A THERMOPLASTIC POLYESTER COMPOSITION

Abstract: Polyester resin composed of terephthalic acid or the like is improved with incorporation of a hydantoin com­ pound in respect to prevention of release of the acid com­ ponent and therefore the molding property.

Description: A Thermoplastic Polyester Composition The present invention relates to a polyester resin composition improved in its molding characgaristic. More particularly, it pertains to a thermoplastic polyester composition having as its major acid component an aromatic dibasic acid such as terephthalic acidr etc., with which such a trouble as corrosion of dies, etc., is relieved by inhibiting release of such an aromatic dibasic acid as terephthalic acid, etc., in the process of molding. High molecular weight polyester or copolymerized polyesters produced from alkylene glycol and terephthalic acid or isophthalic acid are finding wide used as engineering plastics because of their excellent mechanical pro- @ perties electrical properties, molding characteristic, etc. Especially, polybutylene terephthalate resin manufactured from 1,4-butanediol and terephthalàc acid or its derivatives, among other polyester resins above-mentioned, has excellent crystallinity, satisfactory molding characteristic, and high affinity to such inorganic fillers as glass fiber, etc. Then its mechanical properties, temperature of thermal deformation, etc. will be improved by addition of such a filler, and it will readily be made flame retardant vithout accompanying degradation in its physical pro perties. With these advantages, this resin is being widely used as a resin for extrusion molding. However, as such a resin becomes handled in large amounts and for long times, in the process of molding with this resin, a gas containing as its main component such an aromatic dibasic acid as terephthalic acid, etc. is released; this gas adheres on the dies1 thus d@-priving the molded surface of its smoothness, and giving rise to such troubles as corrosion of dies. As a result, frequent cleaning of dies and the like cares are required, posing grave problems in the phases of productivity and economy. Accordingly, the resolution of this issue is very importantly linked to upgrading of productivity and improvement in economy and consequently, resource savings. The present inventions, reflecting on these aspects of the problem, devoted themselves to the study which has led to the completion of this invention Thus the present inventors found out the possibility of inhibiting at a very high efficiency the release of such an aromatic dibasic acid as terephthalic acid. As the hydantoin compound, any compounds having the hydantoin radical may be employed; they may have one or more radicals, or they may be in the high molecular state. As hydantoin compounds bearing radicals as substitute, those having alkyl group or allyl group or some other substitutàng radicals may be mentioned. They include, for < ample, hydantoin or hydantoin compounds derived from a-amwno acids; especially, phenyl hydantoin and p-ydrox7- phenyl hydantoin which are derived from phenyl glycine and p-hydroxyphenyl glycine are useful. Tne amount of such a hydantoin compound added should be more than that sufficient to suppress the release of terephthalic acid. However, some compounds, if added in excess amount, will come out In the released gas in the process of molding. Careful handling is, therefore, necessary in utilizing low molecular weight hydantoin compounds. As for the amount of these compounds to be added, their activity will be well recognized inthe range of 0.01 - 10 parts (parts by weight, the same applies here inafter); generally, they are used in the range of 0.01 - 5 parts, and preferably should selectively be used in 0.01 - 2 parts. -As the polyester resins to be used as the base, polytlkylansiteraphthalates such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, etc. may be named. Besides, , polyester resins denatured 20% with other glycols or dicarboxylic acids are also usable As the glycol component used for denaturing of polyesters, , aliphatic or alicyclic or aromatic glycols in- cluding neopentyl glycol, 1,4 dimethyl-lolcyclohexane, 2-methylpentane diol, 2-methylpropane-(1,3)-diol, hexa methylene glycol and bisphenol A etc., may be listed. Then as the dicarboxylic acids to be used for denaturing, aromatic dicarboxylic acids including isophthalic acid a and naphthalene dicarboxylic acidd,etc., and aliphatic dicarbxylic acids including adipic acid, azelaic acid, dcdecane dicarboxylic acid, etc., are available. Appropriate polyester resins of this invention should have specific viscosities being higher than at least 0.5 At 23 C and 8% concentration in o-chlorophenol It should d be noted that to the polyester resin compositions of this invention, such reinforcing agents as glass fiber, whisker, carbon fiber, glass bead, glass flake, etc. , such inorganic fillers as calcium carbonate, talc, mica, clay, etc., and flame retarders, flame retarded assistants, pigments, dyes, lubricants, antistatic agents, plasticizers, ultraviolet ray absorbers, antioxidants, foaming agents, etc., may be added as desired. In the following, a few embodiments of this invention and a control are presented, but this does not signify that this invention shall be linited, in the modes of its application, to these embodiments. Example 1: One hundred parts of a composition composed of 70 parts of polybutylene terephthalate and 30 parts of glass fiber, with 0.1 part of p-hydroxyphenyl hydantoin added, was kneaded, and extruded by a 40 mm single ascrew extruder. The extruded compositionmwzss pelletized, and dried with a hot air drier; thereafter, the amount of terephthalic acid released in the process of molding was maasured. In dtsraining the amount of terephthalic acid released, pellets weighing 4 kg are subjected to a free flow for 30 minutes, actually using a molder, under a molding condition of the molder cylinder temperature being set at 260 C; the gas released was collected, and absorbed by dimethylsulfoxide; and then, the amount of terephthalic acid contained in the liquid qas determined by maans of ultraviolet ray absorption spectrum. The result showed that the amount of terephthalic acid absorbed in dimethyl sulfoxide awas found to be 0.05 mg/kg of pellets Control I Pellets of the saine composition as that of Example 1 except that -it did not contain p-hydroxyphenyl hydantoin were prepared, and for these pellets, the amount of terephthalic acid released was determined in the similar way to be 0.69 mg/kg of pellets. Examples 2 and 3 Pellets were prepared similarly as in Example 1 ex cept that the amount of p-hydroxyphenyl hydantoin was respectively set to 0.05 parts and 0.15 parts, and the amount of terephthalic acid released was found to be as follows, as determined in the similar way Amount added (parts) Amount of terephthalic of p-hydroxyphenyl acid (mg/kg of hydantoin pellets) 0.05 0.10 0.15 0.06

Claims: what is claimed is 1 A thermoplastic polyester composition formed by adding and mixing a hydantoin compound into a thermoplastic polyester resin having an aromatic dibasic acid as its major acid component. 2 A composition as aspecified in Claim l wherein the aromatic dibasic acid is terephthalic acid. 3 A composition as specified in Claim 2 wherein the thermoplastic polyester resins include polyethylene terephthalate, polytrimethylene terephthalate, and polytetra methylene terephthalate resins or their blends 4 A composition as specified in Claims 1 through 3 wherein as the hydantoin compound, hydantoin or any hydantoin compounds each bearing some radical as a substituent at the fifth posItion may be included 5 A composition as specified in Claim 4 wherein the hydantoin compound is parahydroxphenyl hydantoin.

Inventors: KASUGA, TAKUZO, NAKASHIMA, TSUNEYASU, TAKAHASHI, KATSUHIKO
Applicants: POLYPLASTICS CO. LTD.
Application year: 1982
Main classification: C08L67
IPC codes: C08K5, C08L67