber average molecular weight of from 200 to 2,000, per the polyester resin. 100 parts by weight of the component (A) and 0.01 to 10 Since at least 50% of the terminal radicals of the parts by weight of a crystal nucleating agent for the polycaprolactone molecules are modified to be non component (A) per 100 parts by weight of the compo reactive, the resultant polyester resin composition can nent (A). The polycaprolactone molecules have termi be molded at an elevated temperature without decreas- 65 nal radicals thereof modified to be non-reactive and in ing the degree of polymerization of the polyester resin the number corresponding to 50% or more of the entire and without deteriorating the physical and chemical number of the terminal radicals of the polycaprolactone properties of the molded composition. molecules. 56 The polyethylene terephthalate resins usable for the strength. When the polyester resin composition con present invention consist of at least one member se tains no filler, it is preferable that the polyethylene lected from polyethylene terephthalate homopolymers terephthalate resin have an intrinsic viscosity of from which are obtainable from an acid component, such as 0.35 to 1.5, more preferably, from 0.4 to 1.2. When the terephthalic acid or an ester-forming derivative thereof, 5 intrinsic viscosity of the polyester resin is excessively and a glycol component, such as ethylene glycol or an large, the resultant resin composition exhibits an unsat ester-forming derivative thereof, and polyethylene tere isfactory moldability. phthalate copolymers in which the above-mentioned When the polyester resin composition contains a acid component contains a small amount of at least one large amount of reinforcing fibers, for example, glass copolymerizable dicarboxylic acid in addition to ter 10 fibers, as a filler, it is preferable that the polyethylene ephthalic acid or its derivative, and/or the above-men terephthalate resin have an intrinsic viscosity of from tioned glycol component contains a small amount of at 0.35 to 0.9, more preferably, from 0.4 to 0.8, because the least one copolymerizable diol compound, in addition reinforcing fibers results in a reduced mobility of the to ethylene glycol or its derivative. resultant composition. The copolymerizable dicarboxylic acids may be se 15 The polyethylene terephthalate resins usable for the lected from aromatic dicarboxylic acids, for example, present invention can be prepared by a usual polymeri isophthalic acid, phthalic acid, alkyl-substituted zation method, for example, a melt polymerization phthalic acids, e.g. methylterephthalic acid and me- method or a combination of a melt polymerization and thylisophthalic acid, naphthalene-dicarboxylic acids, solid phase polymerization. e.g. naphthalene-2,6-dicarboxyIic acid, naphthalene-2,7- 20 The polybutylene terephthalate resins usable for the dicarboxylic acid, and naphthalene-1,5-dicarboxylic present invention consist of at least one member se acid, and diphenoxyethane dicarboxylic acids, e.g. 4,4'- lected from polybutylene terephthalate homopolymers diphenoxyethanedicarboxylic acid; aliphatic dicarbox and copolymers. The homopolymers are obtained from ylic acids, for example, succinic acid, adipic acid, seba- an acid component consisting of terephthalic acid or its cic acid, azelaic acid and decadicarboxylic acid; and 25 ester-forming derivative and a glycol component con alicyclic dicarboxylic acids, for example, cyclohex- sisting of tetramethylene glycol or its ester-forming anedicarboxylic acid. derivative. In the polybutylene terephthalate copoly The copolymerizable diol compounds may be se mers, the acid component and/or the glycol component lected from aliphatic and alicyclic diols, such as tri- contain a small amount of copolymerizable compounds, methylene glycol, tetramethylene glycol, hexamethyl- 30 which may be selected from ethylene glycol and the ene glycol, neopentyl glycol, diethylene glycol, 1,4- same the copolymerizable compounds as those usable cyclohexanedimethanol; dihydroxybenzenes, such as for the polyethylene terephthalate copolymers, except hydroquinone and resorcinol; bisphenols, such as 2,2- for tetramethylene glycol. bis(4-hydroxydiphenyl)-propane and 2,2-bis(4-hydrox- It is preferable that the polybutylene terephthalate ydiphenyl)-sulfone and aromatic diols, such as ether 35 resins exhbit an intrinsic viscosity of from 0.4 to 1.5, diols obtainable from bisphenols and glycols such as more preferably, 0.5 to 1.2, determined in ortho-chloro ethylene glycol. phenol at a temperature of 35 C. Also, hydroxycarboxylic acids, such as e-hydroxyca- The polybutylene terephthalate resins usable for the proic acid, hydroxyethoxybenzoic acid and hydroxye- present invention can be produced by usual polymeriza thoxybenzoic acid are usable as a part of the acid com 40 tion methods, for example, a melt polymerization ponent. method or a solid phase polymerization method. These copolymerizable components may be em The polyester resin usable for the present invention ployed alone or as a mixture of two or more thereof. preferably consists of a polyethylene terephthalate resin Preferably, they are employed in an amount of not more or polybutylene terephthalate alone or a mixture of 5 to than 20 molar %, more preferably, 10 molar % or less, 45 95%, more preferably, 20 to 90%, still more preferably, of the total amount of the acid component (hydroxycar 40 to 90%, by weight of a polyethylene terephthalate boxylic acids should be calculated as a half thereof resin and 5 to 95%, more preferably, 10 to 80%, still being the carboxylic acid), or of the glycol component. more preferably, 10 to 60% by weight of a polybutylene The polyethylene terephthalates usable for the pres terephthalate. ent invention may have, in molecular structure, at least 50 The above-mentioned preferable polyester resins one branched chain derived from copolymerization of a exhibit an excellent heat resistance, a reduced shrinkage small proportion of a trifunctional ester-forming acid, and mobility during the molding procedure and an en such as tricarballylic acid, trimesic acid or trimellitic hanced moldability and toughness and are useful for acid; a tetrafunctional ester-forming acid, such as pyro- producing molded products having a satisfactory ap mellitic acid; a trifunctional ester-forming alcohol com 55 pearance. pound, such as glycerine or trimethylolpropane; or a The polyester resin composition of the present inven tetrafunctional ester-forming alcohol compound, such tion contains, as a component (B), a modified polyca- as pentaerythritol. The polyfunctional compounds are prolactone having a number average molecular weight used preferably in a proportion of 1.0 molar % or less, of from 200 to 2,000, preferably from 300 to 1,800, more more preferably, 0.5 molar % or less, still more prefera 60 preferably from 400 to 1,600. The polycaprolactone can bly, 0.3 molar % or less. be prepared by the ring-opening polymerization of e- The polyethylene terephthalate resins usable for the caprolactone in the presence of a cationic or anionic present invention preferably have an intrinsic viscosity polymerization-initiating agent. of 0.35 or more, more preferably 0.45 or more, deter It was found for the first time by the inventors of the mined in a solvent consisting of ortho-chlorophenol at a 65 present invention that the polycaprolactone, which has temperature of 35' C. The use of a polyethylene tere been modified as clarified hereinafter, is highly effective phthalate resin of an intrinsic viscosity less than 0.35 for promoting the crystallization of the polyester resin. sometimes may provide a molded article of a low This effect of the polycaprolactone can be further pro- 4,536,531 8 moted by using a crystal nucleating agent which will be When e-caprolactone is ring-opening polymerized in clarified thereinafter. the presence of the above-mentioned initiator, the ring It was also found by the inventors of the present opening polymerization reaction may be accelerated by invention for the first time that the polycaprolactone using a catalyst consisting of a member selected from tin capable of promoting the crystallization of the polyester 5 compounds, for example, tetraoctyi tin and diphenylresin must have a number average molecular weight of tin-dilaurate, and titanium compounds, for example, from 200 to 2,000. When the number average molecular tetrabutyl titanate. weight is more than 2,000, the polycaprolactone exhib The polycaprolactone usable for the present inven its substantially no, or a very poor, effect of promoting tion is modified in such a manner that at least 50% of the the crystallization of the polyester resin. Also, when the 10 terminal radicals of the polycaprolactone molecules are number average molecular weight is less than 200, the modified with a blocking agent, so that the modified . resultant polyester resin composition results in a practi terminal radicals become non-reactive. cally useless molded product having a significantly The non-modified polycaprolactone molecules have decreased mechanical strength. The reason of the de terminal radicals thereof, each consisting of a free car crease in the mechanical strength of the molded product *5 boxyl radical or hydroxyl radical which is highly reac is not completely clear. It is assumed, however, that in tive. The reactive terminal radicals can be converted to the melt-mixing procedure of the polyester resin with non-reactive radicals by reacting the terminal radicals polycaprolactone to provide a polyester resin composi with a monovalent blocking agent, the molecule of tion or in the molding procedure of the resultant polyes which has a moiety reactive with the carboxylic and/or ter resin composition, the polycaprolactone having a low molecular weight reacts with a polyester resin and this reaction results in a decrease in the molecular weight of the polyester resin. Accordingly, it is necessary that the number average molecular weight of the polycaprolactone to be used 20 ^ hydroxyl radical and another moiety which is non-reactive. The type of the terminal radicals in the polycaprolac tone molecules is variable, depending on the type of the ring-opening polymerization initiator used. When the initiator consists of an alcohol compound, the resultant terminal radicals consist of a hydroxyl radical. When for the present invention is in a range of from 200 to 2,000, preferably from 300 to 1,800, more preferably, the initiator consists of a carboxylic acid compound, the resultant terminal radicals consist of a carboxylic radi 400 to 1,600. cal. When the initiator consists of a hydroxycarboxylic The component (B) is used in an amount of from 0.1 acid or water, the resultant terminal radicals consist of to 30 parts by weight, preferably, from 0.5 to 10 parts by a hydroxyl radical and a carboxyl radical. weight per 100 parts by weight of the polyester resin. If In the above-mentioned compounds usable as the the amount of the component (B) is less than 0.1 parts by weight, the resultant composition exhibits an unsatis factory crystallization rate. The effect of promoting the crystallization of the polyester resin reaches a substan initiator, preferable compounds are glycol compounds. It is necessary that the number of the modified termi nal radicals in the polycaprolactone molecules corre spond to 50% or more, more preferably, 70% or more, tially maximum when the amount of component (B) of the entire number of the terminal radicals in the reaches 20 parts by weight. That is, an increase in the polycaprolactone molecules. It is ideal that the terminal amount of component (B) to more than 30 parts by radicals in the polycaprolactone be entirely modified to weight is not only not effective for increasing the effect 40 non-reactive radicals, in order to completely stabilize of promoting the crystallization of the polyester resin, the polycaprolactone in the molding procedure at an but also results in a decrease in the mechanical proper elevated temperature. ties of the molded product. In the modification, the polycaprolactone is brought The ring-opening polymerization of e-caprolactone is into reaction with a blocking monovalent compound, carried out in the presence of a polymerization initiator 45 which has a reactive moiety capable of reacting the (catalyst). The catalyst may consist of at least one mem terminal carboxyl or hydroxyl radicals in the polyca- ber selected from monohydric alcohols, for example, ploiactone, and a non-reactive moiety which becomes a n-hexylalcohol, n-heptylalcohol, n-octylalcohol, n- non-reactive terminal radical of the modified polyca- nonylalcohol, laurylalcohol and myristylalcohol; glycol prolactone after the blocking compound reacts with the compounds, for example, ethylene glycol, propylene 50 polycaprolactone. glycol, ethylethylene glycol, 2-methyl-1,2-propane- The reaction between the blocking compound with diol, pinacol, e-butylene glycol, diethylene glycol, tetra- the polycaprolactone may be of any type selected from methylene glycol, neopentyl glycol and 1,4-cyclohex- the ester-, ether, urethane and amideforming reactions. ane dimethanol; trihydric alcohols, for example, glycer However, the preferable type of reaction is an ester- ine, 1,2,3-butane-triol and 1,2,3-pentane-triol; tetrahy- 55 forming reaction. The blocking compound usable for dric alcohols, for example, erythritol and pentaerythri- the ester-forming reaction can be selected from, for toi; monovalent carboxylic acids, for example, benzoic example, monovalent carboxylic acids and ester-form acid, p-methylbenzoic acid lauric acid and myricylic ing derivatives thereof, when the terminal radicals are acid; divalent carboxylic acids, for example, isophthalic hydroxyl radicals, and monovalent alcohols or ester- acid, phthalic acid, terephthalic acid, 2,6-naphthalene 60 forming derivatives thereof, when the terminal radicals dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic are carboxyl radicals. The monovalent carboxyl acids acid, citric acid, adipic acid, sebacic acid, azelaic acid, and ester-forming derivatives may be selected from decadicarboxylic acid and cyclohexane dicarboxylic acetic acid, propionic acid, butyric acid, valeric acid, acid; trivalent carboxylic acid, for example, tricarbally- caproic acid, heptanoic acid caprylic acid, lauric acid, lic acid, trimesic acid and trimellitic acid; tetravalent 65 myristicic acid, benzoic acid, toluic acid, dimethyl ben carboxylic acids, for example, pyromellitic acid; and zoic acid, ethyl benzoic acid, cuminic acid, 2,3,4,5- hydroxycarboxylic acid, for example, e-hydroxycar- tetramethylbenzoic acid, and ester-forming anhydrides, boxylic acids and hydroxyethoxybenzoic acids. acid halides and esters of the above-mentioned carbox- 9 10 ylic acids, for example, phenyl acetate, ethyl caproate, filler consisting of glass fibers is blended to the polyester methyl benzoate and ethyl toluate. The monovalent alcohols and ester-forming deriva resin composition, the resultant product exhibits not only a highly enhanced mechanical strength, but also tive thereof involve methyl alcohol, ethyl alcohol, n- highly increased resistances to heat and deformation at propyl alcohol, isopropyl alcohol, isobutyl alcohol, 5 an elevated temperature. The above-mentioned effects n-amylabiohol, lauryl alcohol and esters of the above- of the glass fibers are assisted by the polycaprolactone mentioned alcohols, for example, halo-carbonic esters and the crystal nucleating agent used concurrently with and carboxylic esters of the above-mentioned alcohols. the glass fibers. In order to prepare the terminal-modified polyca- The glass fibers, usable for the above-mentioned pur prolactone, a known ester-forming reaction can be ap- io pose, may be selected from usual reinforcing glass fibers plied between the polycaprolactone and the blocking compound. The preferable terminal-modified polycaprolactone is of the formula (I): for resinous materials, for example, filamentary type glass fibers (glass rovings), and staple type glass fibers, such as chopped strands and milled fibers. The glass fibers may be treated with a fiber bundle-forming agent [R1 C0-fO4-CH^;CC>)-,,0}7))R-(-C0--0-fCH2)- 15 comprising a polyvinyl acetate or a polyester, a cou sCO^OR2], (I) pling agent comprising a silane compound or a boran compound or another surface-treating agent. The glass wherein n and p respectively represent, independently fiber may also be coated with a thermoplastic resin or from each other, an integer of 2 or more; m and q re thermosetting resin. If the glass filaments are used, it is spectively represent, independently from each other, usually preferable for the filaments to be cut into a zero or an integer of from 1 to 4 and the sum of m and desired length before or while the filaments are blended q is 1 or more; R represents an organic radical having a to the polyester resin. valence corresponding to the sum of m + q; and R1 and When the filler is used, it should be considered that R2 respectively represent, independently from each the filler is used in a minimum amount, which is suffi other, a monovalent organic radical. 25 cient for attaining the purpose of using the filler. If the In the formula (I), when R represents a residue of a filler is used in an excessive amount, the content of the glycol compound, q represents zero, m represents an polyester resin in the resultant composition becomes integer of 2, and R'CO-- represents a residue of a relatively small and, therefore, the properties of the monovalent carboxylic acid used as a blocking com resultant composition, which are derived from the poly pound. When R represents a residue of a dicarboxylic 30 ester resin, become unsatisfactory. Also, an excessive acid, m represents zero, q represents an integer of 2 and amount of the filler results in a decrease in moldability, --DR2 represents a residue of a monovalent alcohol especially, in the mobility of the melted composition in used as a blocking compound. When R represents a the molding procedure. In consideration of the above- residue of a hydroxycarboxylic acid, m and q are 1, respectively, R'CO-- is a residue of a monocarboxylic acid used as a blocking compound and --R2 is a residue of a monovalent alcohol used as a blocking agent. The polycaprolactone having modified terminal radi cals thereof, are remarkably effective for promoting the crystallization of the polyester resin. This effect is enhanced by concurrently using the terminal-modified polycaprolactone with the crystal nucleating agent. Also, the terminal-modified polycaprolactone is effec 35 40 mentioned items, it is preferable that the filler be used in n amount of 200 parts by weight or less, more prefera bly, 5 to 200 parts by weight, per 100 parts by weight of the polyester resin. If the filler is used in an amount of more than 200 parts by weight, the melt of the resultant polyester composition exhibits poor mobility and, there fore, the resultant molded product exhbits an unsatisfac tory appearance. Also, the addition of the additional amount of the filler over 200 parts by weight is not tive for enhancing the mobility of the melt of the poly effective for increasing the mechanical strength, heat ester resin and for increasing the mechanical strength, 45 resistance and other properties of the resultant polyester tensile elongation, impact strength and toughness of the resin composition. resultant molded product. The polyester resin composition of the present inven The terminal-modified polycaprolactone have a num tion contains 0.01 to 10 parts by weight of a crystal ber average molecular weight of 200 to 2,000, prefera nucleating agent for the polyester resin per 100 parts by bly not exceeding 1,800, more preferably not exceeding 50 weight of the polyester resin. The crystal nucleating 1,600. agent useable for the present invention can be selected The terminal-modified polycaprolactone is used in an from known crystal nucleating agents for usual polyes amount of from 0.1 to 30 parts by weight, preferably, ter resin, including polyethylene terephthalate resins, from 0.5 to 15 parts by weight, still more preferably, but is not limited to the known crystal nucleating from 0.5 to 10 parts by weight, based on 100 parts by 55 agents. weight of the polyester resin. For example, the crystal nucleating agent comprises The polyester resin composition may contain, as an additional component, 200 parts by weight or less of an at least one member selected from inorganic solid sub stances, for example, carbon powder, neutral clay, and inorganic filler, per 100 parts by weight of the polyester oxides, sulfates, phosphates and silicates of metals of resin. The filler may comprise at least one member 60 Group II in the Periodic Table, which are disclosed in selected from glass fibers, asbestos, carbon fibers, potas Japanese Examined Patent Publication (Kokoku) No. sium titanate fibers and mica, silica, talc calcium carbon 44-7542 (1969), finely divided pyroferrite which is dis ate, glass, clay and wollastonite in the form of particles, closed in Japanese Examined Patent Publication grains, flakes, and small plates. (Kokoku) No. 45-2622 (1970) titanium dioxide disclosed The fillers are used for the purpose of enhancing the 65 in Japanese Examined Patent Publication (Kokoku) No. mechanical strength, surface property, electric property 46-7180 (1971), talc and gypsum disclosed in Japanese and thermal properties of the polyester resin composi Examined Patent Publication (Kokoku) No. 47-3025 tion or molded products thereof. Especially, when a (1972), and boron nitride described in Japanese Exam- 4,536,531 11 12 ined Patent Publication (Kokoku) No. 47-25850 (1970); metal salts of organic carboxylic acids, for example, oxalates, stearates, benzoates, salicylates and tartrates of metals of Group II in the Periodic Table, which are disclosed in Japanese Examined Patent Publication R5 R6 -CH2-CH7rf-CH2--<j% Me+, JMe+ + or JMe+ + H (Kokoku) No. 44-7542 (1969), sodium benzoate dis closed in Japanese Examined Patent Publication (Kokoku) No. 46-29977 (1971), montan wax salts and c=o I O- montan wax ester salts disclosed in Japanese Examined Patent Publication (Kokoku) No. 47-13137 (1972), lith 10 in which R5 represents a hydrogen atom, an alkyl radi ium terephthalate, sodium stearate and potassium ben cal having 1 to 12 carbon atoms or a phenyl radical; R6 zoates described in Japanese Examined Patent Publica represents a hydrogen atom, or a methyl or ethyl radi tion (Kokoku) No. 47-14502 (1972); metal salts of or cal; Me represents metal ion of Group I or II in the ganic sulfonic acids described in Japanese Examined Periodic Table; a, b and c respectively represent, inde Patent Publication (Kokoku) No. 47-27142 (1972); com 15 pendently for each other an integer of 1 or more. pletely or partially neutralized salts and ester salts of Ionic copolymers of an a-olefin and an a.,/3- saturated tert-monocarboxylic acid mixtures described unsaturated dicarboxylic acid salt, for example, of eth in Japanese Examined Patent Publication (Kokoku) No. ylene and maleic acid or itaconic acid, and containing 47- 27780 (1972), sodium, lithium and barium salts of ionic groups of metal of Group I or II in the Periodic mono- and poly-carboxylic acids described in Japanese 20 Table may also be used. Examined Patent Publication (Kokoku) Nos. 47-32435 Other examples of the ionic copolymer are ionic graft (1972), 48-4097 (1973) and 48-4098 (1973) and glyco- copolymers obtained, for example, by grafting an a,j3- lates of alkaline earth metals, titanium, germanium, unsaturated carboxylic acid ester to a polyolefin, by antimony, tungsten and manganese described in Japa nese Examined Patent Publication (Kokoku) No. 25 saponifying the graft polymer and then reacting it with an alkali metal hydroxide. The above-mentioned ionic 48- 12861 (1973); and ionic copolymers of a-olefins with copolymers should preferably have an olefin content of a,/3-unsaturated carboxylic salts described in Japanese at least 50% by weight. Copolymers having an olefin Examined Patent Publication (Kokoku) No. 45-26225 content of 80 to 99% by weight may especially be suit (1970), the crystal nucleating agent consisting of the able. organic carboxylic acid metal salts alone is used prefera Further examples of a ionic copolymers are those bly in an amount of 0.01 to 3 parts by weight per 100 copolymers having the following units (A), (B) and (C), parts by weight of component (A). Also, the crystal nucleating agent consisting of the inorganic substances only is used preferably in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the component (A). Furthermore, the crystal nucleating agent consisting of R5 I -f"CHj CH-)j (A) the ionic copolymers alone is used preferably in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the component (A). 40 In the above-mentioned compounds, preferable com pounds for the crystal nucleating agent to be used, in combination with the terminal-modified polycaprolac- tone, are talc particles having a size of 20 microns or less, carboxylic salts of metals in Groups I and II in the 45 R6 -CH2--C- c=o I \ o- Me+ or !Me+ + (B) Periodic Table and ionic copolymers of -olefins with a, /3-unsaturated carboxylic salts. The carboxylic salts of metals of Groups I and II in R7 I -f-CH2--CJy (C) the Periodic Table may be exemplified metal salts of aliphatic monocarboxylic acids, such as acetic acid, 50 propionic acid, caproic acid, palmitic acid, stearic acid, c=o I o oleic acid, behenic acid, montanic acid, methacrylic acid and acrylic acid; of aliphatic dicarboxylic acids, such as oxalic acid, adipic acid, succinic acid, sebacic in which R5, R6 and Me are as defined above, R7 repre acid, maleic acid and fumaric acid; and of aromatic 55 sents a hydrogen atom or a methyl or ethyl radical, R8 carboxylic acids, such as benzoic acid, terephthalic acid represents a hydrogen atom or an alkyl radical having 1 and phthalic acid. Suitable metals are sodium, potas to 12 carbon atoms, and d, e and f respectively repre sium, lithium, magnesium, calcium barium and zinc. In sent, independently from each other, an integer of 1 or these carboxylic acid salts, it is unnecessary that all the more. These ionic copolymers should preferably have carboxyl groups by converted into salt form thereof, 60 an olefin content of at least 50% by weight, with those but a part of the carboxyl groups may be in a salt form having an olefin content of 80 to 90% by weight being and the remaining groups may be in a free acid or ester especially preferable. Preferably, the total content of form. the ester component ((C)) and the ionic component The ionic copolymers may be prepared by a known ((B)) may be at least 10% by weight and the content of method as described, for example, in Japanese Patent 65 the ionic component ((B)) may be at least 3% of the Application Publication (Kokoku) No. 39-6810 (1964). weight of the ionic copolymer. Ail the carboxyl groups Examples of the ionic copolymer are those polymers of the ionic copolymer need not always be neutralized, having the units of the following structural formula, but at least 10% of the carboxyl groups should be neu- 13 14 tralized by metal ions. The metal ions may be selected above-mentioned compounds, preferable ones are tri- from ions of the metals described in Japanese Examined methyl phosphate and phosphorous esters, such as tri Patent Publication (Kokoku) No. 39-6810 (1964). phenyl phosphite. Especially preferable metal ions are alkali metal ions, The phosphorus compounds can be used singly or in particularly the sodium ion. Especially preferable ionic 5 combination of two or more thereof. copolymers are those of ethylene and methacrylic acid The phosphorus compounds of the formulae (II) and and containing an alkali metal ion, particularly the so (III) are effective for enhancing the heat resistance of dium ion. the resultant polyester resin composition. The phospho The crystal nucleatng agent is used usually in an rus compounds are used in an amount of 2 parts by amount of 0.01 to 10 parts by weight, preferably from 0.05 to 10 parts by weight, per 100 parts by weight of the polyester resin. An excessive amount of over 10 parts by weight of the crystal nucleating agent is not only not effective for 10 weight or less, preferably, from 0.01 to 2 parts by weight of the polyester resin. An excessive amount over 2 parts by weight of the phosphorus compounds is not only not effective for increasing the heat resistance of promoting the crystallization of the polyester resin but 15 the resultant polyester resin composition, but, also, also, results in decreases in the mechanical strength and causes the resultant molded product to exhibit a re other properties of the resultant molded product. A too duced mechanical strength. small amount of less than 0.01% by weight of the crys The polyester resin composition of the present inven tal nucleating agent is unsatisfactory in the promotion tion may contain, in addition to the above-mentioned of the crystallization of the polyester resin. Usually, the 20 phosphorus compounds of the formulae (II) and (III), a crystal nucleating agent is used in an amount as de further additive consisting of at least one epoxy com scribed in Japanese Patent Examined Publication pound selected from those of the formula (IV): (Kokoku) Nos. 44-7542, 45-26222, 45-26225, 46-7180, 46- 29957, 47-3025, 47-13137, 47-14502, 47-25850, 47- 27142, 47-27780, 47-32435, 48-4097, 48-4098, and 25 (IV) 48- 12861, depending upon the type of the crystal nucle ating agent. The polyester resin composition of the present inven tion may contain an additive consisting of at least one CHj------ CH--CH-.0--C \/ -R4 V / phosphorus compound selected from those of the formulae (II) and (III): wherein r represents an integer of 2 or more and R4 represents a r-valent hydrocarbon radical, and when r is 2, R4 may be a radical of the formula Y (II) X--P--z o 35 '0--@r'or ^r- _ and Y 1 X--P--z The epoxy compounds of the formula (IV) are a (HI) certain type of 2,3-epoxypropanol esters of polyfunc 40 tional carboxylic acids. In the formula (IV), the hydrocarbon radicals repre wherein X, Y and Z respectively represent, indepen sented by R4 include aliphatic hydrocarbon radicals dently from each other, a member selected from the having 16 carbon atoms, such as methylene, ethylene group consisting of a hydrogen atom, monovalent hy trimethylene, tetramethylene, peutamethylene, hexa- drocarbon radicals, and radicals of the formula --OR3 45 methylene, heptamethylene, octamethylene, and nona- in which R3 represents a member selected from a hydro methylene; cycloaliphatic hydrocarbon radicals, such gen atom and monovalent hydrocarbon radicals. as cyclophexylene; and aromatic hydrocarbon radicals, The monovalent hydrocarbon radicals represented such as phenylene, naphthylene, methylphenylene and by X, Y, Z and R3 independently from each other, in the radicals of the formulae: formulae (II) and (III), are selected from substituted and 50 unsubstituted alkyl, aralkyl and aryl radicals each hav ing 12 carbon atoms or less. The alkyl radicals include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, octyl and decyl radicals. The aryl radicals include phenyl, napthyl, methyl phenyl, phenylphenyl 55 ch3 and bromated phenyl radicals. The aralkyl radicals include a benzyl radical. The examples of the phosphorus compounds of the CH2CH2 formulae (II) and (III) include phosphoric esters, such as phosphoric acid, trimethyl phosphate, methyldiethyl 60 When r is 2, R4 may be a divalent radical of the for phosphate, triethyl phosphate, triisopropyl phosphate, mula: tributyl phosphate, and triphenyl phosphate; phospho rous esters, such as phosphorous acid, trimethyl phos phite, triethyl phosphite and triphenyl phosphite; phos- ^^-0--@r'or ^@"- phonic compounds, such as, phosphonic acid, phenyl- 65 phosphonic acid and phenyl phenylphosphonate; and phosphinic compounds, such as phosphinic acid, phe- In the formula (IV), r is an integer of 2 or more, prefera nylphosphinic acid and dimethylphosphinic acid. In the bly, from 2 to 6, still more preferably, 2. 4,536,531 15 16 The examples of the epoxy compounds of the formula Furthermore, the polyester resin composition of the (IV) are di-2,3-epoxypropanoI ester of terephthalic present invention may contain still other additives, such acid, di-2,3-epoxypropanol ester of isophthalic acid, as ultraviolet absorbers, coloring agents, lubricants, di-2,3-epoxypropanol ester of phthalic acid, tri-2,3- antistatic agents and blowing agents. epoxypropanol ester of trimeilitic acid, tetra-2,3-epoxy- 5 Still furthermore, the polyester resin composition of propanol ester of pyromellitic acid, di-2,3-epoxy the present invention may contain a small amount of a propanol ester of diphenyl dicarboxylic acid, di-2,3- thermoplastic resin other than the specific polyester epoxypropanol ester of adipic acid, di-2,3-epoxy resin of the present invention and/or a thermosetting propanol ester of succinic acid, di-2,3-epoxypropnaol resin. The other thermoplastic resin may comprise at ester of dodecane dicarboxylic acid, di-2,3-epoxy- 10 least one member selected from styrol resins, acrylic propanol ester of cyclonexane dicarboxylic acid, di-2,3- resins, polyethylene resins, polypropylene resins, fluo epoxypropanol ester of naphthalene dicarboxylic acid rine-containing polymer resins, polyamide resins, poly and di-2,3-epoxypropanol ester of methyl terephthalic carbonate resins, polysulfone resins and soft thermo acid. plastic resins, for example, ethylene-vinyl acetate co The epoxy compounds of the formula (IV) may be 15 polymers and polyester elastomers. used singly or in combination of two or more thereof. The thermosetting resin may comprise at least one The epoxy compound may contain a small amount of member selected from phenol resins, melamine resins, oligomers thereof which are by-products in the prepara unsaturated polyester resins, and silicone resins. tion thereof. The epoxy compounds of the formula (IV) are used in 1 The polyester resin composition of the present inven tion can be prepared by a conventional blending proce an amount of 3 parts by weight or less, preferably, from 0.05 to 3 parts by weight, per 100 parts by weight of the polyester resin. An excessive amount over 3 parts by weight of the epoxy compounds of the formula (IV) results in a re duced mobility of the resultant polyester resin composi tion. The reduced mobility causes difficulty in the mold ^ dure of the polyester resin, polycaprolactone and, op tionally, one or more additives. Usually, it is desirable that the above-mentioned components are uniformly dispersed in each other. For example, entire amounts of the components are mixed and homogenized in a mixing apparatus, such as a blender, kneader, mixing rolls or extruder, in a single procedure. In another procedure, the components are separately homogenized and then ing procedure for a molded product having a compli cated shape. Therefore, the polyester resin composition 3Q the homogenized components are mixed with each other and homogenized by using the mixing apparatus. containing more than 3 parts by weight of the epoxy In still another procedure, two or more of the compo compound is useless for the production of molded prod nents are pre-mixed with each other and then, the re ucts. maining components, which may be premixed with The polyester resin composition of the present inven each other, are admixed to the pre-mixture and the tion may contain other additives which are usually used resultant admixture is homogenized by using the above- for conventional polyester resin compositions. That is, mentioned mixing apparatus. the additives include flame-retardants, antioxidants and It is preferable that the polycaprolactone is uniformly heat-stabilizers. The flame retardant may comprise at kneaded into the body of the polyester resin. That is, it least one member selected from halogenated organic is preferable that a mixture of the polycaprolactone and compounds, for example, decabromobiphenyl ether, 43 the polyester resin are melted at an elevated tempera octabromobiphenyl ether, hexabromobiphenyl ether, ture and the melt is homogenized. halogenated polycarbonate oligomers, for example, In a usual procedure, the components in the form of polycarbonate oligomers produced from bromated bis- powder, particles or grains are dry-blended to each phenol A, and halogenated epoxy compounds; phos other; the resultant dry blend is melt-mixed and homog phorus; phosphorus compounds; and phosphorus-nitro- 45 enized by using an extruder; the homogenized melt is gen compounds, such as phosphonic amide. extruded in the form of a strand; and, then, the strand is The flame retardant may contain a flame retardant cut into a desired length to provide pellets or grains of auxiliary, for example, antimony trioxide or zinc borate. the resultant composition. The antioxidant may comprise at least one member The resultant pellets are fed into a hopper of a mold selected from hindered phenol compounds and sulfur 50 ing apparatus while the pellets are maintained in a dry compounds. condition, and then, the dry pellets are subjected to a The heat stabilizer may comprise other phosphorous molding procedure. compounds than those of the formulae (II) and (III). In another usual procedure, before, during or after The polyester resin composition of the present inven the polyester resin is prepared by a polycondensing tion may further contain still other additives, for exam- 55 process, the other components, excluding polycaprolac pies, epoxy compounds other than the above-mentioned tone, are added to the polycondensing mixture. After epoxy compounds, effective for stabilizing the viscosity the production of the polyester resin composition is of the composition and for enhancing resistance of the completed, polycaprolactone is added to the polyester composition to hydrolysis. The epoxy compounds may resin composition. be bisphenol A type epoxy compounds which have 60 In the case where glass fibers are mixed, as a filler, to been prepared by reacting bisphenol A with epichloro- the polyester resin composition, it is desirable to pre phydrin; aliphatic glycidyl ether compounds which vent breakage of the glass fibers during the blending have been prepared by the reaction of various glycol or procedure so as improve the processability of the blend. glycerol compounds with epichlorohydrin; novolak Accordingly, the glass fibers are preferably mixed with type epoxy compounds which have been produced by 65 the other components in a dry mixing apparatus, except the reaction of novolak resins with epichlorohydrin; or for the extruder or kneader. For example, the polyester cycloaliphatic epoxy compounds obtained from cyclo resin pellets are mixed with glass chopped strands or a aliphatic compounds. pre-mixture of the polyester resin with a large amount 4-,J00,3Ji 17 18 of the glass chopped strands; the mixture is fed into a hopper for a molding apparatus; and, then, subjected to the molding procedure. EXAMPLES 1 THROUGH 5 AND COMPARATIVE EXAMPLES 1 THROUGH 3 The polyester resin composition of the present inven In each of the Examples 1 through 5 and Compara tion is easily molded by using a conventional molding 5 tive Examples 1 through 3, pellets of a polyethylene method and apparatus. Since the polyester resin compo terephthalate having an intrinsic viscosity of 0.65 were sition exhibits a highly enhanced crystallizing property dried at a temperature of 130 C. for 5 hours and then, and mobility, the molding procedure of the polyester uniformly mixed with the amounts indicated in Table 1 resin composition can be effected at a wide range of of glass chopped strands having a length of 3 mm, of a mold temperatures without difficulty. The resultant 10 powder of a terminal-modified polycaprolactone hav molded product exhibits an excellent dimensional stabil ing a number average molecular weight of 1590, and of ity, a superior toughness and a satisfactory appearance. a type indicated in Table 1 of a crystal nucleating agent, The following specific examples are presented for the by using a V type blender. purpose of clarifying the present invention. However, it The mixture was fed into an extruder having a cylin should be understood that these are intended only to be 15 der diameter of 65 mm, melt-kneaded at a barrel temper examples of the present invention and are not intended ature of 270 C. and extruded through a die. The ex to limit the present invention in any way. truded strand of the mixture was solidified by cooling In the examples, the intrinsic viscosity of the polyes and the solidified strand was cut into a length of 3 mm ter resin was determined in ortho-chlorophenol at a to provide molding pellets. The resultant pellets were temperature of 35* C., and the properties of the molded 20 dried at a temperature 130 C. for 5 hours. The dried products are determined as follows. pellets were subjected to a molding procedure to pro (1) Deflection temperature vide test specimens of the polyester resin composition. This was determined in accordance with the method The molding procedure was carried out by using an of ASTM D648 under a load of 264 psi. injection-molding machine having a capacity of 5 (2) Static strength 25 ounces (141.5 g) and equipped with a testing mold. In A. Tensile strength was determined in accordance the molding procedure, the temperature of the cylinder with the method of ASTM D638. was 270 C., the temperature of the mold was 85 C., the B. Flexural strength was determined in accordance injection pressure was 800 kg/cm2, the cooling time with the method of ASTM D790. period was 20 seconds, and the time period of one cycle C. Impact strength was determined in accordance 30 of the injecting and cooling operations was 35 seconds. with the method of ASTM D-256 in which an Izod The terminal-modified polycaprolactone was pro notch having a thickness of inch was used. duced in the following manner. (3) Mobility of melt A mixture of 100 parts by weight of e-caprolactone This was determined in accordance with the method with 4.31 parts by weight of a polymerization initiator of JISfC-7210 in which the testing load was 100 kgf, the 35 consisting of ethylene glycol and 0.09 parts by weight diameter of the die was 1 mm and the length of the die of tin octylate, was stirred at a temperature of-180 C. was 10 mm. for 6 hours. The resultant reaction product comprising (4) Shrinkage polycaprolactone was mixed with 28.4 parts by weight Two or more flat plates were produced by an injec of acetic anhydride. The mixture was heated at a tem tion molding procedure using a flat plate mold having 40 perature of 130' C. for 2 hours while being stirred and an inside length of 110 mm, an inside width of 110 mm while the produced acetic acid was eliminated from the and an inside depth of 2 mm. One of the resultant reaction mixture. Thereafter, the remaining amount of molded plates was conditioned at a temperature of 25 acetic anhydride was eliminated under a reduced pres C. for 48 hours. This plate was referred to as a condi sure. The resultant terminal-modified polycaprolactone tioned plate. The dimensions of the conditioned plate 45 had a hydroxyl value of 2 or less, determined in accor were measured. Also, another molded plate was an dance with the method of Japanese Industrial Standard nealed at a temperature of 130 C. for 2 hours and, then, (JIS) K-1557. conditioned at 25 C. for 48 hours. This plate was re The ionic copolymer used as a crystal nucleating ferred to as an annealed plate. The dimensions of the agent was prepared from 90 parts by weight of ethylene annealed plate were measured. 50 and 10 parts by weight of methacrylic acid and the The molding shrinkage factor (%) and the heat carboxylic radicals in the copolymer molecules were shrinkage factor of the molded plate were calculated in completely converted into the form of sodium salt The accordance with the following equations. ionic copolymer had a melt index of 5.8 g/10 minutes or less, determined in accordance with ASTM D1238-57T, Molding shrinkage factor {%) 55 and a size of from 300 to 500 microns. The sodium montanate, used as a crystal nucleating 110 -- (dimension in mm of conditioned plate) 110 X JUU agent, was comprised mainly of partial sodium suits of a mixture of aliphatic monocarboxylic acids having 22 to Heat shrinkage factor (%) = 32 carbon atoms. 60 The resultant molded test specimens of the polyester (dimension in mm of (dimension in mm of condition plate) annealed plate) (dimension in mm of conditioned plate) resin composition exhibited the properties indicated in Table 1. Polyethylene TABLE 1____________ Composition (part by weight) Terminal-modified Crystal nucleating agent 4,5ib,5il 19 TABLE 1-continued Example No. terephthaiate Glass fiber polycaprolactone type Amount Comparative Example i 2 3 Example 1 2 3 4 5 100 70 69.7 65.7 63.8 66.5 67.7 64.0 0 30 " " " " " 0 None -- 0 None -- 0 Sodium palmitate 0.3 4 "" 6 Sodium benzoate 0.2 3 Calcium stearate 0.5 2 Sodium montanate 0.3 4 Ionic copolymer 2 Example No. Deflection temperature re.) Property of molded product Molding Heat shrinkage shrinkage (%) (%) Appearance Tensile Flexural strength strength (Kg/cm2) (Kg/cm2) Flexural elasticity (Kg/cm2) Comparative Example i 2 3 Example 1 2 3 4 5- 70 72 73 218 212 217 208 206 0.4 .6 Unsatis- 600 1000 36,000 factory 0.5 .6 Unsatis- 1540 2210 100.000 factory 0.4 1.6 Unsatis- 1530 2190 99,000 factory 1.4 0.10 Satisfactory 1560 2220 94,000 1J 0.09 1540 2190 88,000 1.4 0.13 1590 2260 96,000 1.2 0.13 1580 2210 97,000 1.2 0.10 1490 2160 88,000 20 Table 1 shows that the absence of the terminal-modi tion mixture. Thereafter, the residual amount of methyl fied polycaprolactone results in a poor crystallinity, a benzoate was eliminated from the reaction mixture low deflection temperature and a large heat shrinkage ^ under a reduced pressure. The resultant terminal-modi of the resultant molded product. However, the polyes fied polycaprolactone had a number average molecular ter resin compositions containing the terminal-modified weight of 740 and a hydroxyl value of 2.0 or less. polycaprolactone exhibited a satisfactorily enhanced Type B of the terminal-modified polycaprolactone crystallizing property and the resultant molded product was produced by reacting 100 parts by weight of a exhibited a high deflection temperature, a low heat 45 polycaprolactone having hydroxyl radicals as terminal shrinkage and a satisfactory appearance. groups thereof and a number average molecular weight EXAMPLES 6 AND 7 AND COMPARATIVE EXAMPLES 4 AND 5 of 50,000 with 30 parts by weight of methyl benzoate in the presence of 0.1 parts by weight of manganese ace tate in the same manner as that described above. The In each of the Examples 6 and 7 and Comparative 50 resultant terminal-modified polycaprolactone had a Examples 4 and 5, the same procedures as those de number average molecular weight of about 50,000 and a scribed in Example 1 were carried out with the follow hydroxyl value not exceeding 2.0. ing exception. The resultant molded products exhibited properties In the molding pellet preparation, polyethylene tere- indicated in Table 2. phthalate pellets having an intrinsic viscosity of 0.70 Table 2 indicates that in Comparative Example 4, the and dried at a temperature of 140 C. for 4 hours, were terminal-modified polycaprolactone having a large used in the amounts indicated in Table 2. The type and number average molecular weight of 50,000 did not amount of the terminal-modified polycaprolactone used promote the crystallization of the polyester resin and were as indicated in Table 2. Referring to Table 2, type that in Comparative Example 5, an excessive amount of A of the terminal-modified polycaprolactone was pre- ^ the terminal-modified polycaprolactone resulted not pared by reacting 100 parts by weight of a polyca only in an unsatisfactory promotion of the crystalliza prolactone having hydroxyl radicals as terminal groups tion of the polyester resin, but, also, in an unsatisfactory thereof and a number average molecular weight of 550 mechanical strength of the molded product. In Exam with 100 parts by weight of methyl benzoate in the ples 6 and 7, however, the resultant compositions ex presence of 0.14 parts by weight of manganese acetate 65 hibited an enhanced crystallization of the polyester at a temperature of from 190 to 210 C. for 10 hours, resin and the molded products exhibited an excellent while the reaction mixture was stirred and while the dimensional stability at an elevated temperature and an produced methyl alcohol was eliminated from the reac excellent mechanical strength. 21 Example No. Composition (part bv weight) Polyethyl ene terephtha- Glass Terminalmodified polycapro lactone late fiber Type Amount Talc Example 6 7 Comparative Example 4 5 62 60 62 49 30 A "A ff B "A 3 5 5 16 5 4,536,531 22 TABLE 2 Deflec tion temper ature re.) Mold ing shrink age m Property of molded product Heat shrink age (%) Appearance Tensile Flexural strength strength (Kg/cm2) (Kg/cm2) Flexural elasticity (Kg/cm2) 218 1.4 0.14 Satisfactory 1520 2130 103,000 208 1.6 0.12 " 1460 2110 97,000 78 0.6 1.10 Unsatisfactory 1470 2140 98,000 142 1.4 0.11 910 1280 81,000 EXAMPLE 8 hours; 10 parts by weight of glass chopped strands hav ing a length of 3 mm; 5 parts by weight of talc; 30 parts The same procedures as those described in Example 1 by weight of glass flakes having an average mesh size of were carried out, except that the molding pellets were 300; and 4 parts by weight of a terminal-modified prepared from 64 parts by weight of polyethylene tere- 20 polycaprolactone having a number average molecular phthalate pellets having an intrinsic viscosity of 0.64 weight of about 860 and a hydroxy value of 11. and dried with hot air at a temperature of 130" C. for 5 The terminal-modified polycaprolactone was pre hours; 10 parts by weight of glass chopped strands hav pared by reacting 100 parts by weight of a polyca ing a length of 3 mm; 20 parts by weight of a crystal prolactone having a number average molecular weight nucleating agent consisting of talc; and 1 part by weight 25 of 550 and a hydroxyl value of 305 with 148 parts by of a terminal-modified polycaprolactone. weight of methyl benzoate in the presence of 0.19 parts The terminal-modified polycaprolactone used herein by weight of manganese acetate, in the same manner as was prepared by reacting 100 parts by weight of a that described in Example 6. polycaprolactone having a number average molecular The resultant molded product exhibited a glossy sur weight of 850 and a hydroxyl value of 136 with 99.6 30 face thereof and a satisfactory appearance thereof and parts by weight of methyl benzoate in the presence of exhibited the following properties. 0.09 parts by weight of manganese acetate, in the same Deflection temperature: 206" C. manner as that described in Example 6. The resultant Molding shrinkage: 1.2% terminal-modified polycaprolactone had a hydroxyl Heat shrinkage: 0.1 % value of about 5.0 and a number average molecular 35 Tensile strength: 1240 kg/cm2 weight of about 990. Flexural strength: 1810 kg/cm2 The resultant molded product had a glossy surface thereof, a satisfactory appearance and the following satisfactory properties. EXAMPLES 10 THROUGH 13 AND COMPARATIVE EXAMPLE 6 Deflection temperature: 194" C. 40 In each of Examples 10 through 13 and Comparative Molding shrinkage: 0.9% Example 6, the same procedures as those described in Heat shrinkage: 0.1% Example 1 were carried out, except that the molding Tensile strength: 1120 kg/cm2 pellets contained, in addition to the polyethylene tere- Flexural strength: 1490 kg/cm2 phthalate, the glass chopped strands, and the terminal- EXAMPLE 9 45 modified polycaprolactone, a crystal nucleating agent in the type and amount indicated in Table 3 and tri- The same procedures as those described in Example I phenylphosphate in the amount indicated in Table 5. were carried out except that the molding pellets were The properties of the resultant molded products are prepared from 65 parts by weight of polyethylene tere- indicated in Table 5. phthalate pellets having an intrinsic viscosity of 0.64 50 The ionic copolymer used was the same as that de and dried with hot air at a temperature of 140 C. for 4 scribed in Example 5. -E 3 Example No. Compar ative Example 6 Example 10 11 12 Polyethyl ene terephthalate 69.3 65.3 64.6 66.2 Composition (part by weight)_______________ Glass Termi nal-modi fied poly capro Crystal nucleating agent Tri phenyl phos- fiber lactone Type Amount phate 30 0 Sodium 0.3 0.4 palmitate 4 Sodium 0.3 0.4 palmitate 5 Sodium 0.2 0.2 benzoate 3 Calcium 0.5 0.3 stearate _________________ Property of molded product Deflec tion temper ature Mold ing shrink age Heat shrink age Appear Tensile strength co (%> (%) ance (Kg/cm2) 70 0.4 1.5 Unsatis 1510 factory 217 1.4 0.09 Satisfactory 1540 210 1.4 0.10 1530 209 1.2 0.13 1570 Flexural strength (Kg/cm2) 2170 2200 2190 2250 4,536,531 23 24 TABLE 3-continued Example No. 13 Polyethylene terephtha- late 63.8 Composition (pan by weight)_______________ Glass Terminai-modiTied poly- capro- Crystal nucleating agent Triphenyl phos- fiber lactone Type Amount phate 4 Ionic 2 copolymer 0.2 __________________Property of molded product Deflectcion temperature re.) Moldmg shrinkage (%) Heat shrink- age (%> Appearance Tensile strength (Kg/cm2) 206 1.2 0.10 1480 Flexural strength (Kg/cm2) 2150 EXAMPLES 14 THROUGH 17 AND COMPARATIVE EXAMPLES 7 AND 8 modified polycaprolactone was prepared in the follow ing manner. A reaction mixture of 100 parts by weight of a In each of Examples 14 through 17 and Comparative polycaprolactone having a number average molecular Examples 7 and 8, the same procedures as those de- 15 weight of 820 and a hydroxyl value of 136 with 120 scribed in Example 3 were carried out, except that in parts by weight of methyl paratoluate and 0.18 parts by the preparation of the molding pellets, the polyethylene weight of manganese acetate was agitated at a tempera terephthalate resin was used in an amount indicated in ture of from 190 to 210 C. for 10 hours while the Table 4, the type indicated in Table 4 of terminal-modi resultant methyl alcohol was eliminated from the reac fied polycaprolactone was used in an amount indicated 20 tion mixture. Thereafter, the residual amount of methyl in Table 4 and triphenyl phosphate was used as an addi paratoluate was eliminated from the reaction product tional additive in an amount indicated in Table 4. under a reduced pressure. The resultant modification The types A and B of the terminal-modified polyca- had a number average molecular weight of about 1020 prolactones were the same as those described in Exam and a hydroxyl value of 5. ple 6 and Comparative Example 4. 25 The molded product exhibited a satisfactory glossy The type C of the terminal-modified polycaprolac appearance and had the following properties. tone was prepared by reacting 100 parts by weight of a Deflection temperature: 198 C. polycaprolactone having a number average molecular Molding shrinkage: 0.9% weight of 1200 and a hydroxyl value of 93 with 80 parts Heat shrinkage: 0.1% by weight of methyl benzoate in the presence of 0.2 20 Tensile strength: 1130 kg/cm2 parts by weight of manganese acetate, in the same man Flexural strength: 1520 kg/cm2 ner as that described in Example 6. The resultant modi fication had a number average molecular weight of EXAMPLE 19 about 1405 and a hydroxyl value of 2.0 or less. The same procedures as those described in Example 9 The resultant molded products had properties indi- 25 were carried out, except that the molding pellets con cated in Table 4. tained 0.5 parts by weight of an additional additive TABLE 4 Composition (part by weight) Property of molded product Example No. Polyethylene tere phthalate Glass fiber Terminal-modified polycaprolactone Type Amount Talc Triphenyl phos phate Deflection temperature (*C.) Heat Molding shrinkshrinkage age (%) (%) Appear ance Tensile strength (Kg/cm2) Flexural strength (Kg/cm2) Example 14 61 30 A 3 51 216 1.4 0.14 Satisfactory 1510 2110 15 59 A5 210 1.7 0.10 1490 2160 16 59 c,, (1420)f-> (2070)<*> 111 1.5 0.11 1460 2070 Compar- tive Example 7 8 Example 59 48 B A 16 76 0.5 1.10 Unsatis- 1460 2100 factory - 141 1.4 0.10 Unsatis- 890 1250 factory 17 60 A5 0 208 1.6 0.12 Satisfactory 1460 2110 (1020)<*> {1370)<-2 Note; (l*) * The parenthesized flexural strength values were of the molded products prepared at a cylinder temperature of 290* C. in the extruder in the molding procedure. Table 4, especially, Example 15, shows that the tri phenyl phosphate is effective for producing the molded 60 product at a relatively high molding temperature of 290 C. substantially without decreasing the mechanical consisting of trimethyl phosphate. strength of the molded product. The molded product exhibited a satisfactory glossy EXAMPLE 18 appearance and had the following properties. The same procedures as those described in Example 8 65 Deflection temperature: 208 C. were carried out, except that the molding pellets con Molding shrinkage: 1.3% tained 0.5 parts by weight of an additional additive Heat shrinkage: 0.1% consisting of triphenylphosphite, and the terminal- Tensile strength: 1220 kg/cm2 Flexural strength: 1820 kg/cm2 4,536,531 25 26 EXAMPLES 20 THROUGH 25 In the comparison of the results of Example 26 through 28 with those of Comparative Examples 9 In each of the Examples 20 through 25, the same through 11, it is clear that the absence of the terminal- procedures as those described in Example 14 were car modified polycaprolactone resulted in a low deflection ried out, except that the polyethylene terephthalate 5 temperature and in a large heat shrinkage due to the resin was used in an amount of 61.5 parts by weight, and poor crystallization of the polyester resin. This phenom 0.5 parts by weight of a type of phosphorus compound enon is variable, depending on the content of the poly indicated in Table 5 was used in place of triphenylphos- ethylene terephthalate in the polyester resin composi phate. tion. That is, the higher the content of polyethylene The properties of the resultant molded products are 10 terephthalate, the poorer the degree of crystallization of indicated in Table 5. the polyester resin. TABLE 5 Example No. Phosphorus compound Deflection temperature CC.) Property of molded product Molding Heat shrinkage shrinkage (%) <%) Appearance Tensile Flexural strength strength (Kg/cm2) (Kg/cm2) 20 Phosphoric acid 21 Phosphorous acid 22 Phosphonic acid 23 Phosphmic acid 24 Dimethyl phosphinic acid 25 Phenyl phosphonic acid 213 210 212 213 212 214 1.5 0.10 Satisfactory 1520 2240 1.4 0.11 1530 2230 1.4 0.12 1510 2220 1.6 0.13 1520 2230 1.5 0.12 1530 2240 1.5 0.13 1520 2230 EXAMPLES 26 THROUGH 31 AND COMPARATIVE EXAMPLES 9 THROUGH 12 From the comparison of Example 31 with Compara tive Exaple 12, it is evident that even when no glass fiber was used, the presence of the terminal-modified In each of the Examples 26 through 31 and Compara polycaprolactone is effective for reducing the heat tive Examples 9 through 12, the same procedures as shrinkage and for improving the appearance of the those described in Example 1 were carried out, except 30 molded product. for the following items. 1. The molding pellets were produced from a polyes ter resin composed of a mixture of a polyethylene tere EXAMPLES 32 AND 33 AND COMPARATIVE EXAMPLES 13 THROUGH 17 phthalate having an intrinsic viscosity of 0.65 and a In each of Examples 32 and 33 and Comparative polybutylene terephthalate having an intrinsic viscosity 35 Examples 13 through 17, the same procedures as those of 0.85, each being in the amounts indicated in Table 6 described in Example 26 were carried out, except for and each having been dried at a temperature of 130 C. the following items. for 5 hours; the amount indicated in Table 6 of glass 1. The polyester resin was replaced by a blend resin chopped strands; the amount indicated in Table 6 of a consisting of 40 parts by weight of a plybutylene tere terminal-modified polycaprolactone having a number 40 phthalate having an intrinsic viscosity of 1.05 and 50 average molecular weight of 740 which was prepared parts by weight of a polymer resin indicated in Table 7. using the same procedures as those mentioned in Exam 2. No glass fiber was used. ple 6; and the amount indicated in Table 6 of talc. 3. The blending operation was carried out by using a 2. In the molding procedure, the temperature of the Henshel mixer. mold was 70 C. 45 The molding shrinkage and apparatus of each molded The properties of the resultant molded products are product are indicated in Table 7. indicated in Table 6. TABLE 6 Example No Example 20 27 28 29 30 31 Comparative Example 9 10 11 12 Composition (part by weight)_________ _____________________ Property of molded product Poly ethylene tere phthalate Poly butylene tere phthalate Glass fiber Terminalmodified polycapro lactone Talc Deflection temper ature CC.) Molding shrinkage (%) Heat shrink age (%) Appearance Tensile strength (Kg/cm2) 50 10 30 30 30 " 5 5 217 " " 210 1.4 0.10 Highly glossy 1520 1.4 0.15 " 1480 10 50 " " " 208 1.6 0.13 " 1400 55 5 7 " 205 1.4 0.09 1510 34 34 20 7 " 195 1.7 0.18 1270 45 45 0 5 78 1.8 0.21 820 50 10 30 30 30 " 10 50 " 45 45 0 0 10 93 0.4 1.4 Extremely bad 1460 0 146 0.8 1.0 Unsatisfactory 1310 0 192 1.9 0.48 Highly glossy 1230 0 " 65 0.6 1.5 Slightly glossy 850 Flexural strength (Kg/cm2) 2150 2020 1960 2070 1910 1220 2130 1970 1820 1240 4,536,531 27 28 TABLE 7 Example No. Examjjle 32 Comparative Example 13 14 15 16 17 Example 33 Blended polymer resin None Polyacetal Nylon 6 Nylon 66 Polypropylene Polyethylene produced by high pressure method Polyethylene terephthalate having an intrinsic viscosity of 0.72 Molding shrinkage (%) 1.93 -- -- -- 2.10 2.15 1.68 Appearance Satisfactory Not moldable Satisfactory, pearl like gloss Satisfactory, pearllike gloss Satisfactory Table 7 shows that polyacetal, nylon 6 and nylon 66 indicated in Table 8 of triphenylphosphate; and the caused the resultant resin compositions to be not mold- amount and the type indicated in Table 8 of a crystal able and polypropylene and polyethylene caused the 20 nucleating agent. resultant molded products to exhibit a very large mold 2. The terminal-modified polycaprolactone was pro ing shrinkage and a pearl-like gloss. duced by the same method as that described in Example EXAMPLES 34 THROUGH 37 AND COMPARA TIVE EXAMPLE 18 In each of the Examples 34 through 37 and Compara tive Example 18, the same procedures as those de scribed in Example 26 were carried out, except for the 3. The ionic copolymer used as a crystal nucleating agent was the same as that described in Example 5. The properties of the resultant molded products are indicated in Table 8. TABLE 8 Example No. Example 34 Polyethylene cerephthalate 44.3 35 44.6 36 46.2 37 43.8 Comparative Example 18 48.3 Polybutylene terephthalate 21 20 20 20 21 Composition (part by weight) Terminalmodified Glass polycapro- Triphenyl fiber lactone phosphate 30 4 0.4 5 0.2 3 0.3 4 0.2 0 0.4 Crystal nucleating aeent Type Amount Sodium palmitate Sodium benzoate Calcium stearate Ionic copolymer Sodium palmitate 0.3 0.2 0.5 2 0.3 Example No. Example 34 Deflection temperature (c.) 211 35 203 36 202 37 205 Comparative Example 18 70 Molding shrinkage (%> 1.6 1.6 1.4 1.4 0.5 Prooerty of molded product Heat shrinkage (%) Appearance 0.09 Satisfactory glossy 0.10 Satisfactory glossy 0.12 Satisfactory glossy 0.10 Satisfactory glossy 1.6 Unsatisfactory Tensile strength (Kg/cm-) 1490 1480 1520 1440 1460 Flexural strength (Kg/cm-) 2130 2120 2180 2090 2100 following items. 1. The molding pellets were produced from a blend of the amount indicated in Table 8 of a polyethylene tere- 60 phthalate having an intrinsic viscosity of 0.70 and the amount indicated in Table 8 of a polybutylene terephthalate having an intrinsic viscosity of 0.95, each polyester having been dried at a temperature of 140 C. EXAMPLES 38 AND COMPARATIVE EXAMPLES 19 AND 20 for 4 hours; 30 parts by weight of glass chopped strands 65 In each of Example 38 and the Comparative Exam having a length of 3 mm; the amount indicated in Table ples 19 and 20, the same procedures as those described 8 of a terminal-modified polycaprolactone having a in Example 34 were carried out, except for the follow number average molecular weight of 1590; the amount ing items. 4,3.50, DJI 29 30 1. The polyethylene terephthalate and the polybutyl Flexural strength: 1790 kg/cm2 ene terephthalate were used in amounts indicated in Table 9. REFERENTIAL EXAMPLE 1 2. Talc was used as a crystal nucleating agent in an Preparation of bis-2,3-epoxypropanol terephthalic ester, amount of 4 parts by weight. 5 which will be referred to as DGT hereinafter 3. The terminal-modified polycaprolactone used was of the type indicated in Table 9. The types B and C of the terminal-modified polycaprolactones were the same as that described in Comparative Example 4 and Exam ple 16, respectively. 4. Phosphorous acid was used in an amount of one part by weight in place of the triphenyl phosphate. The properties of the resultant molded products are indicated in Table 9. A reaction of 3325 g (2 moles) of terephthalic acid with 3700 g (40 moles) of epichlorohydrin was carried out in the presence of 10 g of triethyl amine at a temper ature of 90' C. for 4 hours. Next, 400 g (4 moles) of an 0 aqueous solution of 50% by weight of sodium hydrox ide were added dropwise to the reaction product over 4 hours, while the reaction mixture was vigorously stirred. After the adding operation was completed, the reaction mixture was additionally stirred for 0.5 hours. TABLE 9 Item Example 38 Example No. Comparative Example 19 20 Composition (part by weight) Property of molded product Polyethylene terephthalate Polybutylene terephthalate Glass fiber Terminal- Type modified Molecular weight polycapro- Amount lactone Talc Phosphorous acid Deflection temperature (*C.) Molding shrinkage (%) Heat shrinkage (%) Appearance Tensile strength (Kg/cm2) Flexural strength (Kg/cm2) 45 15 30 C 1,405 5 4 i 209 1.7 0.11 Satisfactory 1420 2010 45 15 30 B 50,000 5 4 i 73 0.7 1.10 Unsatisfactory 1420 2040 34 15 30 C 1,405 16 4 i 137 1.6 0.10 Unsatisfactory 860 1210 EXAMPLE 39 The same procedures as those described in Example 35 The reaction mixture was washed with water and, then, the residual amount of epichlorohydrin was removed 18 were carried out, except for the following items. 1. The polyester resin was composed of 45 parts by from the reaction mixture under a reduced pressure. The residue was recrystallized by using toluene. The weight of a polyethylene terephthalate resin having an resultant bis-2,3-epoxypropanol terephthalic ester had intrinsic viscosity of 0.64 and 19 parts by weight of a polybutylene terephthalate resin having an intrinsic 40 an epoxy equivalent of 144 which corresponded to a degree of purity of 99% thereof, and a velting point of viscosity of 0.95, both resins having been dried at a 108 C. The yield of bis-2,3-epoxypropanol terephthalic temperature of 130' C. for 5 hours. ester was 57%. 2. Phosphoric acid was used in an amount of 0.5 parts in place of triphenyl phosphite. 3. The same terminal-modified polycaprolactone as 45 REFERENTIAL EXAMPLE 2 Preparation of bis-2,3-epoxid that described in Example 18 was used in an amount of propanol-cyclohexane-1,4-dicarboxyiic ester which 2 parts by weight. will be referred to as DGH, hereinafter The resultant molded product exhibited a glossy ap pearance and the following properties. Deflection temperature: 195 C. 50 A reaction mixture of 86.1 g (0.5 moles) of cyclohex ane- 1,4-dicarboxyiic acid, 924 g (10 moles) of epichloro Molding shrinkage: 0.9% hydrin and 1.72 g of benzyl-trimethyl ammonium chlo Heat shrinkage: 0.1% ride was heated to a temperature of 100 C. to homoge Tensile strength: 1100 kg/cm2 Flexural strength: 1470 kg/cm2 nize it. Thereafter, the homogenized reaction mixture was kept at a temperature of 85 C. for 3 hours to effect 55 the reaction of cyclohexane dicarboxylic acid with epi EXAMPLE 40 chlorohydrin. While the reaction mixture was vigor The same procedures as those described in Example 19 were carried out, except that the polyester resin was composed of 46 parts by weight of a polyethylene tere phthalate having an intrinsic viscosity of 0.65 and 19 b parts by weight of a polybutylene terephthalate having an intrinsic viscosity of 0.95. The resultant molded product exhibited a glossy ap pearance and the following properties. Deflection temperature: 204 C. Molding shrinkage: 1.4% Heat shrinkage: 0.1 % Tensile strength: 1180 kg/cm2 ously agitated at a temperature of approximately 40 C., 100 g of an aqueous solution of 50% by weight of so dium hydroxide were added dropwise to the reaction mixture. After the adding operation was completed, the agitating operation on the reaction mixture was contin ued for 0.5 hours. The non-reacted epichlorohydrin was removed from the reaction product under a reduced pressure. The residual reaction product was mixed with about 1000 g benzene and, then, washed once with an aqueous solu tion of 10% by weight of sodium hydroxide and, then, twice with water. The washed reaction product was 4,536,531 31 32 filtered and thereafter, benzene was removed therefrom 4. Trimethyl phosphate was used in an amount indi under a reduced pressure. cated in Table 10 as an additional additive. In order to completely remove the residual amount of 5. An epoxy compound DGT was used in an amount epichlorohydrin, a small amount of toluene was mixed indicated in Table 10 as a further additional additive. with the reaction product and, then, epichlorohydrin 5 6. The ionic copolymer used in Example 44 was the and toluene were concurrently separated from the reac same as that used in Example 5. tion product by means of azeotropic distillation. 7. In the molding procedure, the temperature of the The resultant bis -2,-epoxid propanol cyclohexane- mold was 80 C. and the injection pressure was 700 1,4-dicarboxylic ester was obtained in an amount of 127 kg/cm2. g which corresponded to a yield of 88% and exhibited 10 The properties of the resultant molded products are an epoxy equivalent of 154 which corresponded to a indicated in Table 10. TABLE 10 Example No. Comparative Example Example 21 41 Polyethylene terephthalate 68.8 64.8 42 64.3 43 65.5 44 63.6 Class fiber 30 30 30 30 30 Composition (part by weight) Terminalmodified polycapro- Crystal nucleating agent Trimethyl lactone Type Amount phosphate 0 Sodium 0.3 palmitate 0.4 4 Sodium palmitate 5 Sodium 0.2 benzoate 3 Calcium 0.5 stearate 4 Ionic 2 copolymer " 0.8 0.3 0.2 Epoxy compound DGT 0.5 " 0.3 0.7 0.2 Example No. Comparative Example Example 21 41 42 43 44 Deflection temperature rc.) 70 216 208 209 203 Molding shrinkage (%) 0.4 Property of molded product Heat shrinkage (%) Appearance 1.5 Unsatisfactory Tensile strength (Kg/cm2) 1520 1.4 0.10 Satisfactory 1560 1.4 0.11 1550 1.3 0.12 1600 1.0 0.13 1510 Flexural strength (Kg/cm2) 2200 2210 2200 2260 2170 degree of purity of 94% thereof, and a melting point of from 35 to 90 C. 40 EXAMPLES 45 AND 46 AND COMPARATIVE EXAMPLES 22 AND 23 EXAMPLES 41 THROUGH 44 AND COMPARATIVE EXAMPLE 21 In each of the Examples 45 and 46 and Comparative Examples 22 and 23, the same procedures as those de In each of the Examples 41 through 44 and Compara scribed in Example 14 were carried out, except that the tive Example 21, the same procedures as these de- 45 molding pellets had the composition indicated in Table scribed in Example 1 were carried out except for the 11. following items. The terminal-modified polycaprolactone D used in 1. The polyethylene terephthalate resin was used in Example 46 was prepared by using 100 parts by weight an amount indicated in Table 10. of polycaprolactone having a number average molecu 2. The terminal-modified polycaprolactone had a 50 lar weight of 1374 and a hydroxy value of 2.4, 80 parts hydroxy value of 1.7 and was used in an amount indi by weight of methyl benzoate and 0.002 parts by weight cated in Table 10. of tetrabutyl titanate by the same method as that used 3. The type indicated in Table 10 of a crystal nucleat for producing type A of the terminal-modified polyca ing agent was used in an amount indicated in Table 10. prolactone in Example 3. The properties of the resultant molded products are indicated in Table II. TABLE 11 Example 45 46 Example No. Comparative Example 22 23 Composition (part by weight) Polyethylene terephthalate Glass fiber Terminal- Type modified Molecular weight polycapro- Hydroxyl value lactone Amount Talc Phosphorous acid Epoxy compound DGT 58 30 A 740 2.1 5 5 i 1 58 30 1374 2.4 5 5 1 1 58 30 B 50,000 1.0 > 5 5 i 1 57 30 A 740 2.1 16 5 l 1 Property of molded product 4,536,531 33 34 TABLE 11-continued Example 45 46 Example No. ______ Comparative Example 22 23 Deflection temperature (*C.) Molding shrinkage {%) Heat shrinkage (%) Appearance Tensile strength (Kg/cm2) Flexural strength (Kg/cm2) 208 1.6 0.10 Satisfactory 1520 2200 209 1.4 0.11 Satisfactory 1490 2110 72 0.4 1.11 Unsatisfactory 1490 2130 128 1.2 0.13 Unsatisfactory 910 1280 EXAMPLES 47 THROUGH 53 2. The terminal-modified polycaproractone had a number average molecular weight of 1020 and a hy In each of the Examples 47 through 53, the same droxyl value of 4.7. procedures as those described in Example 41 were car 15 3. The molding pellets contained 0.5 parts by weight ried out, except that the molding pellets had the compo of the epoxy compound DGT as a further additional sition indicated in Table 12 and the polyethylene tere- additive. phthalate resin was dried at a temperature of 150 C. for The resultant molded product had a satisfactory 3 hours. glossy appearance and the following properties. Also, the molding procedure was carried out twice 20 Deflection temperature: 196 C. cylinder temperatures of 270 C. and 300 C. Molding shrinkage: 1.0% The properties of the resultant molded products are Heat shrinkage: 0.09% shown in Table 12. Tensile strength: 1170 kg/cm2 TABLE 12 Example No. Polyethylene tere* phthaJate Glass fiber Composition (part by weight) Terminal-modified polycaprolactone Crystal nucleating Phosphorus agent_______ ______ compound Type Amount Type Amount Type Amount Epoxy compound DGT 47 62.5 30 A 48 63.1 A 49 62.1 A 50 62.6 A 51 59 D 52 58.7 D 53 63.1 D 6 Sodium 0.4 Triphenyl i palmitate phosphate 6 Sodium " -- palmitate 6 Sodium Triphenyl i palmitate phosphate 6 Sodium " Phosphonic 0.5 palmitate acid 7 Ionic (*) 3 Phosphoric 1 copolymer acid 7 Ionic (*) 3 Phosphoric I copolymer acid 5 Sodium 0.5 Dimethyl 0.1 benzoate phosphinate 0 0.5 0.5 0.5 0 0.3 0.7 Example No. Deflection temperature C c.) Property of molded product Molding shrinkage Heat shrinkage Tensile strength (Kg/cm2) Temperature of cylinder (*C.) (%) (%) 270 300 Flexural strength (Kg/cm2) Temperature of cylinder ____ CLJ_____ 270 300 47 213 1.6 48 210 1.4 49 212 1.5 50 213 1.6 51 214 1.6 52 215 1.6 53 211 1.5 Note: (*) - This was available in a trademark of Serlin A #1555 and made by Du Pont. 0.08 0.12 0.09 0.09 0.06 0.07 0.10 1450 1210 2020 1710 1490 1330 2060 1840 1470 1420 2050 1980 1460 1410 2070 1970 1390 1160 1850 1540 1420 1340 1910 1830 1560 1510 2280 2190 Table 12 shows that the combination of the phospho rus compound with the epoxy compound was effective Flexural strength: 1580 kg/cm2 for obtaining excellent tensile and flexural strengthes of 60 EXAMPLE 55 the molded product even when the cylinder tempera ture was elevated to 300 C. in the molding procedure. The same procedures as those described in Example 19 were carried out, except for the following items. EXAMPLE 54 1. An ionic copolymer, which was available under The same procedures as those described in Example 18 were carried out, except for the following items. 1. The polyethylene terephthalate resin was used in an amount of 63 parts by weight. 65 the trademark of Himilane 1707 made by Mitsui Polychemical Co., Ltd., Japan, was used in an amount of 5 parts by weight in place of talc. 2. Phenyl phenylphosphonate was used in an amount of 0.5 parts by weight in place of trimethyl phosphate. 4,Dib,DJi 35 36 3. The molding pellets contained 0.5 parts by weight of the epoxy compound DGT as a further additional additive. EXAMPLES 59 AND 60 AND COMPARATIVE EXAMPLES 26 THROUGH 33 The resultant molded product exhibited a satisfactory In each of Examples 59 and 60 and Comparative glossy appearance and the following properties. 5 Examples 26 through 33, the same procedures as those Deflection temperature: 203 C. described in Example 1 were carried out, with the fol Molding shrinkage: 1.4% lowing exceptions. Heat shrinkage: 0.1% In the molding pellet preparation, polyethylene tere Tensile strength: 1250 kg/cm2 phthalate pellets having an intrinsic viscosity of 0.72 Flexural strength: 1870 kg/cm2 10 and dried of 140 C. for 6 hours were used in an amount EXAMPLES 56 THROUGH 58 AND COMPARATIVE EXAMPLES 24 AND 25 indicated in Table 14. The type and amount of the ter minal-modified polycaprolactone used were as indi cated in Table 14. Also, the amount of glass chopped In each of the Examples 56 through 58 and Compara strands, the type and amount of the crystal nucleating tive Examples 24 and 25, a blend was prepared from 100 15 agent, the amount of epoxy compound DGT, the parts by weight of a polyethylene terephthalate which amount of triphenyl phosphate, and the amount of the had the intrinsic viscosity indicated in Table 13 and polyethylene terephthalate pellets were as indicated in which was dried at a temperature of 140 C. for 4 hours, Table 14. the amount and the type indicated in Table 13 of a The resultant mixture was fed into an extruder having terminal-modified polycaprolactone and the amount 20 a cylinder diameter of 68 mm and extruded through a and the type of an additive. The blend was melt- die at a barrel temperature of 290 C. The resultant kneaded and extruded with an extruder having a cylin pellets were dried at a temperature of 140 C. for 5 der diameter of 65 mm at a barrel temperature of 270 hours. C., and the extruded strand was converted to molding In the molding procedures, the temperature of the pellets. 25 cylinder was 280 C., the temperature of the mold was The flow value of the melt of the molding pellets was 70 C., the injection pressure was 600 kg/cm2, the cool determined at a temperature of 290 C. Also, the mold ing time was 20 seconds, and the time period of one ing pellets were molded by using an injection molding cycle of the procedures was 35 seconds. apparatus at a cylinder temperature of 270 C., and at a The terminal-modified polycaprolactone having a mold temperature of 70 C. under an injection pressure 30 number average molecular weight of 4,240 was pre of 800 kg/cm2. The molded product was subjected to pared by reacting 100 parts by weight of polycaprolac the measurement of static strength. tone having terminal hydroxyl radicals thereof and a The results are indicated in Table 13. number average molecular weight of 4,000 which was In Examples 57 the ionic copolymer was the same as available under the trademark of Placsel 240 produced that described in Example 45 and the epoxy resin was 35 by Daicel Co., Ltd., with 75 parts by weight of methyl available under to trademark of Epicoat 828 made by benzoate in the presence of 0.16 parts by weight of Shell Chemical. manganese acetate in the same manner as that described In Example 58, the type E of the terminal-modified in Example 6, and had a hydroxy value not exceeding 2. polycaprolactone was the same as that described in The terminal-modified polycaprolactone having a Example 18. 40 number average molecular weight of 10,000 had a hy In view of Example 56 and Comparative Example 24, droxy value not exceeding 2 and was prepared by react it is clear that the addition of the terminal-modified ing 100 parts by weight of polycaprolactone having polycaprolactone is remarkably effective for increasing terminal hydroxyl radicals thereof and a number aver not only the melt mobility (flow value), but also, the age molecular weight of 10,000 which was available static strength of the molded product. under the trademark of Placsel H-l produced by Daicel In Comparative Example 25, the type B of terminal- Co., Ltd., with 56 parts by weight of methyl benzoate in modified polycaprolactone having a number average the presence of 0.12 parts by weight of manganese ace molecular weight of 50,000 is not effective for increas tate in the same manner as that described in Example 6. ing either the melt mobility of the composition or the The results are indicated in Table 14. static strength of the molded product. TABLE 1 Composition (part by weight) ________________ Result Example No. Example 56 57 58 Compartive Example 24 25 Polyethylene terephthalate_____ Terminal-modified Flow Intrinsic polycaprolactone __________Additive___________ value Amount viscosity Type Amount Type Amount at 270' C. 100 1.1 A 7 Talc 2 0.080 0.7 c 5 Ionic copolymer 2 0.068 Epoxy resin 1 0.7 E 10 Sodium palmitate 0.3 0.076 DGT 1 1.1 none -- 1.1 B 7 Talc Talc 2 0.038 2 0.042 ______Static strength Ultimate Impact elongation strength (%) (kg cm/cm) 54 3.5 200 5.4 180 4.8 32 3.2 28 2.6 Example No. PET Example 59 58.5 Example 60 58.5 Compar ative Example 26 Compar ative Example 27 Compar ative Example 28 Compar ative Example 29 Compar ative Example 30 Compar ative Example 31 Compar ative Example 32 Compar ative Example 33 63.5 63.5 63.5 63.5 63.5 58.5 58.5 58.5 Glass Fiber 30 30 30 30 30 30 30 30 30 30 37 38 ________________ TABLE 14___________________________________ Composition (part by weight) Terminal modified polycaprolactone Crystal nucleating agent Epoxy compound DGT MW Amount Type Amount Amount ___________ Property of molded product Triphenyl phos Deflection temperature Molding Heat shrink shrink Tensile strength Flexural strength phate <-c.) age age (Kg/cm2) (Kg/cm2) 740 6 Talc (Type A) 1405 6 (TypeC) 740 6 none (Type A) 5 5 i 0.5 209 1.7 0.10 1470 2150 i 0.5 210 1.6 0.12 1460 2140 i 0.5 76 0.5 1.3 1500 2170 1405 (Type C) 6 I 0.5 75 0.5 1.3 1510 2170 4240 6 i 0.5 77 0.6 1.2 1500 2160 10000 6 i 0.5 73 0.5 1.3 1520 2180 50000 (Type B) 6 4240 6 Talc 5 i 0.5 70 0.5 1.3 1500 2170 i 0.5 156 1.1 0.4 1450 2140 10000 6 5 i 0.5 118 0.7 0.8 1460 2150 50000 (Type B) 6 5 i 0.5 78 0.6 1.10 1470 2150 In Comparative Examples 26 to 30, wherein no talc We claim: was used as a crystal nucleating agent, the resultant 1. A polyethylene terephthalate resin composition molded products exhibited an undesirably low deflec comprising: tion temperature and an excessively large molding (A) per 100 parts by weight of said polyethylene shrinkage independently from the value of the number terephthalate resin, 0.1 to 30 parts by weight of a average molecular weight of the terminal modified polycaprolactone having a number average molec polycaprolactones used. This phenomena suggested ular weight of from 200 to 2000 and 50% or more that the polyester resins in the molded products were of its entire number of terminal radicals modified to not satisfactorily crystallized. 40 be non-reactive and In Examples 59 and 60 in accordance with the present wherein said polyethylene terephthalate resin has an invention, the resultant molded products exhibited a intrinsic viscosity of from 0.35 or more determined satisfactorily high deflection temperature and small in orthochlorophenol at a temperature of 35 C.; molding shrinkage. (B) 0.01 to 10 parts by weight of a crystal nucleating In Comparative Examples 31 to 33, in which the 45 agent for said polyethylene terephthalate resin, per terminal-modified polycaprolactones used had a large 100 parts by weight of said resin; and number average molecular weight, the resultant molded (C) 5 to 200 parts by weight of an inorganic filler, per products exhibited a large molding shrinkage and a low 100 parts by weight of said polyethylene tere deflection temperature. This phenomenon suggests that phthalate resin. the polyester resin in the molded products was not 50 2. A polyethylene terephthalate resin composition as sufficiently crystallized. claimed in claim 1, wherein said modified terminal radi cals of the polycaprolactone molecules are of the for COMPARATIVE EXAMPLE 34 mula (I) The same procedures as those described in Compara tive Example 3 were carried out except that the poly 55 ethylene terephthalate was used in an amount of 65 [R`C0+04CH2)5C0riC%,R-fC0-t-0+-CH2)-3CO)TOR2k (I) parts by weight, the same type of terminal-modified wherein n and p respectively represent, independently polycaprolactone as that described in Example 1 was from each other, an integer of 2 or more; m and q re- used in an amount of 5 parts, and no sodium palmitate 60 spectively represent, independently from each other, was used. zero or an integer o from 1 to 4, the sum of m-and q The resultant molded product exhibited an unsatisfac being 1 or more; R represents an organic radical having tory appearance and the following properties. a valence corresponding to the sum of m and q; and R1 Deflection temperature: 75" C. and R2 respectively represent, independently from each Molding shrinkage: 0.5% 65 other, a monovalent organic radical. Heat shrinkage: 1.6% 3. A polyethylene terephthalate resin composition as Tensile strength: 1530 kg/cm2 claimed in claim 1, wherein said inorganic filler com Flexural strength: 2180 kg/cm2 prises at least one member selected from the group Flexural elasticity: 90,000 kg/cm2 39 40 consisting of glass fibers, asbestos, carbon fibers, potas from substituted and unsubstituted alkyl, aralkyl and sium titanate fibers, and mica, silica, talc, calcium car aryl radicals each having 12 carbon atoms or less. bonate, glasses, clay and wollastonite in the forms of particles, grains, flakes and small plates. 4. A polyethylene terephthalate resin composition as claimed in claim 1, wherein said crystal nucleating agent comprises at least one member selected from the 8. A polyethylene terephthalate resin composition as claimed in claim 5, which additionally contains, per 100 parts by weight of said polyethylene terephthalate resin, 3 parts by weight or less of at least one epoxy com pound selected from those of the formula (IV): group consisting of salts of carboxylic acids with metals of Groups I and II in the periodic table, talc and ionic copolymers of a-olefins with salts of a, /3-unsaturated 10 carboxylic acid with metals of Group I and II in the periodic table. (CH2----- CH--CH2OC-)7R4 o (IV) 5. A polyethylene terephthalate resin composition as claimed in claim 1, which additionally contains, per 100 wherein r represents an integer of 2 or more and R4 parts by weight of said polyethylene terephthalate resin, 0.01 to 2 parts by weight or less of at least one phospho rus compound selected from those of the formulae (II) 15 represents a r-valent hydrocarbon radicals together with said phosphorus compound. 9. A polyester resin compositon as claimed in claim 8, wherein said hydrocarbon radical represented by R4 is and (III): selected from alkylene radicals having 1 to 16 carbon 20 atoms, cyclic alkylene radicals having 5 to 16 carbon 00 atoms, phenylene, naphthylene, methylphenylene, and X--P--z II o aromatic radicals of the formulae: and X--P--z wherein X, Y and Z respectively represent, indepen dently from each other, a member selected from the group consisting of a hydrogen atom, monovalent hy drocarbon radials and radicals of the formula --OR3 in which R3 represents a member selected from a hydro gen atom and monovalent hydrocarbon radicals. 6. A polyethylene terephthalate resin composition as claimed in claim 5, wherein said monovalent hydrocar bon radicals represented by R3 are selected from substi tuted and unsubstituted alkyl, aralkyl and aryl radicals each having 12 carbon atoms or less. 7. A polyethylene terephthalate resin composition as claimed in claim 5, wherein said monovalent hydrocar bon radicals represented by X, Y and/or Z are selected 45 ***** 50 55 60 65