JP3136743B2 - Copolyester and molded product thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a copolymerized polyester useful for bottles, films, sheets, cups and the like. Specifically, P in an undrawn state or a low drawn state
Improves the impact resistance of ET and can be easily manufactured with conventional general polyester production equipment. It is particularly suitable not only for continuous polymerization equipment, but also improves productivity, and has the same or higher thermal stability as PET. The present invention relates to a copolyester having heat resistance and heat resistance and a molded product thereof.

[0002]

2. Description of the Related Art Polyethylene terephthalate (hereinafter, referred to as "polyethylene terephthalate")
It is called "PET". ) Is excellent in mechanical strength, chemical stability, transparency, hygiene and the like, and is lightweight and inexpensive, so that it is widely used as a packaging material for various sheets and containers. Particularly in recent years, from the viewpoints of waste disposal problems and environmental protection, applications to extruded sheets, deep drawn containers, direct blow bottles, and the like, in which polyvinyl chloride, polystyrene, and the like have conventionally been frequently used, have been remarkable.

[0003] In the case of such a PET, for example, in the case of a direct blow bottle, it is general that a tubular pipe is extruded by an extruder and then fused and bottomed, and at the same time, blown in a mold having a predetermined shape. . However, conventional PET
In applications used in an unstretched state or in a low stretched state, such as a direct blow bottle, it is difficult to say that the impact resistance is sufficient, and cracks and breakage are liable to occur, particularly in a part that is easily impacted such as the bottom. There was a problem.

[0004] On the other hand, there is a method of improving the impact resistance by extremely increasing the intrinsic viscosity of PET, but there are problems such as a decrease in productivity and an increase in resin cost. As a method for improving the impact resistance of PET, a method of copolymerizing cyclohexane dimethanol has been proposed. However, since the cyclohexane dimethanol component is distilled out together with ethylene glycol during the polymerization, a recycled material of the recovered fraction is used. However, the production process had to be complicated, and it could not be easily produced with conventional general polyester continuous production equipment.

On the other hand, it is known that a copolymer polyester having properties similar to PET, for example, a copolymer polyester obtained using terephthalic acid and cyclohexanedicarboxylic acid as dicarboxylic acid components and ethylene glycol and diethylene glycol as diol components. Have been. However, specific copolymerized polyesters having impact resistance higher than PET and improved productivity have not been specifically known.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to improve the impact resistance in a non-stretched state or a low-stretched state as compared with conventional PET, and to facilitate the production using conventional polyester continuous polymerization equipment. Another object of the present invention is to provide a copolymerized polyester having improved productivity.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that a specific physical property in which a small amount of cyclohexanedicarboxylic acid units and ethylene glycol units are contained in conventional PET. A range of copolymerized polyesters has been found and the present invention has been reached. That is, the gist of the present invention is a copolymerized polyester containing terephthalic acid as a dicarboxylic acid component and ethylene glycol as a diol component, and (1) cyclohexanedicarboxylic acid as a dicarboxylic acid component in an amount of 0.5 to 10 mol%. (2) 1.0 to 4.0 mol% of diethylene glycol as a diol component, and (3) an intrinsic viscosity of 0.6 to
2.0 dl / g, (4) a copolymerized polyester characterized by having a terminal carboxyl group concentration of 40 eq / ton or less, and a molded article thereof.

Further, the method for producing the copolymerized polyester includes a copolymerized polyester containing terephthalic acid as a dicarboxylic acid component and ethylene glycol as a diol component, and (1) cyclohexanedicarboxylic acid as a dicarboxylic acid component. 0.5-10 mol%,
(2) 1.0 to 4.0 mol% of diethylene glycol as a diol component, and (3) intrinsic viscosity of 0.5 to 4.0.
A method of solid-phase polymerization of a copolyester (hereinafter, referred to as “prepolymer”) having 0.8 dl / g and (4) a terminal carboxyl group concentration of 10 to 60 eq / ton is preferable. Hereinafter, the present invention will be described in detail.

In the copolymerized polyester of the present invention, as for terephthalic acid and ethylene glycol as main components, known raw materials used in PET may be used. The raw materials for the cyclohexanedicarboxylic acid unit include 1,2-, 1,3
-And 1,4-cyclohexanedicarboxylic acid, and esters thereof such as dimethyl ester and diethyl ester; alkyl such as 2-methyl-1,4-cyclohexanedicarboxylic acid and 5-methyl-1,3-cyclohexanedicarboxylic acid Substituents and alicyclic substituents such as alkoxy, aryl, aralkyl and halogen are exemplified. In addition, the cis-trans ratio may be a mixture in any ratio. Of these, the cis / trans ratio is usually (0 to 80) / (100 to 20), preferably (0 to 7).
1,4-cyclohexanedicarboxylic acid or its dimethyl ester having a ratio of 0) / (100 to 30) is particularly preferably used.

Further, diethylene glycol (hereinafter referred to as "D
EG ". In the case of), ethylene glycol is partially produced as a by-product during the polymerization reaction. Therefore, in addition to using a predetermined amount of DEG or its ester-forming derivative as a raw material for polymerization, reaction conditions, additives, and the like are appropriately selected. Only with this, the content of the DEG component can be controlled. In particular, in the case of the copolymerized polyester of the present invention, the melt polymerization temperature can be lowered by the effect of adding cyclohexanedicarboxylic acid (hereinafter referred to as “CHDA”),
It is easy to keep the EG component content low. Also,
As the additive, for example, triethylamine, tri-n
-Tertiary amines such as butylamine and benzyldimethylamine; quaternary ammonium hydroxides such as tetraethylammonium hydroxide, tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide; and lithium carbonate, sodium carbonate, potassium carbonate and sodium acetate. By adding a small amount of the basic compound of the above, the generation of DEG can be suppressed. On the other hand, if a small amount of an inorganic acid such as sulfuric acid is added to the polymerization raw material, the generation of DEG can be promoted and the content can be increased.

If necessary, these additives for controlling the amount of DEG produced are usually used in an amount of 0.001 to 1% of the total amount of the polymerization raw materials.
0% by weight, preferably 0.005 to 1% by weight. In the copolymerized polyester of the present invention, the ratio of cyclohexanedicarboxylic acid in all dicarboxylic acid components is 0.5 to
10 mol%, preferably 1.0 to 5.0 mol%, particularly preferably 1.0 to 4.0 mol%, and the proportion of DEG in all diol components is 1.0 to 4.0 mol%. Mol%, preferably 1.0 to 3.5 mol%, particularly preferably 1.
5 to 3.5 mol%.

When the ratio is less than the above range, the effect of improving impact resistance is small, and superiority over conventional PET is not recognized. On the other hand, when the ratio exceeds the above range, the wet heat resistance and the thermal stability are lowered, and the glass transition temperature (Tg) is lowered. The glass transition temperature of the copolymerized polyester of the present invention is usually 65 ° C. or higher, preferably 70 ° C. or higher.

Next, the intrinsic viscosity of the copolymerized polyester of the present invention is phenol / tetrachloroethane (weight ratio 1/1).
It measured at 30 degreeC in the mixed solvent of 1), and was 0.60-2.
00 dl / g, preferably 0.70 to 1.50 dl / g
g. If it is less than 0.60 dl / g, the obtained copolyester cannot have sufficient practical strength when formed into a molded article. On the other hand, if it exceeds 2.00 dl / g, the melt viscosity becomes too high, and the heat generated by shearing in the bubble during injection or extrusion becomes large, so that the decomposition reaction becomes remarkable, and the generation of air bubbles and the like is preferred. Absent.

Further, the concentration of the terminal carboxyl group of the copolymerized polyester of the present invention is 40 eq / ton or less, preferably 30 eq / ton or less, particularly preferably 5 to 2 eq / ton.
5 eq / ton. If the concentration of the terminal carboxyl group exceeds the above range, it is not preferable because the moisture resistance and the thermal stability are lowered and the oligomer adheres to a mold at the time of molding.

The above-mentioned copolymerized polyester of the present invention comprises P
ET is produced by performing melt polymerization and subsequent solid phase polymerization according to a conventionally known method. As the melt polymerization method, for example, there is a method in which after a direct esterification reaction is performed under pressure using terephthalic acid, cyclohexanedicarboxylic acid and ethylene glycol, the temperature is further raised, and the pressure is gradually reduced to carry out a polycondensation reaction. Alternatively, an ester derivative of terephthalic acid, for example, terephthalic acid dimethyl ester, cyclohexanedicarboxylic acid dimethyl ester, and transesterification using ethylene glycol, and then can be produced by further polycondensation of the obtained reaction product. . In these polycondensation reactions, the cyclohexanedicarboxylic acid component can be added at any time at the beginning of the esterification reaction, transesterification reaction, or polycondensation reaction. For example, a transesterification reaction of a terephthalic acid ester derivative and ethylene glycol may be performed in advance, and cyclohexanedicarboxylic acid may be added to the transesterification reaction product for polycondensation.

Such a polycondensation reaction may be performed in one stage or may be performed in a plurality of stages. When the reaction is carried out in a plurality of stages, the polycondensation reaction conditions are such that the reaction temperature of the first stage polycondensation is usually 250 to 290 ° C, preferably 260 to 280 ° C.
The pressure is usually 500 to 20 mmHg, preferably 200 to 30 mmHg, and the temperature of the final stage polycondensation reaction is usually 265 to 300 ° C, preferably 270 to 300 mmHg.
295 ° C., and the pressure is usually 10 to 0.1 mmHg, preferably 5 to 0.5 mmHg.

When the polycondensation reaction is carried out in two stages,
The conditions of the polycondensation reaction of the first and second stages are respectively in the above ranges.
The conditions between the stage and the final stage reaction conditions are also conditions. For example, when the polycondensation reaction is carried out in three stages, the reaction temperature of the second stage polycondensation reaction is usually from 260 to 295C, preferably from 270 to 285C, and the pressure is usually from 50 to 2C.
mmHg, preferably in the range of 40-5 mmHg.
The intrinsic viscosity reached in each of these polycondensation reaction steps is not limited, but it is preferable that the degree of increase in the intrinsic viscosity in each stage is smoothly distributed, and furthermore, the final stage polycondensation reactor Has a limiting viscosity of usually 0.45 to 0.85 dl / g, preferably 0.50 to 0.80 dl / g, particularly preferably 0.1 to 0.8 dl / g.
It is 50 to 0.70 dl / g.

Below this range, it is difficult to make chips,
On the other hand, above this range, it is difficult to extract the prepolymer from the reactor. Normal. The prepolymer is withdrawn from the molten state into strands and then cut into granular chips. Such granular chips are usually 2.0-5 m
m, preferably 2.2 to 4.0 mm.

In the above esterification reaction, transesterification reaction and polycondensation reaction, it is preferable to use necessary amounts of an esterification catalyst, a transesterification catalyst, a polycondensation catalyst, a stabilizer and the like. As the transesterification catalyst, known compounds, for example, one or more of calcium, titanium, manganese, zinc, sodium and lithium compounds can be used, but manganese compounds are particularly preferred from the viewpoint of transparency. Examples of the polymerization catalyst include known ones such as germanium, antimony, titanium and cobalt compounds.
More than one kind can be used, but a germanium compound or an antimony compound is preferably used. The amount of the catalyst used in the esterification catalyst and the polymerization catalyst is usually 5 to 2000 ppm, preferably 10 to 500 ppm in the total amount of the polymerization raw materials in terms of metal amount. In particular, when using a germanium catalyst as a polymerization catalyst, when it is desired to greatly reduce the amount of oligomers contained in the copolymerized polyester after solid-phase polymerization for the purpose of improving contamination of a mold or the like during molding. The amount of germanium atoms contained in the copolymerized polyester is usually 30
６０60 ppm, preferably 35 to 55 ppm, particularly preferably 38 to 50 ppm.

Examples of the stabilizer include phosphates such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate and tricresyl phosphate, triphenyl phosphite, trisdodecyl phosphate and the like. Phosphites such as phytite and trisnonylphenyl phosphite; acid phosphates such as methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate and dioctyl phosphate; and phosphoric acid and phosphorous acid And phosphorus compounds such as hypophosphorous acid and polyphosphoric acid. The stabilizer is used as a weight of phosphorus atom in the stabilizer, usually 10 to 10
1000 ppm by weight, preferably 20 to 200 parts by weight pp
m.

Furthermore, a small amount of a dicarboxylic acid component other than the above-mentioned terephthalic acid and cyclohexanedicarboxylic acid, and a diol component other than ethylene glycol and diethylene glycol may be contained. These dicarboxylic acid components include phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenylsulfonedicarboxylic acid,
4'-biphenyldicarboxylic acid, 1,3-phenylenedioxydiacetic acid, and their structural isomers, malonic acid, succinic acid, aliphatic dicarboxylic acids such as adipic acid,
Examples of the oxyacid or a derivative thereof include p-hydroxybenzoic acid, p-hydroxybenzoic acid esters, and glycolic acid. As the diol component,
Aliphatic glycols such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, etc .; alicyclic glycols such as cyclohexanedimethanol; Further, aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S can be exemplified. An amount that is substantially equivalent to all diol components and all dicarboxylic acid components is used.

In addition, a monofunctional compound such as benzoyl benzoic acid or a small amount of a polyfunctional component having three or more functional groups may be contained without departing from the constitutional requirements of the present invention. Examples of the trifunctional or higher polyfunctional component include trimellitic acid, trimesic acid, and their structural isomers, pyromellitic acid and its structural isomers, or anhydrides and core-substituted products of these polyfunctional compounds, Examples include polyhydroxy compounds such as trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol; and polyfunctional compounds such as glycidyl ethers of aromatic dihydroxy compounds, for example, bisiphenol A diglycidyl ether. These monofunctional compounds and trifunctional or higher polyfunctional compounds are usually used in an amount of usually 5 mol% or less, preferably 0.001 to 2.0 mol%, based on the repeating units constituting the polymer.
It is used in the range of mol%. In particular, by using a polyfunctional compound having three or more functional groups, the drawdown property during extrusion molding can be improved.

As described above, the composition (structural unit) of the prepolymer produced by melt polymerization is substantially the same as the copolymerized polyester of the present invention obtained by subjecting the prepolymer to solid-state polymerization. The concentration of the terminal carboxyl group in the prepolymer is usually 10 to 60 eq.
/ Ton, preferably 15 to 50 eq / ton. If the ratio is less than the above range, the solid phase polymerizability is poor, and it takes a long time to increase the intrinsic viscosity. On the other hand, if it exceeds the above range, the thermal stability and wet heat resistance of the copolymerized polyester of the present invention obtained by solid phase polymerization are undesirably reduced. further,
With the aim of improving contamination of molds and the like during molding,
When it is desired to significantly reduce the amount of oligomers contained in the copolymerized polyester after the solid phase polymerization to be subjected to molding, the concentration of the terminal carboxyl group of the corresponding prepolymer is adjusted to 10 to 30 e.
q / ton, preferably 15 to 25 eq / ton.

Next, in order to obtain the copolymerized polyester of the present invention, it is necessary to further subject the prepolymer chips obtained by the melt polymerization as described above to a solid phase polymerization treatment. The prepolymer chips to be subjected to solid-phase polymerization may be preliminarily crystallized by heating to a temperature lower than the temperature at which solid-phase polycondensation is performed, and then supplied to the solid-phase polycondensation step.
In such a pre-crystallization step, the copolyester chips are dried in a dry state, usually at 120 to 200 ° C., preferably 1 to 200 ° C.
It can be carried out by heating to a temperature of 30 to 180 ° C. for about 1 minute to 4 hours, or by heating the chip to a temperature of 120 to 200 ° C. for 1 minute or more under an atmosphere of steam or an inert gas containing steam. You can do it too.

The solid-state polymerization step in which the prepolymer chips are supplied as described above comprises at least one stage, and the polymerization temperature is usually 190 to 230 ° C., preferably 195 to 230 ° C.
25 ° C., pressure is usually 1 kg / cm ² G to 10 mm
Hg, preferably under normal pressure to 100 mmHg, is carried out in an atmosphere of an inert gas such as nitrogen, argon or carbon dioxide. The polymerization time reaches the desired physical properties in a shorter time as the temperature is higher, but is usually 1 to 100 hours, preferably 5 to 70 hours, particularly preferably 10 to 50 hours.

By appropriately selecting the conditions for the above solid phase polymerization treatment, a predetermined intrinsic viscosity can be reached in a shorter time as compared with the case where solid state polymerization is performed under the same conditions as PET, and the copolymerized polyester of the present invention can be obtained. Good productivity can be obtained. The polyester of the present invention thus obtained can be used to form films, sheets, containers, and other packaging materials by using a melt molding method generally used for PET.
If necessary, the mechanical strength can be improved by stretching the copolymerized polyester at least in a uniaxial direction.

In producing the hollow molded article, the copolymer polyester of the present invention is formed by extrusion blow molding, and an apparatus conventionally used for blow molding of polystyrene or polyvinyl chloride can be used. Specifically, for example, after once forming a tubular preform by extrusion molding, immediately after one end is melted while hot and bottomed,
A method of performing blow molding in a mold having a predetermined shape is applied. In this case, the molding temperature, specifically, the temperature of each part of the cylinder and the nozzle of the molding machine is usually set to 260 to 280 ° C.
Within this range, the temperature can be set lower by 1 to 20 ° C. than in the case of general PET, and it is easy to suppress thermal degradation to a low level. further,
It is also easy to keep the amount of by-product acetaldehyde low.

In manufacturing a deep drawn container, a sheet formed from the copolymer polyester of the present invention is formed by deep drawing, and is conventionally used in sheet forming or deep drawing of polystyrene or polyvinyl chloride. Can be used. The molding temperature in the case of sheet molding, specifically the temperature of each cylinder and nozzle of the molding machine,
Usually, the temperature can be set in the range of 260 to 280 ° C., which is lower by 1 to 20 ° C. than in the case of general PET, and it is easy to suppress the thermal degradation to a low level. In deep drawing, the processing temperature is usually 7
The temperature is 0 to 150 ° C., preferably 80 to 130 ° C., and the deep drawing rate may be set at a commonly used setting, but is preferably 0.1
It is about 10 to 10 times.

[0029]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist. In addition, various measurement methods used in this example are described below. The method for measuring the intrinsic viscosity is as described above. (1) Amount of cyclohexanedicarboxylic acid (hereinafter “CHD”)
A amount ”. ) After methanolysis by a conventional method, the produced dimethyl ester component was quantified by gas chromatography. (2) Diethylene glycol amount (hereinafter referred to as "DEG amount") The diol component produced by hydrolysis by a conventional method was quantified by gas chromatography. (3) Terminal carboxyl group concentration (hereinafter referred to as “AV”) 100 mg of a copolymerized polyester sample was heated and dissolved in 5 ml of benzyl alcohol.
After adding and diluting the mixture, use phenol red as an indicator,
It was titrated with a 0.1 N sodium hydroxide / benzyl alcohol solution and quantified. (4) A 2.0 g sample of a germanium atom content (hereinafter referred to as “Ge amount”) copolymerized polyester was prepared in the presence of sulfuric acid.
After incineration and complete decomposition by a conventional method, the volume of the solution was adjusted to 100 ml with distilled water, and quantified by emission spectroscopy. (5) Antimony atom content (hereinafter referred to as “Sb amount”) Quantification was performed by emission spectroscopy in the same manner as in the analysis of germanium atom content.

(6) Glass transition temperature (hereinafter referred to as “Tg”) Tg is SELKO I & E, SSC / 580
It was measured using a (DSC20) type differential scanning calorimeter (manufactured by Seiko Denshi Kogyo KK). (7) Inert gas flow rate The inert gas flow rate is defined as the amount of gas circulated per unit time (hr) and per unit resin weight (kg) is 1 atm.
It was shown by volume (L) converted to. (8) lzod impact strength Notched, 1/8 inch wide ASTM for lzod test
Using a test piece, the humidity was measured in an atmosphere at a temperature of 23 ° C. and a relative temperature of 50%, and the measurement was performed. (9) Drop impact test Fill the container with demineralized water at 23 ° C, attach a metal lid to the opening to prevent the contents from leaking out of the container, and keep the temperature outside the container at 23 ° C and relative temperature. Was dropped vertically from a height of 1.5 m or 2.0 m onto an iron plate having a thickness of 5 cm ten times continuously in an atmosphere of 50%, and the presence or absence of cracks or breakage was confirmed. This was performed for 10 containers, and the drop impact resistance was evaluated based on the number of containers that finally did not crack or break.

Example 1 16.47 kg (99.2 mol) of terephthalic acid, 1,4
-Cyclohexanedicarboxylic acid (cis / trans ratio = 6
0/40) Prepare a slurry of 0.626 kg (3.64 mol) and 7.65 kg (123 mol) of ethylene glycol, and add 0.30 kg (1.18 mol) of bis (2-hydroxyethyl) terephthalate in advance. Then, the mixture was sequentially supplied to the esterification tank maintained at 250 ° C. over 4 hours.

After the completion of the supply, the esterification reaction was allowed to proceed for an additional hour, and half of the mixture was transferred to a polycondensation tank, and phosphoric acid was added to 1.5 parts by weight.
0 g (based on polymer 150 ppm) and 1.20 g germanium dioxide (based on polymer 120 ppm)
The temperature was gradually increased from 250 ° C. to 280 ° C., and the pressure was gradually reduced from normal pressure, and the pressure was maintained at 0.5 mmHg. Reaction 3
After performing for a time, the formed prepolymer is drawn out in a strand form from a discharge port provided at the bottom of the polycondensation tank, and after water cooling,
It was cut into chips. The prepolymer chip had an intrinsic viscosity of 0.59 dl / g and AV35 eq / ton. The esterification reaction and the polycondensation reaction proceeded smoothly, and the distillate distilled off during each reaction was analyzed, but no cyclohexanedicarboxylic acid or a compound derived therefrom was found.

Next, the surface of the prepolymer chip was crystallized at 150 ° C. using a stirring crystallizer (manufactured by Bepex Co.) and transferred to a stationary solid-state polymerization tower under a nitrogen flow of 20 L / kg · hr. After drying at about 150 ° C. for 3 hours, solid-phase polymerization was performed at 208 ° C. for 15 hours to obtain a solid-phase polymerization chip. Table 1 shows the main analysis results of the solid-state polymerization chip. Next, using the solid-state polymerization tip, injection molding was performed under the following conditions: the temperature of each part of the cinder and the nozzle head was set at 275 ° C., the screw rotation speed was set at 100 rpm, the injection time was set at 10 seconds, and the mold cooling water temperature was set at 10 ° C. A 1/8 inch wide ASTM test piece for lzod impact test was molded. The test piece had high transparency, no whitening or clouding was observed, and no bubbles were generated. The test piece was conditioned for 4 days in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and then subjected to an lzod impact test in the same atmosphere. The results are shown in Table 1.

Example 2 The prepolymer chip obtained in Example 1 was subjected to solid-state polymerization at 208 ° C. for 40 hours in the same manner as in Example 1 to obtain a solid-state polymerization chip. Table 1 shows the main analysis results of the solid-state polymerization chip. Next, an lzod test piece was formed from the solid-phase polymerization chip in the same manner as in Example 1 except that the temperature of each part of the cylinder and the nozzle of the injection molding machine were set to 280 ° C. This test piece also has high transparency like the test piece of Example 1,
No whitening or clouding was observed, and no bubbles were generated.
Using the test piece, an lzod impact test was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, using the solid-state polymerization tip, the temperature of each part of the cylinder and the nozzle of the injection molding machine were set to 275 ° C.
When the zod test piece was molded, a good test piece could be molded by slightly increasing the injection pressure from that in Example 1.

Example 3 Except that 2.30 g of antimony trioxide (based on 230 ppm of polymer) was used instead of germanium dioxide.
Operating in the same manner as in Example 1, the limiting viscosity was 0.59 dl / g,
AV33eq / ton prepolymer chips were obtained. Next, solid-state polymerization was performed at 208 ° C. for 40 hours in the same manner as in Example 1 to obtain a solid-phase polymerization chip. Table 1 shows the main analysis results of the solid-state polymerization chip. Further, the solid-state polymerization chip was prepared in the same manner as in Example 1 except that the temperature of each part of the cylinder and the nozzle of the injection molding machine were set to 280 ° C.
od test pieces were molded. Using the test piece, an lzod impact test was performed in the same manner as in Example 1, and the results are shown in Table 1.

Example 4 19.27 kg (99.3 mol) of dimethyl terephthalate, 0.936 kg of dimethyl 1,4-cyclohexanedicarboxylate (cis / trans ratio = 10/90)
(4.68 mol), 12.9 kg of ethylene glycol
(208 mol) and 3.60 g of manganese acetate tetrahydrate
(180 ppm of polymer) was charged into a reaction vessel, and 160
The temperature was gradually increased from 4 ° C. to 230 ° C. over 4 hours, and a transesterification reaction was carried out while distilling off methanol generated during the process.

To this reaction product, 3.00 g of phosphoric acid (150 ppm based on polymer) and 3.00 g of germanium dioxide (150 ppm based on polymer) were added.
A prepolymer chip having an intrinsic viscosity of 0.63 dl / g and an AV of 23 eq / ton was obtained at a polymerization time of 3 hours under 0.5 mmHg. Next, in the same manner as in the first embodiment, 208
Solid-state polymerization was performed at 40 ° C. for 40 hours to obtain a solid-state polymerization chip.
Table 1 shows the main analysis results of the solid-state polymerization chip. Example 1 was repeated except that the temperature of each part of the cylinder and the nozzle of the injection molding machine was 280 ° C.
An lzod test piece was formed in the same manner as in the above. Using the test piece, an lzod impact test was performed in the same manner as in Example 1, and the results are shown in Table 1.

Example 5 16.83 kg (101.4 mol) of terephthalic acid was
The same operation as in Example 1 was carried out except that 0.269 kg (1.56 mol) of 1,4-cyclohexanedicarboxylic acid (cis / trans ratio = 0/100) was used.
A 1 dl / g, AV32 eq / ton prepolymer chip was obtained. Next, in the same manner as in Example 1,
Solid phase polymerization was carried out for 0 hour to obtain a solid phase polymerization chip. Table 1 shows the main analysis results of the solid-state polymerization chip. Further, an lzod test piece was formed from the solid-phase polymerization chip in the same manner as in Example 1 except that the temperature of each part of the cylinder and the nozzle of the injection molding machine were set to 280 ° C. Using the test piece, an lzod impact test was performed in the same manner as in Example 1, and the results are shown in Table 1.

Example 6 15.67 kg (94.4 mol) of terephthalic acid, 1,
4-cyclohexanedicarboxylic acid (cis / trans ratio =
40/60) was used in the same manner as in Example 1 except that 1.43 kg (8.31 mol) was used, and the intrinsic viscosity was 0.60 dl.
/ G, AV34eq / ton prepolymer chips were obtained. Next, solid-state polymerization was performed at 208 ° C. for 40 hours in the same manner as in Example 1 to obtain a solid-phase polymerization chip. Table 1 shows the main analysis results of the solid-state polymerization chip. Further, an lzod test piece was formed from the solid-phase polymerization chip in the same manner as in Example 1 except that the temperature of each part of the cylinder and the nozzle of the injection molding machine were set to 280 ° C. Using the test piece, an lzod impact test was performed in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 The same operation as in Example 1 was carried out except that 17.10 kg (103.0 mol) of terephthalic acid was used without using cyclohexanedicarboxylic acid, and the limiting viscosity was 0.60 dl / g.
A V35 eq / ton prepolymer chip was obtained. Next, solid-state polymerization was performed at 208 ° C. for 20 hours in the same manner as in Example 1 to obtain a solid-phase polymerization chip. Table 1 shows the main analysis results of the solid-state polymerization chip. Further, an lzod test piece was formed from the solid-phase polymerization chip in the same manner as in Example 1. Using this test piece, lzod was performed in the same manner as in Example 1.
Table 1 shows the results of the impact test.

Comparative Example 2 The prepolymer chip obtained in Comparative Example 1 was subjected to solid-state polymerization at 208 ° C. for 50 hours in the same manner as in Example 1 to obtain a solid-phase polymerized chip. Table 1 shows the main analysis results of the solid-state polymerization chip. Next, an lzod test piece was formed from the solid-state polymerization chip in the same manner as in Example 1 except that the temperature of each part of the cylinder and the nozzle of the injection molding machine were set to 280 ° C. Using this test piece, lzod was performed in the same manner as in Example 1.
Table 1 shows the results of the impact test. In addition, using the solid phase polymerization chip, the temperature of each part of the cylinder and the nozzle of the injection molding machine was set to 275 ° C., and in the same manner as in Example 1,
An attempt was made to mold the lzod test piece, but even if the injection pressure, injection speed, molding cycle, etc. were changed, the test piece suffered sink marks and whitening, and good molding could not be performed.

Comparative Example 3 The same operation as in Example 1 was carried out except that the holding time after the completion of the slurry supply was set to 20 minutes, and the limiting viscosity was set to 0.61 dl /
g, AV69eq / ton prepolymer chips were obtained. Next, solid-state polymerization was performed at 208 ° C. for 20 hours in the same manner as in Example 1 to obtain a solid-phase polymerization chip. Table 1 shows the main analysis results of the solid-state polymerization chip. Further, an lzod test piece was formed from the solid-phase polymerization chip in the same manner as in Example 1 except that the temperature of each part of the cylinder and the nozzle of the injection molding machine were set to 280 ° C. Using the test piece, an lzod impact test was performed in the same manner as in Example 1, and the results are shown in Table 1. In this example, it is assumed that the intrinsic viscosity greatly decreased during molding and the polymer was considerably decomposed.

As shown in the above examples, the copolymerized polyester of the present invention has a higher impact resistance in an unstretched state than PET, so that it is used for molded articles having unstretched portions and low stretched portions. Not only is it suitable as a material, but in its production, the intrinsic viscosity in solid-state polymerization rises quickly, and the solid-state polymerization time required to reach the target intrinsic viscosity can be shortened. Is high. Or even more
It has molding heat stability equal to or higher than PET. Next, the following examples show that the containers molded using the copolymerized polyester of the present invention have improved impact strength as compared with containers made of PET.

[0044]

[Table 1]

Example 7 Using the solid-phase polymerization chip obtained in Example 1, a T-die
The temperature of each part of the gear pump and cylinder was set to 290 ° C., the screw rotation speed was set to 40 rpm, and the extrusion rate was set to 80 g / min.
A sheet having a thickness of 500 μm was formed with an extruder at 0 mmφ. Further, after pre-heating the extruded sheet at 110 ° C., the extruded sheet was 7 cm long, 10 cm wide and 3 cm deep by a vacuum forming machine.
cm deep drawn containers were molded. The intrinsic viscosity of the container is
0.77 dl / g. Next, the drop impact test was performed on the ten containers from a height of 2.0 m as described above, but no cracks or breakage were observed in all of the ten containers.

Comparative Example 4 Using the solid-state polymerization chip obtained in Comparative Example 1, Example 7
In the same manner as in the above, a deep drawn container was formed. The intrinsic viscosity of the container was 0.77 dl / g. Then, the container 10
A drop impact test was performed on the pieces from a height of 2.0 m in the same manner as in Example 7. As a result, a phenomenon in which the bottom portions of the two pieces were cracked and the content liquid leaked was observed.

Example 8 Using the solid-phase polymerization chip obtained in Example 2, 30 mmφ-extrusion at a temperature of each part of the die head and cylinder of 280 ° C., a screw rotation speed of 40 rpm, and a throughput of 80 g / min. A tubular pipe is extruded by a machine, and then, the blow pressure is set to 8 kg / cm ³ and the molding cycle is set to 1
With a blow mold set at 0 second and having a mechanism capable of bottoming the pipe, blow molding is performed immediately after the extrusion tube is bottomed while it can be fused to obtain an extrusion blow bottle of 100 ml size. Was. The intrinsic viscosity of the extrusion blow bottle was 1.07 dl / g. Then, the extruded blow bottle was subjected to the drop impact test described above from a height of 1.5 m from a height of 1.5 m. As for one container, a phenomenon in which the bottom was cracked and the contents liquid leaked was observed. It was only.

Comparative Example 5 Using the solid-phase polymerization chip obtained in Comparative Example 2, Example 8
An extrusion blow bottle was formed in the same manner as described above. The intrinsic viscosity of the extrusion blow bottle was 1.07 dl / g.
Next, a drop impact test was performed on the ten containers from a height of 1.5 m in the same manner as in Example 8. As a result, with respect to five containers, a phenomenon in which the bottom was cracked and the contents liquid leaked was recognized. Was done.

[0049]

The copolymer polyester of the present invention is made of PET.
Since the impact resistance is improved as compared with the above, the impact resistance of a molded article such as a container having an unstretched portion or a low stretched portion, a lid thereof, a film, a sheet, and the like can be improved. Therefore, it is particularly suitable as a molding material for molded articles manufactured by extrusion blow molding, deep drawing, or the like. In the production of the copolymerized polyester of the present invention, not only can it be easily produced with conventional ordinary polyester production equipment, but also the productivity is improved. From the above points, the copolymerized polyester of the present invention has high industrial value.

────────────────────────────────────────────────── (5) References US Patent 4,356,299 (US, A) US Patent 4,340,721 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 63/00-63 / 91 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A terephthalic acid as a dicarboxylic acid component,
A copolymerized polyester containing ethylene glycol as a main component as a diol component, wherein (1) cyclohexanedicarboxylic acid is 0.5 to 10 mol% as a dicarboxylic acid component, and (2) diethylene glycol is 1.0 to 4.0 as a diol component. 0 mol%, (3) intrinsic viscosity is 0.6
(4) A copolymer polyester having a terminal carboxyl group concentration of 40 eq / ton or less. 2. Terephthalic acid as a dicarboxylic acid component;
A copolymerized polyester containing ethylene glycol as a main component as a diol component, wherein (1) cyclohexanedicarboxylic acid is 0.5 to 10 mol% as a dicarboxylic acid component, and (2) diethylene glycol is 1.0 to 4.0 as a diol component. 0 mol%, (3) intrinsic viscosity is 0.5
The copolymerized polyester according to claim 1, which is produced by solid-phase polymerization of a prepolymer having a concentration of terminal carboxyl groups of 10 to 60 eq / ton. 3. A hollow container made of a copolyester formed by extrusion blow molding the copolyester according to claim 1. 4. A copolyester container formed by deep drawing a sheet obtained by extrusion-molding the copolyester according to claim 1. 5. A copolyester container obtained by injection molding the copolyester according to claim 1.