HEAT RESISTING POLYESTER COMPOSITION

Abstract: The present invention relates to fire retardant thermo­ plastic polyester compositions having improved moldability, mechanical properties, heat-resistive property in melting or long-term heat aging and color durability, in particular to thermoplastic polyester compositions consisting of fire retardant polyalkylene terephthalate resins blended with polyolefins or copolymers of olefin.

Description: HEAT RESISTING POLYESTER COMPOSITION The present invention relates to fire retardant the= plastic polyester compositions having improved moldability, mechanical properties, heat-resistive property in melting or long-term heat aging and color durability, in particular to thermoplastic polyester compositions consisting of fire retardant polyalkylene terephthalate resins blended with polyolefins or copolymers of olefin. High molecular weight polyesters or copolymerized polyesters consisting of glycol and terephthalic acid or iso- phthalic acid are widely used as engineering plastics because they have superior mechanical properties, electric properties moldability and the like. However, the uses of these thermcplastic polyesters are limited owin to their indicental inflammability. Accordingly, various methods have been tried in order to obtain fire retardant thermoplastic poly ester, Conventionally halogen contained organc compounds such as decabromodiphenylether, brominated polycarbonate, brcrimated esters of cyanuric acid, brominated epoxy compounds zr.d the like have been blended with thermoplastic polyesters in order to obtain fire retardant thermoplastic polyesters, chiefly. Also it is known that the use of assistant fire retardants such as oxides, hydroxides and the like of metals, including antony trioxide, antimony halogenides, aluminium hydroxide, magnesium hydroxide and the like, together with said fire retardants leads to still more superior fire retardant effects. However, these compounds are disagreeable in respect of heat-resisting property of resins. That is to say, the above described halogen contained organic compounds are gradually decomposed by the action of heat or light to generate halogen radicals and then hydrogen-extracting reaction is carried out to generate hydrogen halogenides. The resulting radicals or hydrogen halogenides lead to the deterioration of resins because they accelerate the radical decomposition, hydrolysis, ester exchanges and the like of polyester resins. On the other hand, also inorganic compounds represented by antimony trioxide give bad influences upon heat-resistive property of Polyester resins because they act as catalyzers of hydrolysis and ester-exchanging reactions essentially. Accordingly, mechanical properties of resins containing these fire retardants added thereto are remarkably lowered when they reside in an extruder or a molder for a long time or are subjected to heat aging for a long time. Accordingly, if the bad influences of said fire retardants on resins can be controlled without spoiling the fire retardant affests thereof, not only the compositions of said resine will be more widely used but also the molded products of hot-liner type, which have nevar been used owing to an insufficient heat-restive property thereof and are advantageous in respect of resource-saving, can be attained. The inventors found that heat resistance owing to the deterioration of resins, moldability, mechanical properties and the like of fire retardant polyesters can be remarkably improved by blending them with polyolefins or copolymers of olefin. This recovery led to the present invention. Also it was found by the inventors that the use of said fire retardants and assistant fire retardants, which were previously blended with polyolefins or copolymers of olefin at teriperatures higher than melting points thereof followed by ccoling and then grinding, still further improved the above described effects. That is to say, the present invention relates to thermo- plastic polyester compositions consisting of thermoplastic polyester resins containing fire retardants, assistant fir retardants and inorganic fillers added thereto and polyolefins or copolymers of olefin blended therewith, in particnlar to compositions containing fire retardants and assistant fire retardants which were previously blended with polyolefins or copolymers at temperatures higher than pelting points thereof followed by cooling and then grinding According to the present invention, heat resistance, color durability and mechanical properties of thermo plastic polyester resins can be remarkably improved, in particular when melting or heat aging for a long time. This effect of the present invention can not be attained by uslng stabilizers which have been generally used for polyester compositions. It is, perhaps, the reason for this fact that radical decomposition, hydrolysis, ester exchange and the like can be controlled thereby resins can be prevented from deteriorating by blending thermoplastic polyester resins with polyolefins or Co- polymers of olefin said polyolefins used in the present invention are preferably polyethylene, polypropylene and the like while said copolymers of olefin are preferably copolymers con taining ethylene as their main component such as ethylene/ propylene copolymer, ethylene/vinyl acetate copolymer, ethylene/acrylic ester copolymer, ethylene/acrylic acid copolymer and the like. The kinds of said polyolefins or copolymers of olefin are not limited but low molecular weight polyolefins, which are not self-moldable, in particular polyethylene wax are preferably used owing to easy wetting and molting/blending of fire retardants and assistant fire retardants while extrusion. Polyethylene wa=, as known well, is manufactured by thermal decomposition or polyethylene resin or polymerization of ethylene. In particular, polyethylene wax manufactured by thermal decomposition of polyethylene resin is suitable for the object of the present invention in respect of its dispersability because it contains some polar groups. The mixtures consisting of two kinds or more of these polyolefins or copolymers of olefin may be usec The amount of said polyolefins or copolymers of olefin used may be appropriately selected within a range of 0.5 to 100% by weight based on said fire retardants and assistant fire retardants, preferably a range of 2 to 509 by weight. Accordingly, a remarkably small amount of said polyolefins or copolymers of olefin based on the whole polyester composition is sufficient. Even 5e or Iss by weight, further 18 or less by weight of said polyolefins or copolymers of olefin based on the whole polyester co-position can give the above described effect. The compositions of the present invention can contain further antioxidants which are various kinds of derivatives of hindered phenols and hindered amines and the like; phosphorus contained stabilizers which are aromatic phophite such as triphenylphosphite, tricresylphosphite and the like, alkyphosphite such as tridodecylphosphite and the like or phosphonate and the like; as well as generally available antioxidants, ultraviolet ray absorbents, hydrolysis inhibitors, heat stabili=ers and the like. Polyester compositions of the present invention can contain further reinforcing agents such as glass fibers, carbon fibers and the like; pigments; dyes; fillers such as talc, potassium titanate and the like; lubricants; antistatic agents; crystalline nuclei; plasticizers; foaming agents s and the like; Generally available halogen contained organic compounds, phosphorus contained organic compounds and the like, prefer- ably bromine contained organic compounds are used for fire retardants in the present invention. Said brine contained organic co=rounds include bromine contained diphenylether, ethylene-bis-phenylether of which 5 to 10 hydrogens in aromatic rings are replaced by bromine atoms, arcnatic carbonates derived from bis-phenol A and the like, bromides of monomers or their polymers of epoxy compounds of said aromatic carbonates, bromides of polystyene oligomers, brominated cyanuric esters and the like. It is desired to use said fire retardants at a ratio as small as possible because a large amount of them leads to the deterioration of mechanical properties of composi- tians The amount thereof is generally 2 to 50% by weight, preferably 3 to 20% by weight based on the whole composi- tion. The kinds or said assistant fire retardants are not limited but they include antimony trioxide, aluminium hydroxide, magnesium hydroxide and the like. The mixtures consisting of two kinds or more of said fire retardants also l so can be used Said mixtures include the mixture of decabromodiphenylether and brominated polycarbonate, the mixture of decabromodiphenylether and brommated epoxy compounds, and the like. It is found that brominated cyanuric acid ester com- pounds, which have been used generally as fire retardants, exhibit an additional beat resistive effect in melting when used together with other fire retardants and they exhibit an effect also as stabilizers. In this case the amount thereof used is not limited. Brominated cyanuric acid ester compounds containing triazine rings represented by the following general formula therein or their mixtures may be suitably used as said brominated cyanuric acid ester compounds in the present invention: EMI8.1 wherein n: Degree of polymerization, R: H, R1, R2, EMI8.2 a + b + c + d # 8 Z: Alkylidene, alkylene, - SO2 -, - SO -, - S -, - O -, Z = ( R3: H, lower alkyl group, halogenized lower alkyl group, and R2: EMI8.3 e + g # 5 At least one of R is R1 and the end portion of R1 is H, OH or R2 said polyester resins used in the present invention can be obtained from glycols and terephthalic acid or its derivatives as acidic components. However, these components may be denatured by other glycols or dicarboxylic acids. Said dicaboxylic acids used for denaturing said polyester resins include alkyl derivatives of phthalic acids such as those of isophthalic acid, naphthalene dicarboxylic acid and the like; aronatic dicarboxylic acids; aliphatic or cycloaliphatic dicarboxylic acids such as succinic acid, adipic acid, azeiaic acid, dodecanoic acid, cyclohexane dicarboxylic acid and the like Said glycols used for denaturing include aliphatic or cycloaliphatic glycols such as neopentyl glycol, 1, 4 dimethylolcyclohexane, 2 - methylpentanol, bisphenol A and the live. Also the mixtures consisting of two kinds or more of these denaturing conponents may be used. Said polyester resins preferably used in the present invention include polyalkylene terephthalate resins such as polyethylene terephthalate, polybutylene terephthalate and the like. Also the mL=tres consisting of two kinds or more of said polyester resins may be used. In particular, the mixture of polyethylene terephtnalate and polybutylene terephthalate is desirable. Said polyesters used in the present invention have inherent viscosity of at least 0.4 to 1.5 dl/g, preferably 0.7 to 1.2 dl/g measured in o - chlorophenol at 23 C and their concentration of 8E. Although said polyester resins are generally blended with b said polyolefins or copolymers of olefin by preliminarily dry-blending said polyolefins or copolymers of olof in with said polyester resins, fire retardants, assistant fire retardants and other additives, then melting/mixing by means of an extruder heated followed by extruding to pellet other various mixing methods also may be used The preliminary blend of said polyolefins or copolymers of olefin with said fire retardants and said assistant fire retardants is particularly desirable In this case, the blend is carried in Henschel mixer provided with a jacket, Banbury mixer, extruder and the like at temperatures higher than its melting point. The resulting blend is cooled and then ground¯ The resulting blend is further blended with said polyester resins together with other additives and then the resulting composition is pelletized by means of the above described general method. Also said fire re- tardants and said assistant +ire retardants as well as other additives may be preliminarily blended with said polyolefins and/or copolymers of olefin. The present invention will be in detail described by reference to examples hereafter. However, the present invention is not limited by such examples. Examples 1 to 5 and Comparative Examples 1 to 4 The component havina the compositions as shown in Table I was obtained by mixing polybutylene terephthalate (PBT) having inherent viscosity of 0.80 dl/g with polyethylene terephthalate (PET) having inherent viscosity of 0.68 dl/g. In these examples, said fire retardants and said assistant fire retardants were preliminarily blended with low molecular weight polyethylene in the following manner: The appointed amount of said low molecular weight polyethylene was blended with said halogen contained organic compounds, which are fire retardants, and antimony trioxide, which is an assistant fire retardant, at temperatures higher than melting points of said low molecular weight polyethylene in Henschel mixer provided with a jacket heated by water vapor. Alter the blend was sufficiently carried out, the resulting blend was ccoled by water and then ground. The compositions consisting of components at ratios as shown in Table I were extruded to pelletize by means of a 65 ms extruder of single type heated up to 240 to 250 C The resulting pellets were dried in a hot blast dryer and then injection molded by means of an injection molding machine, of which cylinder tem.perature was adjusted to 260 C, ot obtain test pieces for Ash tensile tests. The test pieces obtained by molding according to the general molding cycle (injection of 20 seconds + cooling of 10 seconds) were compared with the test pieces obtained by molding after the compositions were resided inside an extruder for 30 minutes on heat resistance. In addition, the test pieces were tested on tensile strength after heat aging for a long time in a hot blast dryer kept at 2000C. Color durability in melting was compared on the basis of the degree of discoloration AE. That is to say, Hunter's color indicating system L, a, b or the test pieces was measured by means of 2 digital color measuring machine (ND504AA type, Nippon Denshoku Xogyo it. K.) and said degree of discoloration #E was calculated by the following equation: The smaller the value of AE is, the more superior color durability is. EMI12.1 wherein L0, a0, b0: the values of the test pieces molded without residing in an extruder, and L, a, b: the values of the test pieces molded after the compositions were resided inside an extruder for 30 minutes. The results are shown in Table I and Table II. The values of composition shown in Table I are all expressed by percentages by weight based on the whole com- position excluding the amount of polyethylene to be previously treated. Table I EMI13.1 Examples <SEP> Comparative <SEP> examples <tb> Composition| <SEP> and <tb> physical <SEP> properties <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 4 <SEP> 5 <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 4 <tb> B <SEP> T <SEP> 58.5 <SEP> 58.5 <SEP> 42.5 <SEP> 58.2 <SEP> 69.1 <SEP> 58.5 <SEP> 42.5 <SEP> 69.1 <SEP> 58.2 <tb> E <SEP> T <SEP> 14.1 <SEP> 14.1 <tb> ass <SEP> fibers <SEP> 31.0 <SEP> 31.0 <SEP> 31.0 <SEP> 31.0 <SEP> 18.0 <SEP> 31.0 <SEP> 31.0 <tb> bestos <SEP> 2.5 <SEP> 2.5 <SEP> 2.5 <SEP> 2.5 <SEP> 3.0 <SEP> 2.5 <SEP> 2.5 <SEP> 3.0 <SEP> 2.5 <tb> 3.3*2 <SEP> 3.3*2 <tb> logen <SEP> contained <SEP> compounds <SEP> 3.8*2 <SEP> 3.8*2 <SEP> 5.8*3 <SEP> # <SEP> 4.7*2 <SEP> 3.8*2 <SEP> 5.8*3 <SEP> 4.7*2 <SEP> # <tb> 0.8*3 <SEP> 0.8*3 <tb> Amount <SEP> of <SEP> PE <SEP> to <SEP> be <SEP> previously <SEP> treated <tb> (% <SEP> by <SEP> weight <SEP> based <SEP> on <SEP> halogen <SEP> 13 <SEP> - <SEP> 10 <SEP> 10 <tb> contained <SEP> compounds) <tb> timony <SEP> trioxide <SEP> 4.2 <SEP> 4.2 <SEP> 4.1 <SEP> 4.2 <SEP> 5.2 <SEP> 4.2 <SEP> 4.1 <SEP> 5.2 <SEP> 4.2 <tb> Amount <SEP> of <SEP> PE <SEP> to <SEP> be <SEP> previously <SEP> treated <tb> (% <SEP> by <SEP> weight <SEP> based <SEP> on <SEP> antimony <SEP> 10 <SEP> 40 <SEP> 40 <SEP> 10 <SEP> 10 <tb> trioxide) <tb> anges <SEP> of <SEP> physical <SEP> properties <SEP> in <tb> pendence <SEP> upon <SEP> residence <SEP> time <SEP> of <tb> npositions <SEP> in <SEP> an <SEP> extruder <SEP> prior <tb> molding <tb> Tensile <SEP> strongth <SEP> 0 <SEP> minute <SEP> 1458 <SEP> 1385 <SEP> 1180 <SEP> 1435 <SEP> 1230 <SEP> 1285 <SEP> 1035 <SEP> 1230 <SEP> 1298 <tb> (kg/cm2) <SEP> 30 <SEP> minutes <SEP> 1296 <SEP> 1193 <SEP> 1013 <SEP> 1378 <SEP> 1058 <SEP> 835 <SEP> 777 <SEP> 743 <SEP> 979 <tb> Degree <SEP> of <tb> 30 <SEP> minutes <SEP> 3.72 <SEP> 3.77 <SEP> 4.02 <SEP> 3.50 <SEP> 4.96 <SEP> 9.51 <SEP> 9.62 <SEP> 9.03 <SEP> 0.96 <tb> discoloration <tb> at <SEP> aging <SEP> at <SEP> 200 C <SEP> 1385 <SEP> 1274 <SEP> 944 <SEP> 1363 <SEP> 1143 <SEP> 1028 <SEP> 757 <SEP> 981 <SEP> 1160 <tb> Low molecular weight polyethylene (molecular weight of 5,000, manufactured by thermal decomposition method) Decabromodiphenylether Brominated cyanuric acid ester compounds (AFR3001-H manufactured by Asahi Glass Co., Ltd.) Table II EMI14.1 <SEP> Cases <SEP> .e <SEP> II <SEP> ComFar'ative <SEP> euanple <SEP> 1 <tb> Physical <SEP> Pronerties7¯¯¯¯¯ <SEP> | <tb> Izod <SEP> -pact <SEP> strength <tb> <SEP> (kg <SEP> . <SEP> cm/cm) <tb> <SEP> With <SEP> notch <SEP> 7.8 <SEP> 8.0 <tb> <SEP> Without <SEP> notch <SEP> 64 <SEP> | <SEP> 60 <tb> <SEP> . <tb> Bending <SEP> strength <SEP> 2044 <SEP> 2068 <tb> <SEP> (kg/cm2 <SEP> ) <tb> Elastic <SEP> modulus <SEP> in <SEP> 1 <SEP> 11 <SEP> x <SEP> 104 <SEP> 11.5 <SEP> x <SEP> 104 <tb> bending <SEP> (kg/cn2) <tb> The molding temperature of the test pieces was set to the cylinder temperature of 240 C. Example 6 The compositions, preparation and tests of the test pieces were carried out in the same manner as described in Examples 1 to 5 excepting that low molecular weight polyethylene (molecular weight of 4,000) manufactured by a poly merization method was used instead of low molecular weight polyethylene manufactured by a thermal decomposition method (molecular weight of 5,000). The results are shown in the following table EMI14.2 <SEP> Tensile <SEP> strength <SEP> (kg/cm2) <tb> Method <SEP> of <tb> Example <tb> <SEP> manufacturing <SEP> PE <SEP> Without <SEP> residing <SEP> After <SEP> residing <SEP> in <SEP> an <tb> <SEP> in <SEP> an <SEP> extruder <SEP> extruder <SEP> for <SEP> 30 <SEP> minutes <tb> <SEP> Polymerization <tb> 6 <SEP> 1468 <SEP> 1248 <tb> <SEP> method <tb> Examples 7, 8 The test pieces were prepared from the compositions, which wcre obtained by adding low molecular weight polyethylene used in Examples 1 to 5 to the composition used in the comparative example 1 at 2 ratio of n.° and 2 parts by weight based on the latter of 100 parts by weight, respectively, by means of a biaxial extruder of 28 mm. The test results are shown in the followincr table: EMI15.1 <tb> <SEP> Tensile <SEP> strength <SEP> (kg/cm2) <tb> <SEP> Amount <SEP> added <tb> <SEP> Without <SEP> residing <SEP> After <SEP> the <SEP> composition <tb> Example <tb> <SEP> in <SEP> an <SEP> extruder <SEP> was <SEP> resided <SEP> in <SEP> an <tb> <SEP> (parts <SEP> by <SEP> weight) <tb> <SEP> extruder <SEP> for <SEP> 30 <SEP> minutes <tb> 7 <SEP> 0.9 <SEP> 1482 <SEP> 1215 <tb> <SEP> 8 <SEP> 2 <SEP> 1285 <SEP> 1028 <tb> Examples 9 to 11 The test pieces were prepared in the same manner as described in Example 2 by means of a biaxial extruder of 28 mm excepting that polyethylene having different molecular weight3 were used. The test results are shown in the following table= EMI15.2 <tb> <SEP> Tensile <SEP> strength <SEP> (kg/cm2) <tb> Molecular <SEP> weight <tb> After <SEP> the <SEP> composition <tb> <SEP> Example <tb> <SEP> of <SEP> polyethylene <SEP> Without <SEP> residing <SEP> was <SEP> resided <SEP> inside <SEP> an <tb> <SEP> extruder <SEP> for <SEP> 25 <SEP> minutes <tb> <SEP> 9 <SEP> 1500 <SEP> 1296 <SEP> 1079 <tb> <SEP> 10 <SEP> 5000 <SEP> 1365 <SEP> 1174 <tb> <SEP> 11 <SEP> 40000 <SEP> 1338 <SEP> 1004 <tb> Low molecular weight polyethylenes having molecular weight of 1,500 and 5,000 were manufactures by thermal decomposition method. Examples 12 to 15 and Comparative Example 5 The test pieces were prepared from the compositions as shown in the following table, which uere obtained by adding low molecular weight polyethylene used in examples 1 to 5 to the systems in which one kind cr two kinds or more of fire retardants were used and brominated cyanuric acid ester compounds were added, by means of a monoaxial type extruder of 65 mm and tested in the sane manner as described in Examples 1 to 5. The test results are shown in Table III. The values of composition are represented by parts by weight based on th2 whole composition of 100 parts. Blso the case, in which brominated cyanuric acid esters were not used. were shown for comparative examples. Table III EMI17.1 Cmposition <SEP> and <SEP> physical <SEP> Comparative <tb> Examples <tb> examples <tb> properties <SEP> 12 <SEP> 13 <SEP> 14 <SEP> 15 <SEP> 5 <tb> P <SEP> B <SEP> T <SEP> 58.2 <SEP> 58.4 <SEP> 58.3 <SEP> 58.9 <SEP> 59.9 <tb> Glass <SEP> fibers <SEP> 31.0 <SEP> 31.0 <SEP> 31.0 <SEP> 31.0 <SEP> 31.0 <tb> Asbestos <SEP> 2.5 <SEP> 2.5 <SEP> 2.5 <SEP> 2.5 <SEP> 2.5 <tb> 2.6 <SEP> *2 <SEP> 2.6 <SEP> *2 <SEP> 2.6 <SEP> *2 <tb> Halogen <SEP> contained <SEP> compounds <SEP> 3.3 <SEP> *2 <SEP> 2.7 <SEP> *2 <SEP> # <SEP> # <SEP> # <tb> 0.6 <SEP> *4 <SEP> 0.6 <SEP> *4 <SEP> 0.6 <SEP> *4 <tb> Antimony <SEP> trioxide <SEP> 3.6 <SEP> 3.0 <SEP> 3.4 <SEP> 3.4 <SEP> 3.4 <tb> Brominated <SEP> cyanuric <SEP> acid <SEP> *3 <tb> 0.8 <SEP> 0.8 <SEP> 0.8 <tb> ester <SEP> compounds <tb> Polyethylene <SEP> *1 <SEP> 0.8 <SEP> 1.6 <SEP> 0.8 <SEP> 1.0 <tb> Changes <SEP> of <SEP> physical <SEP> properties <tb> in <SEP> dependence <SEP> upon <SEP> residence <tb> time <SEP> of <SEP> compositions <SEP> in <SEP> an <tb> extruder <SEP> prior <SEP> to <SEP> molding <tb> Tensile <SEP> strength <SEP> 0 <SEP> minute <SEP> 1400 <SEP> 1454 <SEP> 1421 <SEP> 1393 <SEP> 1362 <tb> (kg/cm2) <SEP> 30 <SEP> minutes <SEP> 1281 <SEP> 1352 <SEP> 1272 <SEP> 1143 <SEP> 833 <tb> *1 Low molecular weight polyethylene (molecular weight of 5,000, manufactured by thermal decomposition method) *2 Decabromodiphenylether *3 AFR 3001-H manufactured by Asahi Glass Co., Ltd. *4 Brominated polycarbonate

Claims: The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows: 1. Thermoplastic polyester compositions consisting of thermoplastic polyester resins containing fire retardants, assistant fire retardants and inorganic fillers blended with polyolefins or copolymers of olefin. 2. Thermoplastic polyester compositions as set forth in claim 1, in which said polyolefins or copolymers of olefin are preliminarily blended with said fire retardants and said assistant fire retardants at temperatures higher than the melting points thereof and the resulting blend is cooled followed by grinding. 3. Compositions as set forth in claim 1, in which said thermoplastic polyester resins are polyalkylene terephthaláte resins 4. Compositions as set forth in claim 2, which said polyalkylene terephthalate resins are polybutylene terephthalate. 5. Compositions as set forth in claims 1 to 4, in which said polyolefins are low niolecular weight polyethylene which has not self-moldability. 6. Compositions as set forth in claims 1 to 5, in which said fire retardants are chlorine con-emined organic compounds and said assistant fire retardants are inorganic compounds. 7. Compositions as set forth in claim 6, in which said fire retardants are decabromodiphenylether, bromina ted polycarbonate, brominated esters of cyanuric acid, brominated epoxy compounds or the mixtures thereof. 8. Compositions as set forth in claims 1 to 7, in which said inorganic fillers are glass fibers.*

Inventors: KASUGA, TAKUZO, NAKASHIMA, TUNEYASU, TAKAHASHI, KATSUHIKO
Applicants: POLYPLASTICS CO. LTD.
Application year: 1982
Main classification: C08L67
IPC codes: C08K3, C08L67, C08L21, C08K5, C08L101, C08L23, C08L7, C08L33