JPH05339350A - Copolyester, and hollow container and stretched film produced therefrom - Google Patents

Abstract

PURPOSE:To obtain a molding excellent in resistance to impact and heat. CONSTITUTION:A molding is produced from a copolyester which is produced from a dicarboxylic acid component mainly comprising terephthalic acid and contg. 0. 5-3.5mol% cyclohexanedicarboxylic acid and a diol component mainly comprising ethylene glycol and contg. 1.0-2.5mol% diethylene glycol and which has an intrinsic viscosity of 0.6-1.5dl/g, a concn. of the terminal carboxyl groups of 18 eq/ton or lower, and a content of a cyclic trimer of 0.35wt.% or lower.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a copolyester useful for bottles, films, sheets and the like. Specifically, because the oligomer content is low and the amount of oligomer by-products during molding is small, not only is it less likely to cause contamination of the mold during molding, but it is also excellent in productivity, heat resistance, mechanical strength, etc. The present invention relates to a copolyester having improved impact resistance in a stretched state or a low stretched state as compared with PET and a molded product thereof.

[0002]

2. Description of the Related Art Polyethylene terephthalate (hereinafter referred to as
It is called "PET". ) Has excellent mechanical strength, chemical stability, transparency, hygiene, etc., and since it is lightweight and inexpensive, it is widely used as packaging materials for various sheets and containers, especially carbonated drinks and fruit juices. Significant growth in containers for beverages, liquid seasonings, edible oils, liquors and wines.

In the case of PET, for example, in the case of a bottle, a preform for a hollow molded body is molded by an injection molding machine, and the preform is stretch-blown in a mold having a predetermined shape. Further, in the case of a content liquid that needs hot filling such as a fruit juice beverage, it is generally molded in a bottle by further heat fixing in the blow mold or in a mold separately provided. is there. When molding a bottle by an extrusion blow method, a tubular pipe (preform) for a hollow molded body is extruded by an extruder to make a fusion-bonded bottom and at the same time blow in a mold of a predetermined shape. Is common.

However, in a conventional PET chip used for molding, as an amount of a cyclic trimer containing an oligomer as a main component,
The melt-polymerized chips usually contain 1 to 2% by weight, and the solid-state polymerized chips usually contain 0.5 to 1.0% by weight. These oligomers adhere to and contaminate devices such as a mold during molding. Contamination of the mold or the like causes the surface of the molded product to become rough or white. Therefore, it is necessary to clean the mold and the like as often as possible.

Therefore, conventionally, the solid-phase polymerization time is extended,
Attempts have been made to reduce oligomers by increasing the amount of catalyst, but there is a limit to the reduction of oligomers by such a method, and it is not an economical method. On the other hand, conventional PE
T is not enough to say that the impact resistance is sufficient in the mouth portion and bottom portion of a biaxially stretched blow bottle, or in a portion or application used in an unstretched state or a low stretched state such as a direct blow bottle, it is difficult to say that the impact resistance is particularly low. As described above, there is a problem that cracks and breakage are likely to occur in a portion that is easily subjected to impact.

On the other hand, there is a method of improving impact resistance by increasing the intrinsic viscosity of PET extremely, but there are problems that productivity is lowered and resin cost is increased. Further, as a method for improving the impact resistance of PET, a method of copolymerizing cyclohexanedimethanol has been used. However, since the cyclohexanedimethanol component is distilled out together with ethylene glycol during the polymerization, the recovered raw material is recycled. The chemical conversion process has to be complicated, and it has not been possible to easily produce it using conventional general polyester continuous production equipment.

On the other hand, a copolyester having properties similar to PET, for example, a copolyester using terephthalic acid and cyclohexanedicarboxylic acid as dicarboxylic acid components and a copolyester using ethylene glycol and diethylene glycol as diol components. Is also well known. However, a copolymerized polyester in which the amount of oligomer is reduced to some extent or more and which has impact resistance equal to or higher than PET has not been specifically known.

[0008]

The object of the present invention is to prevent contamination of molds and the like during molding, to have a low oligomer content, and to reduce by-products of oligomer during molding, and to compare with conventional PET. Impact resistance is improved in unstretched state or low stretched state, and it can be easily produced by conventional polyester continuous polymerization equipment.
It is to provide a highly productive copolyester having heat resistance equal to or higher than the above.

[0009]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the inventors of the present invention have found that the conventional PET has a specific physical property range in which a small amount of cyclohexanedicarboxylic acid unit and diethylene glycol unit are contained. The inventors have found a polymerized polyester and reached the present invention. That is, the gist of the present invention is terephthalic acid as a dicarboxylic acid component,
A copolymerized polyester containing ethylene glycol as a main component as a diol component, wherein (1) a dicarboxylic acid component is cyclohexanedicarboxylic acid in an amount of 0.5 to 3.5 mol%, and (2) a diol component is diethylene glycol in an amount of 1.0 to 2.5 mol%, (3) intrinsic viscosity of 0.6 to
1.5 dl / g, (4) Terminal carboxyl group concentration is 1
8 eq / ton or less, (5) the content of the cyclic trimer is 0.
The present invention relates to a copolyester having a content of 35% by weight or less, and a molded product made of the same. The method for producing the copolymerized polyester is a copolymerized polyester containing terephthalic acid as a dicarboxylic acid component and ethylene glycol as a diol component,
(1) Cyclohexanedicarboxylic acid as a dicarboxylic acid component is 0.5 to 3.5 mol%, (2) Diethylene glycol is 1.0 to 2.5 mol% as a diol component,
(3) Copolymerized polyester (hereinafter referred to as “prepolymer”) having an intrinsic viscosity of 0.5 to 0.7 dl / g and (4) a terminal carboxyl group concentration of 10 to 30 eq / ton is solid-state polymerized. The method is preferred.

The present invention will be described in detail below. With respect to the terephthalic acid and ethylene glycol as the main components of the copolyester of the present invention, known raw materials used in PET may be used. Examples of the raw material for the cyclohexanedicarboxylic acid unit include 1,2-, 1,3-, and 1,4-cyclohexanedicarboxylic acid, and their esters such as dimethyl ester and diethyl ester, 2-methyl-1,4-cyclohexane. Examples thereof include alkyl substitution products such as dicarboxylic acid and 5-methyl-1,3-cyclohexanedicarboxylic acid, and alicyclic substitution products such as alkoxy, aryl, aralkyl and halogen. Further, the cis / trans isomer ratio may be a mixture in any ratio. Of these, usually, preferably the cis / trans ratio is (0 to
80) / (100-20), more preferably (0-7)
The ratio of 0) / (100 to 30), 1,4-cyclohexanedicarboxylic acid or its dimethyl ester form is particularly preferably used.

Diethylene glycol (hereinafter referred to as "D
EG ”. ) Is partially produced as a by-product from ethylene glycol during the polymerization reaction, and therefore, in addition to the case where a predetermined amount of DEG or its ester-forming derivative is used as a polymerization raw material, reaction conditions, additives, etc. should be appropriately selected. It is possible to control the content of the DEG component only by itself. In particular, in the case of the copolyester of the present invention, the melt polymerization temperature can be lowered by the effect of adding cyclohexanedicarboxylic acid (hereinafter referred to as “CHDA”), and D
It is easy to keep the EG component content low. Also,
Examples of the additive include triethylamine and tri-n.
-Tertiary amines such as butylamine and benzyldimethylamine, quaternary ammonium hydroxide such as tetraethylammonium hydroxide, tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide, and lithium carbonate, sodium carbonate, potassium carbonate, sodium acetate, etc. The generation of DEG can be suppressed by adding a small amount of the basic compound of. 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.

Additives for controlling the amount of DEG produced are usually added to the total amount of the polymerization raw material in an amount of 0.00
It is used in an amount of 1 to 10% by weight, preferably 0.005 to 1% by weight. The copolymerized polyester of the present invention has a ratio of cyclohexanedicarboxylic acid in all dicarboxylic acid components,
0.5-3.5 mol%, preferably 1.0-3.0 mol%, more preferably 1.2-2.7 mol%, particularly preferably 1.5-2.5 mol%, In addition, the proportion of DEG in the total diol component is 1.0 to 2.5 mol%, preferably 1.2 to 2.4 mol%, and more preferably 1.
It is 5 to 2.3 mol%.

If the amount is less than the above range, the effect of reducing oligomers adhering to the mold during molding is small and the effect of improving impact resistance is small, so that superiority to conventional PET cannot be recognized. On the other hand, if it exceeds the range,
When the stretched body obtained by molding is heat-set, the heat setting effect is small and the heat resistance tends to decrease, which is not preferable. In particular, the amount of cyclohexanedicarboxylic acid is 10
When it exceeds mol%, the glass transition temperature of the copolyester itself is significantly lowered.

Next, the intrinsic viscosity of the copolyester of the present invention is phenol / tetrachloroethane (weight ratio 1 /
Measured at 30 ° C. in the mixed solvent of 1), 0.60 to 1.
50 dl / g, preferably 0.65 to 1.20 dl /
g, and more preferably 0.70 to 1.00 dl / g. When it is less than 0.60 dl / g, when the obtained copolyester is used as a molded article, it cannot have practically sufficient strength. If it exceeds 1.50 dl / g,
The melt viscosity becomes too high, and the shearing heat generation in the valve becomes large during injection and extrusion molding, so a large amount of oligomers once reduced is generated again, and as a result, contamination of molds etc. is improved. Not recognized and not preferable.

Further, the concentration of the terminal carboxyl group of the copolyester of the present invention can be controlled by the esterification reaction conditions and the like, but the range is 18 eq / ton or less, preferably 16 eq / ton or less, more preferably 14 eq / ton.
It is less than or equal to ton. When the concentration of the terminal carboxyl group exceeds the above range, the effect of reducing the oligomers adhering to the mold or the like at the time of molding is small, and the moisture resistance and the thermal stability are deteriorated, which is not preferable.

All of the above conditions are satisfied, and the content of the cyclic trimer which is the main component of the oligomer is 0.35.
By providing the copolymerized polyester in an amount of not more than 0.3% by weight, preferably not more than 0.32% by weight, and more preferably not more than 0.30% by weight, it is possible to improve the contamination of the mold and the like.
When the content of the cyclic trimer exceeds 0.35% by weight, for example, when it is about 0.40% by weight, some improvement in contamination can be seen, but it cannot be said to be sufficient. Contamination such as is noticeable.

The above-mentioned copolyester of the present invention is P
It is produced by performing melt polymerization and subsequent solid-phase polymerization according to a conventionally known method for ET. Hereinafter, the manufacturing method will be described in detail. Examples of the melt polymerization method include a method in which a direct esterification reaction is performed under pressure using terephthalic acid, cyclohexanedicarboxylic acid and ethylene glycol, and then the temperature is further raised and the pressure is gradually reduced to perform a polycondensation reaction. Alternatively, it can be produced by performing an ester exchange reaction using an ester derivative of terephthalic acid, for example, dimethyl terephthalic acid, dimethyl ester of cyclohexanedicarboxylic acid, and ethylene glycol, and then further polycondensing the obtained reaction product. .. In these polycondensation reactions, the cyclohexanedicarboxylic acid component can be added at any time in the initial stage of the esterification reaction, transesterification reaction, or polycondensation reaction. For example, a transesterification reaction between 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 polycondensation reaction may be carried out in one step or in a plurality of steps. When carrying out in multiple 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 polycondensation reaction is usually 265 to 300 ° C., preferably 270 to 270 ° C.
The temperature is 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 steps,
The polycondensation reaction conditions of the first stage and the second stage are within the above ranges, respectively.
It is a condition between the reaction conditions of the first stage to the final stage. For example, when the polycondensation reaction is carried out in three stages, the reaction temperature of the second stage polycondensation reaction is usually 260 to 295 ° C, preferably 270 to 285 ° C, and the pressure is usually 50 to 2 ° C.
mmHg, preferably in the range of 40-5 mmHg.
The intrinsic viscosity reached in each of these polycondensation reaction steps is not particularly limited, but it is preferable that the degree of increase in the intrinsic viscosity in each stage is smoothly distributed, and further from the polycondensation reactor at the final stage. The intrinsic viscosity of the obtained prepolymer is usually 0.45 to 0.80 dl / g, preferably 0.50 to 0.70 dl / g, and more preferably 0.50 to 0.65 dl / g. If the intrinsic viscosity of the prepolymer is below this range, it becomes difficult to form chips, and if it is above this range, it is difficult to extract the prepolymer from the reaction vessel, and reduction of oligomers when subjected to solid phase polymerization Less effective. Usually, the prepolymer is drawn from the molten state into strands and then cut into granular chips.

Such granular chips are usually 2.0 to
It is desirable to have an average particle size of 5 mm, preferably 2.2-4.0 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, one or more known compounds such as calcium, titanium, manganese, zinc, sodium and lithium compounds can be used, but a manganese compound is particularly preferable from the viewpoint of transparency. As the polymerization catalyst, there are known ones such as germanium, antimony, titanium and cobalt compounds.
Although more than one species can be used, preferably a germanium compound or an antimony compound, most preferably a germanium compound is used. The amount of the catalyst, as both the esterification catalyst and the polymerization catalyst, is usually 5 to 2000 ppm, preferably 10 to 500 ppm as the metal amount in the whole polymerization raw material.
Used in the ppm range.

To further specify the germanium compound, the compound is a germanium oxide,
Examples thereof include inorganic acid salts, organic acid salts, halides and sulfides, and germanium dioxide is usually preferably used. The amount of these germanium compounds used is such that the germanium atom is usually 10 to 100 weight pp in the prepolymer to be produced and the copolyester after solid state polymerization.
m, preferably 30 to 60 ppm by weight, more preferably 35 to 55 ppm by weight, and most preferably 40 to 50 ppm by weight from the viewpoint of suppressing oligomer by-product and thermal stability. ..

If the antimony compound is further specified, examples of the compound include an antimony oxide, an inorganic acid salt, an organic acid salt, a halide and a sulfide, and usually, antimony trioxide is preferably used. It The amount of these antimony compounds used is such that the antimony atom in the prepolymer to be produced and the copolyester after the solid phase polymerization is usually 100 to 350 ppm by weight, preferably 150 to 270 ppm by weight, more preferably 170 ppm by weight.
To be used in an amount of up to 250 ppm by weight,
It is desirable from the viewpoints of suppressing oligomer by-products and thermal stability.

The stabilizers include phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, triphenyl phosphite, trisdodecyl phosphate. Phosphite esters such as phyto and trisnonylphenyl phosphite, methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate, dioctyl phosphate, and other acidic phosphate esters, and phosphoric acid and phosphorous acid. Phosphorus compounds such as hypophosphorous acid and polyphosphoric acid are preferred. The stabilizer is usually 10 to 10 parts by weight based on the weight of phosphorus atom in the stabilizer.
1000 ppm by weight, preferably 20-200 ppm by weight
Used in the range of m. The weight ratio of the phosphorus atom contained in the prepolymer and the copolyester after the solid-phase polymerization to the germanium atom contained together is usually 0.3 to 1.5 times, and preferably 0.1. 4-1.0
It is desirable to use it in a double range.

Further, a dicarboxylic acid component other than terephthalic acid and cyclohexanedicarboxylic acid, and a diol component other than ethylene glycol and diethylene glycol may be contained in a small amount as long as they do not deviate from the above-mentioned constitutional requirements of the present invention. Examples of these dicarboxylic acid components include phthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, 4,4′-biphenyl dicarboxylic acid, 1,3-phenylenedioxydiacetic acid, and structural isomers thereof. Aliphatic dicarboxylic acids such as malonic acid, succinic acid, and adipic acid, oxyacids or derivatives thereof include p-hydroxybenzoic acid and p-hydroxybenzoic acid.
-Hydroxybenzoic acid esters, glycolic acid and the like can be mentioned. The diol components include 1,2-propanediol, 1,3-propanediol and 1,4-propanediol.
Examples include aliphatic glycols such as butanediol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol, and aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S. it can. An amount that is substantially equivalent to the total diol component and the total dicarboxylic acid component is used.

The composition (constituent unit) of the prepolymer produced by melt polymerization and the concentration of germanium atoms are substantially the same as those of the copolyester of the present invention obtained by subjecting the prepolymer to solid phase polymerization. It is the same. The concentration of the terminal carboxyl group in the prepolymer is usually 10 to 30 eq / ton, preferably 13 to 27 eq / ton, and more preferably 15 to 25 e.
It is preferably q / ton. If the amount is less than the range, the solid-phase polymerizability is poor, and it may take a long time to increase the intrinsic viscosity. On the other hand, if the amount exceeds the range, the oligomer is subjected to the solid-state polymerization. In some cases, the effect of reducing

Next, in order to obtain the copolyester of the present invention, it is necessary to further subject the prepolymer chips obtained by the melt polymerization as described above to solid phase polymerization treatment. The prepolymer chips used for the solid phase polymerization may be heated to a temperature lower than the temperature at which the solid phase polycondensation is performed in advance to perform pre-crystallization and then supplied to the solid phase polycondensation step.
In such a pre-crystallization step, the copolyester chip is usually dried at 120 to 200 ° C., preferably 1
It can also be carried out by heating at 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 in the atmosphere of steam or an inert gas containing steam. You can also do it.

The solid-phase polymerization step in which the above-mentioned prepolymer chips are supplied comprises at least one stage, and the polymerization temperature is usually 190 to 230 ° C., preferably 195 to 22.
5 ° C. and pressure is usually 1 kg / cm ² G to 10 mmH
g, preferably under normal pressure to 100 mmHg under an atmosphere of an inert gas such as nitrogen, argon or carbon dioxide. The higher the temperature, the shorter the polymerization time to reach the desired physical properties, but it is usually 1 to 50 hours, preferably 5 to 30 hours, more preferably 10 to 25 hours.

The copolymerized polyester of the present invention can be obtained by appropriately selecting the conditions of the above solid-phase polymerization treatment. The polyester of the present invention thus obtained can be used for forming films, sheets, containers, and other packaging materials by using the melt molding method generally used for PET. Further, it is possible to improve the mechanical strength by stretching the copolyester at least uniaxially.

In producing a stretched film, the stretching temperature may be set between the glass transition temperature of the copolyester of the present invention and a temperature 70 ° C. higher than that, usually 40 to 170 ° C., preferably 60 to 140. ℃. The stretching may be uniaxial or biaxial, but biaxial stretching is preferable from the viewpoint of practical physical properties of the film. In the case of uniaxial stretching, the stretching ratio is usually 1.1 to 10 times, preferably 1.5 to
In the case of biaxial stretching, the stretching is performed in the range of 8 times, and in the case of biaxial stretching, it is usually 1.1 to 8 times, preferably 1.5 to 5 times in the longitudinal direction and the transverse direction, respectively. Also, vertical magnification /
The lateral magnification is usually 0.5 to 2, preferably 0.7 to 1.
It is 3. The obtained stretched film can be further heat-fixed to improve heat resistance and mechanical strength. The heat setting is usually 120-melting point under tension, preferably 150-
It is carried out at 230 ° C. for usually several seconds to several hours, preferably several tens of seconds to several minutes.

In producing a hollow molded article, a preform formed from the copolyester of the present invention is stretch blow molded, and an apparatus conventionally used for PET blow molding can be used. .. Specifically, for example, a preform is once molded by injection molding or extrusion molding, and then it is reheated as it is or after processing the plug portion and the bottom portion, and biaxial stretching such as hot parison method or cold parison method. Blow molding method is applied. In this case, the molding temperature, specifically, the temperature of each part of the cylinder and nozzle of the molding machine can be set in the range of 260 to 280 ° C., which is lower than that of general PET by 1 to 10 ° C., and the amount of oligomers can be kept low. Is easy. Further, it is possible to suppress the decrease in the intrinsic viscosity to be low, and it is easy to suppress the amount of acetaldehyde produced as a by-product to be low.
The stretching temperature is usually 70 to 120 ° C., preferably 80 to 1
At 10 ° C., the draw ratio is usually 1.5 to 3.5 in the machine direction.
It may be performed in a range of 2 to 5 times in the circumferential direction.

The obtained hollow molded article can be used as it is, but in the case of a content liquid such as fruit juice, oolong tea, etc. which requires heat filling, it is generally further heat-set in a blow mold, Further, it is used with heat resistance.
Heat fixation is usually 100 to 200 under tension such as compressed air.
C., preferably 120 to 180.degree. C., for a few seconds to a few hours, preferably a few seconds to a few minutes.

[0033]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Various measuring methods used in this example are shown below. The method for measuring the intrinsic viscosity is as described above.

(1) Amount of cyclohexanedicarboxylic acid (hereinafter referred to as "CHDA amount") After methanol-decomposition by a conventional method, the produced dimethyl ester component was quantified by gas chromatography. (2) Diethylene glycol amount (hereinafter referred to as "DEG amount") Hydrolysis was carried out by a conventional method, and the produced diol component was quantified by gas chromatography.

(3) Cyclic trimer amount (hereinafter referred to as "CT amount") 200 mg of a copolymerized polyester sample was added to chloroform /
It was dissolved in 2 ml of a mixed solution of hexafluoroisopropanol (volume ratio 3/2) and further diluted with 20 ml of chloroform. To this, 10 ml of methanol was added to reprecipitate a sample, and a filtrate after filtration was obtained. After the filtrate was dried and solidified, a liquid obtained by dissolving the residue in 25 ml of dimethylformamide was analyzed and quantified by liquid chromatography.

(4) Terminal carboxyl group concentration (hereinafter referred to as "A
V ”. ) 100 mg of the copolymerized polyester sample was dissolved in 5 ml of benzyl alcohol by heating, and 5 ml of chloroform was added to the solution to dilute it.
It was titrated with an N-sodium hydroxide / benzyl alcohol solution and quantified.

(5) Content of germanium atom (hereinafter referred to as "G
e ”amount. ) A sample of 2.0 g of the copolyester was ashed by a conventional method in the presence of sulfuric acid, completely decomposed, and then made into a constant volume of 100 ml with distilled water. (6) Antimony atom content (hereinafter referred to as "Sb content") The content was determined by emission spectroscopic analysis in the same manner as the analysis of the germanium atom content.

(7) Phosphorus atom content (hereinafter referred to as "P amount") It was quantified by optical emission spectroscopy in the same manner as the analysis of the germanium atom content. (8) Inert gas flow rate The inert gas flow rate is the amount of gas flowing per unit time (hr) and per unit resin weight (kg) at 1 atm and 25 ° C.
The volume amount (L) converted to

(9) Izod Impact Strength Notched, 1/8 inch wide Izod test ASTM
Using the test piece, the humidity was measured after being conditioned in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%.

Example 1 16.73 kg (100.8 mol) of terephthalic acid, 1,
4-cyclohexanedicarboxylic acid (cis / trans ratio =
60/40) 0.358 kg (2.08 mol) and ethylene glycol 7.63 kg (123 mol) were prepared as a slurry, and 0.30 kg (1.18 mol) was prepared in advance.
Bis (2-hydroxyethyl) terephthalate of was added and sequentially supplied to the esterification tank kept at 250 ° C. over 4 hours. After the completion of the supply, the esterification reaction was allowed to proceed for another 1 hour, and then half of the amount was transferred to a polycondensation tank to remove phosphoric acid
0 g (150 ppm by weight of polymer) and 1.20 g (120 ppm by weight of polymer) of germanium dioxide were charged, the temperature was gradually raised from 250 ° C. to 280 ° C., and the pressure was gradually reduced from normal pressure to 0.5 mmHg.
After the reaction was carried out for 3 hours, the produced prepolymer was withdrawn in a strand form from an outlet provided at the bottom of the polycondensation tank,
After cooling with water, it was cut into chips. The prepolymer chip had a CT amount of 0.94% by weight and an intrinsic viscosity of 0.56 dl /
g, AV23eq / ton, Ge amount 43 weight ppm, P
The amount was 23 ppm by weight. The esterification reaction and 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. by a stirring crystallization machine (manufactured by Bepex Co.), and then transferred to a stationary solid phase polymerization tower, and 20 L / kg · hr of nitrogen was passed through. After drying at about 150 ℃ for 3 hours, at 208 ℃ 20
Solid phase polymerization was carried out for a time to obtain a solid phase polymerization chip. Table 1 shows the main analysis results of the solid-state polymerization chip. The solid-state polymerized chip had a Ge content of 43 weight ppm and a P content of 23 weight pp.
It was m.

Next, using the solid-state polymerization chip, the temperature of each part of the cylinder and the nozzle head was set to 275 ° C., the screw rotation speed was 100 rpm, the injection time was 10 seconds, and the mold cooling water temperature was 10 ° C. Injection molding machine IS-6
A preform was molded with 0B. The plug part of this preform was heated and crystallized by a self-made crystallizer, and then the preheating furnace temperature was 90 ° C., the blow pressure was 20 kg / cm ² , and the molding cycle 1
Blow molding with a stretch blow molding machine set to 0 seconds to form a bottle with an average wall thickness of 300 μm and an internal volume of 1.5 liters,
Then, pneumatic pressure tensioning is performed in the mold set at 150 ° C, 1
Heat set for 0 seconds. Table 1 shows the physical properties of the bottle.
The bottle was highly transparent, and neither whitening nor clouding was observed, and no bubbles were observed. Further, although 1000 bottles were continuously molded, no contamination was found in the injection molding, stretch blow molding, and heat setting molds.

Further, the above-mentioned bottle was filled with the orange juice liquid which had been sterilized at 90 ° C. and allowed to cool to 85 ° C., and after sealing, 15
It was placed upside down for a minute, but no liquid leakage or deformation of the mouth plug, shoulder, or body was observed. On the other hand, using the solid-state polymerized chip, injection molding was performed under the following conditions: the temperature of each part of the cylinder and the nozzle head was 275 ° C, the screw rotation speed was 100 rpm, the injection time was 10 seconds, and the mold cooling water temperature was 10 ° C. , 30 1/8 inch wide ASTM test pieces for Izod impact test were molded, and 10 to 20th to 29th molded pieces were used for the Izod test. The test piece had an intrinsic viscosity of 0.78 dl / g, high transparency, and no whitening, clouding, generation of bubbles, etc. were observed. The test piece,
After conditioning the humidity for 4 days in an atmosphere having a temperature of 23 ° C. and a relative humidity of 50%, an Izod impact test was performed in the same atmosphere, and the average value of the test results of 10 pieces was taken as the Izod impact strength. The results are shown in Table-1.

Example 2 The prepolymer chip obtained in Example 1 was subjected to solid phase polymerization at 215 ° C. for 20 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. The solid-state polymerized chip had a Ge content of 43 weight ppm and a P content of 23 weight ppm.

Then, using the solid-state polymerization chip, the temperature of each part of the cylinder and nozzle of the injection molding machine was changed to 265 ° C., and in the same manner as in Example 1, a heat-fixing bottle having a capacity of 1.5 liters was used. Got The physical properties of the bottle are shown in Table-1. Further, the bottle was completely good in appearance without whitening. Further, no contamination of the mold was observed even when the continuous operation was performed as in Example 1. Further, in the heat filling test carried out in the same manner as in Example 1, no change was observed in the bottle.

On the other hand, Izod test pieces were molded in the same manner as in Example 1 using the solid-state polymerized chips. The test piece had an intrinsic viscosity of 0.84 dl / g, and like the test piece of Example 1, had high transparency, and whitening, clouding, generation of bubbles, etc. were not observed. Using the test piece, an Izod impact test was conducted in the same manner as in Example 1. The results are shown in Table-1.

Example 3 Dimethyl terephthalate 19.90 kg (102.6 mol), dimethyl 1,4-cyclohexanedicarboxylate (cis / trans ratio = 10/90) 0.312 kg
(1.56 mol), ethylene glycol 12.9 kg
(208 mol) and manganese acetate tetrahydrate 3.60 g
(180 ppm by weight of polymer) was charged into a reaction can and 1
The temperature was gradually raised from 60 ° C. to 230 ° C. over 4 hours, and the transesterification reaction was carried out while distilling off the methanol that was generated on the way.

3.00 g of phosphoric acid (150 ppm by weight of polymer), 3.00 g of germanium dioxide were added to the reaction product.
(150 ppm by weight of polymer) was added and finally 28
CT at 0.5 ° C, 0.5 mmHg, polymerization time 3 hours, CT
Amount 0.96% by weight, intrinsic viscosity 0.55 dl / g, AV1
A prepolymer chip having 7 eq / ton, a Ge content of 48 weight ppm and a P content of 30 weight ppm was obtained.

Then, using the prepolymer chip, solid phase polymerization was carried out 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. The solid-state polymerization chip has a Ge amount of 48 weight pp.
m, P amount was 30 weight ppm. Using the solid-state polymerization chip, a heat-fixing bottle having a capacity of 1.5 liter was obtained in the same manner as in Example 1. The physical properties of the bottle are shown in Table-1. Further, the bottle was completely good in appearance without whitening.

No contamination of the mold was observed even when continuous operation was carried out as in Example 1. Further, in the heat filling test carried out in the same manner as in Example 1, no change was observed in the bottle. On the other hand, using the solid-state polymerized chip, an Izod test piece was molded in the same manner as in Example 1. The test piece had an intrinsic viscosity of 0.72 dl / g, and like the test piece of Example 1, was highly transparent, and whitening, clouding, generation of bubbles, etc. were not observed. Using the test piece, an Izod impact test was conducted in the same manner as in Example 1. The results are shown in Table-1.

Further, using this solid-state polymerization chip, the temperature of each part of the cylinder and nozzle was set to 275 ° C., the screw rotation speed was 40 rpm, and the extrusion rate was 80 g / min.
A sheet having a wall thickness of 300 μm was formed using an mmφ-extruder. The extrusion molding was continuously continued for 10 hours, but the cooling drum was not contaminated. Furthermore, a long stretching machine (TM Lo
(manufactured by ng Co., Ltd.) was simultaneously biaxially stretched 3 × 3 times, and then heat-set in an oven under tension at 200 ° C. for 120 seconds to obtain a stretched film having a thickness of 100 μm. The film had an intrinsic viscosity of 0.70 dl / g and a CT of 0.30% by weight.

Example 4 16.65 kg (100.3 mol) of terephthalic acid,
1,4-cyclohexanedicarboxylic acid (cis / trans ratio = 0/100) was used in the same manner as in Example 1 except that 0.447 kg (2.60 mol) was used, and the CT amount was 0.93.
% By weight, intrinsic viscosity 0.56 dl / g, AV24 eq / t
On, a prepolymer chip having a Ge content of 45 weight ppm and a P content of 25 weight ppm was obtained.

Then, using the prepolymer chip, solid phase polymerization was carried out 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. The solid-state polymerization chip has a Ge content of 45 weight pp
m, P amount was 25 weight ppm. Using the solid-state polymerization chip, a heat-fixing bottle having a capacity of 1.5 liter was obtained in the same manner as in Example 1. The physical properties of the bottle are shown in Table-1. Further, the bottle was completely good in appearance without whitening.

No contamination of the mold was observed even when continuous operation was carried out as in Example 1. Further, in the heat filling test carried out in the same manner as in Example 1, no change was observed in the bottle. On the other hand, using the solid-state polymerized chip, an Izod test piece was molded in the same manner as in Example 1. The test piece had an intrinsic viscosity of 0.73 dl / g, and like the test piece of Example 1, had high transparency, and whitening, clouding, generation of bubbles, etc. were not observed. Using the test piece, an Izod impact test was conducted in the same manner as in Example 1. The results are shown in Table-1.

Example 5 16.56 kg (99.76 mol) of terephthalic acid,
0.537 kg (3.12 mol) of 1,4-cyclohexanedicarboxylic acid (cis / trans ratio = 40/60),
Using the same procedure as in Example 1 except that 1.10 g of germanium dioxide (110 ppm by weight of polymer) was used, C
T amount 0.91% by weight, intrinsic viscosity 0.59 dl / g, AV
A prepolymer chip having 26 eq / ton, a Ge amount of 38 wt ppm and a P amount of 20 wt ppm was obtained.

Next, using the prepolymer chip, solid phase polymerization was carried out 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. The solid-state polymerization chip has a Ge amount of 38 weight pp
The amount of m and P was 20 ppm by weight. Using the solid-state polymerization chip, a heat-fixing bottle having a capacity of 1.5 liter was obtained in the same manner as in Example 1. The physical properties of the bottle are shown in Table-1. Further, the bottle was completely good in appearance without whitening.

Even when continuous operation was carried out as in Example 1, the mold was hardly contaminated. Further, in the heat filling test carried out in the same manner as in Example 1, no change was observed in the bottle. On the other hand, using the solid-state polymerized chip, an Izod test piece was molded in the same manner as in Example 1. The test piece had an intrinsic viscosity of 0.80 dl / g and had high transparency as in the test piece of Example 1, and whitening, clouding, generation of bubbles, etc. were not observed. Using the test piece, an Izod impact test was conducted in the same manner as in Example 1. The results are shown in Table-1.

Example 6 16.92 kg (101.9 mol) of terephthalic acid,
0.179 kg (1.04 mol) of 1,4-cyclohexanedicarboxylic acid (cis / trans ratio = 30/70),
Using the same procedure as in Example 1 except that 1.50 g of germanium dioxide (150 ppm by weight of polymer) was used, C
T amount 0.97% by weight, intrinsic viscosity 0.56 dl / g, AV
23 eq / ton, Sb amount 190 weight ppm, P amount 25
Prepolymer chips with weight ppm were obtained.

Then, using the prepolymer chip, solid phase polymerization was carried out 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. The solid-state polymerized chip had an Sb content of 190 weight pp
m, P amount was 25 weight ppm. Using the solid-state polymerization chip, a heat-fixing bottle having a capacity of 1.5 liter was obtained in the same manner as in Example 1. The physical properties of the bottle are shown in Table-1. Further, the bottle was completely good in appearance without whitening.

Even when the continuous operation was carried out as in Example 1, the mold was hardly contaminated. Further, in the heat filling test carried out in the same manner as in Example 1, no change was observed in the bottle. On the other hand, using the solid-state polymerized chip, an Izod test piece was molded in the same manner as in Example 1. The test piece had an intrinsic viscosity of 0.77 dl / g and had high transparency as in the case of the test piece of Example 1, and whitening, clouding, generation of bubbles, etc. were not observed. Using the test piece, an Izod impact test was conducted in the same manner as in Example 1. 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 CT amount was 1.00% by weight and the intrinsic viscosity was 0.56dl / g, AV23eq / ton, Ge amount 4
A prepolymer chip having 3 weight ppm and a P amount of 23 weight ppm was obtained.

Then, using the prepolymer chip, solid phase polymerization was carried out 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. The solid-state polymerization chip has a Ge amount of 43 weight pp
The amount of m and P was 23 ppm by weight.

Using the solid-state polymerization chip, a heat-fixed bottle having a capacity of 1.5 liter was obtained in the same manner as in Example 1. The physical properties of the bottle are shown in Table-1. The same hot-filling test results as in Example 1 were good for the bottle, but a large amount of thin white film-like deposits were observed when the mold after molding was observed as a continuous molding test. On the other hand, using the solid-state polymerization chip,
An Izod test piece was molded in the same manner as in Example 1. The test piece had an intrinsic viscosity of 0.75 dl / g and
Similar to the test piece of No. 1, it was highly transparent, and whitening, cloudiness, and generation of bubbles were not observed. Using the test piece, Example 1
An Izod impact test was conducted in the same manner as in. The results are shown in Table-1.
Shown in.

Comparative Example 2 The prepolymer chip obtained in Comparative Example 1 was subjected to solid phase polymerization at 208 ° C. for 35 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. The solid-state polymerized chip had a Ge content of 43 weight ppm and a P content of 23 weight ppm.

Using the solid-state polymerization chip, a heat-fixing bottle having a capacity of 1.5 liter was obtained in the same manner as in Example 1. The physical properties of the bottle are shown in Table-1. The same hot-filling test results as in Example 1 were good for the bottle, but a thin white film-like deposit was observed when the mold after molding was observed as a continuous molding test. On the other hand, using the solid-state polymerized chip, an Izod test piece was molded in the same manner as in Example 1. The test piece had an intrinsic viscosity of 0.84 dl / g, and like the test piece of Example 1, had high transparency, and whitening, clouding, generation of bubbles, etc. were not observed. Using the test piece, an Izod impact test was conducted in the same manner as in Example 1. The results are shown in Table-1.

Comparative Example 3 The same operation as in Example 1 was carried out except that the esterification reaction time after the feed of the raw material slurry was shortened to 30 minutes, and the CT amount was 0.94% by weight, the intrinsic viscosity was 0.56 dl / g, and the AV34.
eq / ton, Ge amount 43 weight ppm, P amount 23 weight p
A pm prepolymer chip was obtained.

Then, using the prepolymer chip, solid phase polymerization was carried out 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. The solid-state polymerization chip has a Ge amount of 43 weight pp
The amount of m and P was 23 ppm by weight.

Using the solid-state polymerization chip, a heat-fixing bottle having a capacity of 1.5 liter was obtained in the same manner as in Example 1. The physical properties of the bottle are shown in Table-1. The same hot-filling test results as in Example 1 were good for the bottle, but a large amount of thin white film-like deposits were observed when the mold after molding was observed as a continuous molding test. On the other hand, using the solid-state polymerization chip,
An Izod test piece was molded in the same manner as in Example 1. The test piece had an intrinsic viscosity of 0.79 dl / g.
Similar to the test piece of No. 1, it was highly transparent, and whitening, cloudiness, and generation of bubbles were not observed. Using the test piece, Example 1
An Izod impact test was conducted in the same manner as in. The results are shown in Table-1.
Shown in.

Comparative Example 4 0.220 k of diethylene glycol was added to the prepared slurry.
The same operation as in Example 1 except that g (2.08 mol) was added, and the CT amount was 0.88% by weight and the intrinsic viscosity was 0.56 dl.
/ G, AV23eq / ton, Ge amount 44 weight ppm,
A prepolymer chip having a P amount of 24 ppm by weight was obtained.

Then, using the prepolymer chip, solid phase polymerization was carried out 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. The solid-state polymerization chip has a Ge amount of 44 weight pp
The amount of m and P was 24 ppm by weight. Table 1 shows the physical properties of the heat-fixing bottle having a capacity of 1.5 liter obtained in the same manner as in Example 1 using the solid-state polymerization chip. When the same heat-filling test as in Example 1 was performed on the bottle, deformation of the bottle and liquid leakage from the plug portion were observed. Further, when the mold after molding was observed as a continuous molding test, a thin white film-like deposit was observed.

On the other hand, Izod test pieces were molded in the same manner as in Example 1 using the solid-state polymerized chips. The test piece had an intrinsic viscosity of 0.80 dl / g and had high transparency as in the test piece of Example 1, and whitening, clouding, generation of bubbles, etc. were not observed. Using the test piece, an Izod impact test was conducted in the same manner as in Example 1. The results are shown in Table-1.

Comparative Example 5 16.03 kg (96.55 mol) of terephthalic acid,
The same operation as in Example 1 was carried out except that 1.07 kg (6.22 mol) of 1,4-cyclohexanedicarboxylic acid (cis / trans ratio = 30/70) was used, and the CT amount was 0.83% by weight and Viscosity 0.56dl / g, AV23eq / to
A prepolymer chip having n, Ge content of 43 weight ppm and P content of 24 weight ppm was obtained.

Next, using the prepolymer chip, solid phase polymerization was carried out 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. The solid-state polymerization chip has a Ge amount of 43 weight pp
The amount of m and P was 24 ppm by weight. Table 1 shows the physical properties of the heat-fixing bottle having a capacity of 1.5 liter obtained in the same manner as in Example 1 using the solid-state polymerization chip. Further, in the continuous molding test similar to Example 1, almost no contamination of the mold was observed, but when the same heat filling test as in Example 1 was performed, the deformation of the bottle and the liquid from the plug portion were observed. A leak was noted.

On the other hand, an Izod test piece was molded in the same manner as in Example 1 using the solid-state polymerization chip. The test piece had an intrinsic viscosity of 0.81 dl / g, and like the test piece of Example 1, had high transparency, and whitening, clouding, generation of bubbles, etc. were not observed. Using the test piece, an Izod impact test was conducted in the same manner as in Example 1. The results are shown in Table-1.

[0075]

[Table 1]

[0076]

EFFECT OF THE INVENTION The copolymerized polyester of the present invention has a low oligomer content and a small amount of oligomer by-product during molding, so that contamination of the mold during molding is unlikely to occur. Therefore, since it is not necessary to frequently wash the molding device when manufacturing the molded product, it is possible to improve the productivity of the molded product such as a bottle, a film or a sheet. Moreover, since the copolyester of the present invention has improved impact resistance as compared with conventional PET, it is possible to improve the impact resistance of a molded product having an unstretched portion or a low stretched portion. Furthermore, the copolyester of the present invention is also excellent in heat resistance and is suitable as a molding material for a container for fruit juice drinks requiring heat resistance.

Further, the copolymerized polyester of the present invention is characterized in that, in its production, not only it can be easily produced by the conventional ordinary polyester production equipment, but also the productivity is improved. From the above points, the copolyester of the present invention has high industrial value.

Continuation of front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location // B29K 67:00 B29L 7:00 4F 22:00 4F (72) Inventor Osamu Kishiro Midori, Yokohama, Kanagawa 1000 Kamoshida-cho, Ward Sanritsu Kasei Co., Ltd.

Claims (4)

[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) a dicarboxylic acid component is cyclohexanedicarboxylic acid in an amount of 0.5 to 3.5 mol%, and (2) a diol component is diethylene glycol in an amount of 1.0 to 2.5 mol%, (3) intrinsic viscosity of 0.6 to
1.5 dl / g, (4) Terminal carboxyl group concentration is 1
8 eq / ton or less, (5) the content of the cyclic trimer is 0.
35% by weight or less, a copolymerized polyester. 2. A terephthalic acid as a dicarboxylic acid component,
A copolymerized polyester containing ethylene glycol as a main component as a diol component, wherein (1) a dicarboxylic acid component is cyclohexanedicarboxylic acid in an amount of 0.5 to 3.5 mol%, and (2) a diol component is diethylene glycol in an amount of 1.0 to 2.5 mol%, (3) intrinsic viscosity 0.5 to
0.7 dl / g, (4) terminal carboxyl group concentration is 1
The copolyester according to claim 1, which is produced by solid-phase polymerizing a prepolymer having a content of 0 to 30 eq / ton. 3. A copolymer polyester hollow container obtained by subjecting the copolymer polyester according to claim 1 to preform molding by injection molding or extrusion molding, and then biaxially stretch blow molding. 4. A stretched film made of a copolyester obtained by injection-molding or extrusion-molding the copolyester according to claim 1 and stretching a sheet-like material in at least one direction.