JP2001002774A - Production of polyester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester hardly causing a mold stain in molding, further causing excellent transparency of bottle. SOLUTION: In this method for producing a polyester by subjecting polyester chips to water treatment in a treating layer, the water treatment is carried out by introducing water having 0.01-30 CaCO3 mg/l total hardness from the outside of a system to a treating tank.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing polyester used for molding bottles, films, sheets and the like. The present invention relates to a method for producing a polyester having excellent controllability.

[0002]

2. Description of the Related Art As materials for containers such as seasonings, oils, beverages, cosmetics, and detergents, various resins are employed depending on the type of filling content and the purpose of use.

[0003] Among them, polyester is excellent in mechanical strength, heat resistance, transparency and gas barrier properties, and is therefore particularly suitable as a material for containers for filling beverages such as juices, soft drinks and carbonated drinks.

[0004] Such polyester is supplied to a molding machine such as an injection molding machine to form a preform for a hollow molded body, and the preform is inserted into a mold having a predetermined shape and stretch blow-molded. Heat treatment (heat set)
Then, it is general that the plug portion of the bottle is heat-treated (the plug portion is crystallized) if necessary.

However, conventional polyesters contain oligomers such as cyclic trimers and the like, and these oligomers adhere to the inner surface of the mold, the gas exhaust port of the mold, and the exhaust pipe. Dirt was easy to occur.

[0006] Such mold stains cause the surface roughness and whitening of the obtained bottle. If the bottle becomes white, it must be discarded. For this reason, mold contamination must be removed frequently, and there has been a problem that the productivity of the bottle is reduced.

As a solution to these problems, Japanese Patent Laid-Open Publication No.
Japanese Patent No. 4441 discloses a method of treating polyester with water.

However, in the stage of water treatment, if the total hardness of the industrial water is high, metal-containing substances adhere to the walls of the processing tank and the pipes, causing clogging of the pipes and difficulty in cleaning the processing tanks and pipes. And other problems.

Further, fine particles of the metal-containing substance floating and settling in the treated water and adhering to the walls of the treatment tank and pipes adhere to and penetrate the polyester chips, which promotes crystallization during molding, resulting in poor transparency. Problems such as bottles occurred.

[0010] Even in the case of a bottle resin in which the catalyst has not been deactivated by the conventional water treatment, water having high hardness was sometimes used when the strands were formed into chips, but no significant decrease in transparency was observed. However, the decrease in transparency due to the above foreign matter was particularly remarkable in bottles in which the catalyst was deactivated by water treatment or the like. This is not clear,
It is considered that the deactivation of the catalyst causes the germanium compound contained in the resin as a catalyst to react with water to form particles insoluble in the resin, which become crystal nuclei and have a synergistic effect with the action of promoting crystallization.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art, and to provide a polyester which is less likely to cause mold stains during molding and has a good bottle transparency. It is intended to be.

[0012]

In order to achieve the above object, a method for producing a polyester according to the present invention is directed to a method for producing a polyester in which a polyester chip is treated with water in a treatment layer, wherein the total hardness is 0.01 to ₃₀ CaCO _3. mg / l
Water treatment by introducing water into the treatment tank from outside the system.

In this case, at least a part of the treatment water discharged from the treatment tank can be returned to the treatment tank and used repeatedly.

In this case, the polyester chips can be continuously supplied to the processing tank.

In this case, the polyester chips can be intermittently supplied to the treatment tank.

In this case, the entire amount of the polyester chips can be filled in the treatment layer, and after the water treatment, the entire amount of the polyester chips can be extracted.

In this case, the discharge of the treated water from the treatment tank and the return of the discharged treated water to the treatment tank can be continued.

In this case, the discharge of the treated water from the treatment tank and the return of the discharged treated water to the treatment tank can be intermittent.

In this case, new treated water to be supplied to the treatment tank can be supplied to the treatment tank after the ion exchange treatment.

In this case, the polyester is
The polyester having an intrinsic viscosity of 0.55 to 1.30 deciliters / gram in which the main repeating unit is composed of ethylene terephthalate can be used.

According to the polyester production method of the present invention, it is possible to advantageously produce a polyester which is less likely to cause mold stains during molding and which has good bottle transparency.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester used in the present invention is preferably a polyester whose main repeating unit is composed of ethylene terephthalate, and more preferably a linear polyester containing at least 85 mol% of ethylene terephthalate units. Particularly preferred is a linear polyester containing 95 mol% or more of ethylene terephthalate units.

Examples of the dicarboxylic acid used as a copolymer in the polyester include aromatic dicarboxylic acids such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid and diphenoxyethane dicarboxylic acid. Acids and their functional derivatives, oxyacids and their functional derivatives such as p-oxybenzoic acid and oxycaproic acid, aliphatic dicarboxylic acids and their functional derivatives such as adipic acid, sebacic acid, succinic acid and glutaric acid, cyclohexane Alicyclic dicarboxylic acids such as dicarboxylic acids and functional derivatives thereof;

Glycols used by copolymerization in the polyester include aliphatic glycols such as diethylene glycol, trimethylene glycol, tetramethylene glycol and neopentyl glycol; alicyclic glycols such as cyclohexanedimethanol; bisphenol A; Aromatic glycols such as an alkylene oxide adduct of bisphenol A and the like can be mentioned.

Further, as other copolymerization components comprising a polyfunctional compound in the polyester, trimellitic acid and pyromellitic acid can be mentioned as acid components, and glycerin and pentaerythritol can be mentioned as glycol components. Can be. The amount of the above-mentioned copolymer component to be used must be such that the polyester resin maintains a substantially linear shape.

The intrinsic viscosity of the polyester used in the present invention, particularly the polyester whose main repeating unit is composed of ethylene terephthalate, is 0.55 to 1.3.
0 deciliter / gram, preferably 0.60 to 1.2
0 deciliter / gram, more preferably 0.65 to
It is in the range of 0.90 deciliter / gram. If the intrinsic viscosity is less than 0.55 deciliter / gram, the mechanical properties of the obtained molded article and the like are poor. On the other hand, if it exceeds 1.30 deciliters / gram, the resin temperature rises during melting by a molding machine or the like, and thermal decomposition becomes severe, so that free low-molecular-weight compounds that affect fragrance retention increase, Causes problems such as coloring of yellow.

The shape of the polyester chip may be any of a cylinder type, a square type, a flat plate shape, and the like.
Range. For example, in the case of a cylinder type, it is practical that the length is about 1.5 to 4 mm and the diameter is about 1.5 to 4 mm.

The acetaldehyde content of the polyester used in the present invention is 10 ppm or less, preferably 8 ppm.
ppm or less, more preferably 5 ppm or less, the formaldehyde content is 7 ppm or less, preferably 6 ppm or less,
More preferably, it is 4 ppm or less. The method for reducing the acetaldehyde content of the polyester used in the present invention to 10 ppm or less and the formaldehyde content to 7 ppm or less is not particularly limited. A method of performing solid phase polymerization at a temperature of 230 ° C. can be mentioned.

The amount of diethylene glycol in the polyester used in the present invention is 1.0 to 1.0 of the glycol component.
It is 5.0 mol%, preferably 1.3 to 4.5 mol%, more preferably 1.5 to 4.0 mol%. When the amount of diethylene glycol exceeds 5.0 mol%, the thermal stability deteriorates, the molecular weight decreases during molding, and the acetaldehyde content and the formaldehyde content increase unfavorably.

The content of the cyclic trimer of the polyester used in the present invention is 0.50% by weight or less, preferably 0.45% by weight or less, more preferably 0.40% by weight.
It is as follows. When molding a heat-resistant hollow molded article or the like from the polyester of the present invention, heat treatment is performed in a heating mold,
When the content of the cyclic trimer is 0.50% by weight or more, the adhesion of the oligomer to the surface of the heating mold rapidly increases, and the transparency of the obtained hollow molded article or the like is extremely deteriorated.

The above polyester can be produced by a conventionally known production method. That is, a direct esterification method in which terephthalic acid and ethylene glycol and, if necessary, other copolymerization components are directly reacted to distill off water and esterify, followed by polycondensation under reduced pressure, or dimethyl terephthalate and ethylene glycol It is produced by a transesterification method in which methyl alcohol is distilled off and transesterification is carried out by reacting other copolymerization components if necessary, followed by polycondensation under reduced pressure. Solid-state polymerization may be further performed to increase the intrinsic viscosity and decrease the acetaldehyde content and the like.

The melt polycondensation reaction may be carried out in a batch reactor or a continuous reactor. In any of these methods, the melt polycondensation reaction may be performed in one step or may be performed in multiple steps.
The solid-state polymerization reaction can be performed in a batch-type apparatus or a continuous-type apparatus as in the melt polycondensation reaction. The melt polycondensation and the solid phase polymerization may be performed continuously or may be performed separately.

In the case of the direct esterification method, compounds of Ge, Sb and Ti are used as a polycondensation catalyst, and a Ge compound is particularly advantageous. As the Ge compound, amorphous germanium dioxide, crystalline germanium dioxide powder or a slurry of ethylene glycol, a solution obtained by heating and dissolving crystalline germanium dioxide in water, or a solution obtained by adding ethylene glycol to this solution and performing a heat treatment, are used. In particular, in order to obtain the polyester used in the present invention, it is preferable to use a solution in which germanium dioxide is dissolved in water by heating, a colloidal solution, a solution in which ethylene glycol is added thereto and heated, or a solution of germanium dioxide in ethylene glycol. These polycondensation catalysts can be added during the esterification step. When a Ge compound is used, the amount used is 20 to 150 ppm, preferably 23 to 10 ppm, as the amount of Ge remaining in the polyester resin.
0 ppm, more preferably 25-70 ppm.

It is preferable to use phosphoric acid, phosphoric acid esters such as polyphosphoric acid and trimethyl phosphate as stabilizers. These stabilizers can be added during the esterification reaction step from a slurry preparation tank of terephthalic acid and ethylene glycol.

In order to control the DEG content in the polyester, a basic compound such as a tertiary amine such as triethylamine or tri-n-butylamine is used in the esterification step.
A quaternary ammonium salt such as tetraethylammonium hydroxide can be added.

In the present invention, polyester is used to prevent mold contamination due to oligomers such as cyclic trimers adhering to the inner surface of the mold, the exhaust port of the mold gas, the exhaust pipe, etc. during molding. Then, a contact treatment with water is performed after the solid phase polymerization. As a method of the contact treatment with water, a method of immersing in water may be mentioned. The time for performing the contact treatment with water is 5 minutes to 2 days, preferably 10 minutes to 1 day, more preferably 30 minutes to 10 hours, and the water temperature is 20 to 180 ° C, preferably 40 to 150 ° C. ° C, more preferably 50 to 120 ° C.

In the case of industrially treating polyester chips with water, natural water (industrial water) and wastewater are often reused because of the large amount of water used for the treatment. Normally, this natural water is collected from river water, groundwater, or the like, and refers to water that has been subjected to treatment such as sterilization and removal of foreign substances without changing the shape of water (liquid). Further, natural water generally used for industrial use has a high total hardness and contains a large amount of metal-containing substances such as sodium, magnesium, calcium, and silicon dioxide. When the water treatment is performed using natural water, it adheres to and penetrates the polyester chips to form crystal nuclei, and the transparency of the hollow molded container using such polyester chips becomes extremely poor.

The following is an example of a method for industrially performing water treatment, but the method is not limited thereto. The processing method may be either a continuous method or a batch method, but the continuous method is preferable for industrial use.

Regardless of whether the water treatment method is continuous or batch, if all or most of the treated water discharged from the treatment tank is converted into industrial wastewater, a large amount of fresh water is required. In addition to the above, there is a concern about the impact on the environment due to increased wastewater. That is, at least a part of the treated water discharged from the treatment tank is returned to the water treatment tank and reused, thereby reducing the required amount of water and reducing the effect on the environment by increasing the amount of wastewater. If the wastewater returned to the water treatment tank maintains a certain temperature, the amount of heating of the treated water can be reduced, so that the treated water discharged from the treatment layer is preferably returned to the water treatment layer and reused. . In addition, by reusing water, the flow rate of the treated water in the treated layer can be increased, and as a result, fines attached to the polyester chips can be washed out, thereby producing a fine removing effect.

When the polyester chips are to be continuously treated with water, the polyester chips are continuously treated in a tower-type treatment tank, or the polyester chips are intermittently received from above, and water is continuously supplied in parallel or countercurrently to treat the water. Can be done. The treated polyester chips are continuously or intermittently extracted from the lower part of the treatment layer.

In the case of treating the polyester chips with water in a batch system, a silo-type treatment tank may be used. That is, the chips of polyester are received in a silo in a batch system and water treatment is performed. Alternatively, it is also possible to receive a polyester chip in a rotating cylindrical processing tank and perform water treatment while rotating the chip, thereby making contact with water more efficient.

In this case, the entire amount of the polyester chips is charged and filled in the treatment tank, and the treated water is filled with the treated water, and the treated water is circulated continuously or intermittently as needed (generally referred to as continuous). In addition, part of the treated water is discharged continuously or intermittently, and new treated water is additionally supplied. After the water treatment, the entire amount of the polyester chips is extracted from the treatment layer.

Regardless of whether the method of water treatment is continuous or batch, the total hardness of new water introduced into the treatment tank is 0.01 to ₃₀ CaCO ₃ mg / l, preferably 0.1 to ₃₀ CaCO ₃ . 02~15CaCO ₃ mg / l, more preferably 0.05~2.0CaCO ₃ mg / l, more preferably 0.05~1.0CaCO ₃ mg / l. When the total hardness exceeds 20 CaCO ₃ mg / l, a metal-containing substance adheres to the processing tank wall and the pipe wall, causing problems such as clogging of the pipe and making the cleaning of the processing tank and the pipe difficult. In addition, fine particles of metal-containing substances floating and settling in the treated water and adhering to the treatment tank walls and piping walls adhere to and penetrate the polyester chips, which promotes crystallization during molding, resulting in bottles with poor transparency. Problems can occur.

Regardless of whether the water treatment method is continuous or batchwise, when the total hardness of new water introduced into the treatment tank is less than 0.01 CaCO ₃ mg / l, It is necessary to perform a treatment such as distillation. In this case, equipment costs and manufacturing costs are increased, and economical water treatment becomes impossible.

A method for reducing the total hardness of new water introduced into the treatment tank will be described below, but the present invention is not limited to this.

In order to reduce the total hardness of the new water introduced into the treatment tank, the total hardness of the water is reduced to at least one or more locations in the process before the industrial water is sent to the treatment tank to be supplied to the treatment tank. Install the equipment. Further, in the process until the treated water discharged from the treatment tank is returned to the treatment tank again, a device for reducing the total hardness may be installed at at least one or more places. An apparatus for reducing the total hardness includes an ion exchange apparatus.

The treated water discharged from the treatment tank in the water treatment includes fines that have already adhered to the polyester chips at the stage of receiving the polyester chips in the treatment tank, polyester chips between water treatments, or the walls of the treatment tank. Contains fines of polyester generated by friction with. Therefore, at least one or more devices for removing fines are installed in the process until the treated water discharged from the treatment tank is returned to the treatment tank again. Examples of the device for removing fines include a filter filtration device, a membrane filtration device, a sedimentation tank, a centrifugal separator, and a foam entrainer. For example, in the case of a filter filtration device, a filtration device such as a belt filter system, a bag filter system, a cartridge filter system, and a centrifugal filtration system may be used. Above all, a belt filter system, a centrifugal filtration system, and a bag filter system are suitable for continuous operation. In the case of a filter device of a belt filter type, examples of the filter medium include paper, metal, cloth, and the like. In addition, in order to efficiently remove fines and flow the treated water, the mesh size of the filter is 5 to 100 μm, preferably 10 to 70 μm.
m, more preferably 15 to 40 μm.

The water-treated polyester chips are drained by a draining device such as a vibrating sieve or a Simon Carter and transferred to a drying step. Naturally, the water separated from the polyester chips by the draining device is sent to the above-mentioned fine removing device, and can be used again for water treatment.

For drying the polyester chips, a commonly used drying treatment of the polyester chips can be used. As a method for continuous drying, a hopper-type through-air dryer that supplies a polyester chip from the upper portion and allows a drying gas to flow from the lower portion is usually used. As a method of reducing the amount of drying gas and drying efficiently, a rotating disk type continuous dryer is selected, and heating steam, heating medium, etc. are supplied to the rotating disk and the outer jacket while passing a small amount of drying gas. The dried granular polyester chips can be dried indirectly.

As a dryer for drying in a batch system, a double cone type rotary dryer is used, and drying can be carried out under vacuum or while passing a small amount of drying gas under vacuum. Alternatively, the drying may be performed while passing a drying gas under atmospheric pressure.

As the dry gas, atmospheric air may be used, but dry nitrogen and dehumidified air are preferred from the viewpoint of preventing molecular weight reduction due to hydrolysis or thermal oxidative decomposition of polyester.

[0052]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In addition, the measuring method of the main characteristic value in this specification is demonstrated below.

(1) Intrinsic Viscosity of Polyester (IV) It was determined from the solution viscosity at 30 ° C. in a 1,1,2,2-tetrachloroethane / phenol (2: 3 weight ratio) mixed solvent.

(2) Density: 25 using a density gradient tube of a mixed solvent of carbon tetrachloride / n-heptane.
Measured in ° C.

(3) Content of Polyester Cyclic Trimer A sample is dissolved in a mixed solution of hexafluoroisopropanol / chloroform, and further diluted by adding chloroform. After adding methanol to precipitate a polymer, the mixture is filtered. The filtrate was evaporated to dryness, made up to a constant volume with dimethylformamide, and a cyclic trimer composed of ethylene terephthalate units was quantified by liquid chromatography.

(4) Haze (% haze) A sample was cut from the body (thickness: about 0.4 mm) of the hollow molded article, and measured with a haze meter manufactured by Toyo Seisakusho.

(5) Total hardness of new water to be introduced into the treatment tank (CaCO ₃ mg / l) Water was collected from the treatment water inlet of the treatment tank, and calcium in the water was measured using an inductively coupled plasma emission spectrometer manufactured by Shimadzu Corporation. The amount of element and the amount of magnesium element were measured and corrected to the value of total hardness. Total hardness CaCO ₃ mg / l = magnesium amount (mg / l) × 4.11 + calcium amount (mg
/L)×2.5

(Example 1) Raw material chip supply port (1) in the upper part of processing tank, inlet (8) of water through ion exchange device (10) for reducing the total hardness of industrial water (9), processing tank The discharge outlet located at the upper limit level of the treated water (2), the outlet for the mixture of polyester chips and treated water at the lower part of the treatment tank (3), the treated water discharged from the overflow outlet, and the outlet at the lower part of the treatment tank A pipe (6) for sending treated water from a polyester chip draining device (4) discharged from the tank to a water treatment tank again through a filtering device (5), which is a 30-μm belt-type filter made of paper. A polyethylene terephthalate (hereinafter abbreviated as PET) chip is treated with water using a treatment tank shown in FIG. 1 having a capacity of 320 liters and having an inlet port (7) for the treated water after fine removal. It was.

The limiting viscosity is 0.75 deciliter / gram.
With a density of 1.400 g / cm ^ThreeAnd the cyclic 3 quantity
PET chips with a body content of 0.33% by weight
50kg / h into a water treatment tank controlled at 95 ° C
Water from the upper part of the treatment tank (1)
After 5 hours, the PET chip was discharged from the outlet (3) at the bottom of the processing tank.
Process water at 50 kg / hour
I started. At this time, the total hardness of the industrial water was 41.73 Ca
CO_Threemg / l. Draining after 72 hours of continuous operation
PET chip from device (4) and new water inlet
Water from (8) was sampled.

The sampled PET chips were dried under reduced pressure, and preformed bottles were molded using an M-100 injection molding machine manufactured by Meiki Seisakusho. Injection molding temperature is 295
° C. Next, this preformed body was biaxially stretched and blown at a magnification of about 2.5 times in the vertical direction and about 5 times in the circumferential direction using an LB-01E molding machine manufactured by COPOPLAST, and the capacity was 1500 c.
The container of c was molded. The stretching temperature was controlled at 100 ° C.

The properties of the polyester container obtained in Example 1 and the total hardness of fresh water are shown in Table 1 together with Comparative Examples.

(Examples 2 and 3) Ion exchange apparatus (10)
The procedure was the same as in Example 1, except that the capacity (the number of theoretical plates, the type of ion exchange resin) was changed. Table 1 shows the results.

[0063]

[Table 1]

As is clear from Table 1, the total hardness of new water introduced into the treatment tank of the present invention is 0.01 to 30 CaCO 3.
_By adjusting the amount to ₃ mg / l, the obtained molded article has excellent transparency.

Comparative Example 1 The procedure of Example 1 was repeated, except that the ion exchange device for reducing the total hardness of the industrial water used in Example 1 was removed, and that part was changed to a direct connection pipe. As shown in Table 1, the total hardness of new water is high,
The transparency of the molded article obtained by the treatment was poor.

[0066]

According to the present invention, there is provided a method in which polyester chips are supplied to a water treatment tank, and a part of the treatment water discharged from the treatment tank is returned to the treatment tank again for repeated use.
The new water introduced into the treatment tank is 0.01 to ₃₀ CaCO ₃
Since it is mg / l, it is difficult to generate mold stains during molding, and furthermore, it can be advantageously used as a polyester having good bottle transparency.

[Brief description of the drawings]

FIG. 1 is a schematic view of an apparatus used for a method for producing a polyester of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Raw material chip supply port 2 Overflow discharge port 3 Polyester chip and treated water discharge port 4 Drainer 5 Fine removal device 6 Piping 7 Treated water inlet 8 Hardness-reduced water inlet 9 Industrial water inlet 10 Underwater Equipment for removing metal-containing substances

 ──────────────────────────────────────────────────の Continued on the front page F term (reference) 4J029 AA01 AB04 AC01 AC02 AD01 AE01 AE03 BA03 BA04 BA05 BA10 BB13A BD06A BF09 BF26 CA02 CA06 CB05A CB06A CB10A CC06A CD03 EA02 EB05A KH03 KH05 KH08

Claims (9)

[Claims] 1. A method for producing a polyester in which a polyester chip is water-treated in a treatment layer, wherein the total hardness is 0.0
A process for producing a polyester, characterized in that water treatment is carried out by introducing water having a concentration of 1 to ₃₀ CaCO ₃ mg / l from outside the system into the treatment tank. 2. The method for producing polyester according to claim 1, wherein at least a part of the treated water discharged from the treatment tank is returned to the treatment tank and used repeatedly. 3. The method according to claim 1, wherein the polyester chips are continuously supplied to the treatment tank. 4. The method for producing polyester according to claim 1, wherein the polyester chips are intermittently supplied to the treatment tank. 5. The method for producing polyester according to claim 1, wherein the whole amount of the polyester chips is filled in the treatment layer, and the whole amount of the polyester chips is extracted after the water treatment. 6. The production of the polyester according to claim 1, wherein discharge of the treated water from the treatment tank and return of the discharged treated water to the treatment tank are continuous. Method. 7. The method for producing a polyester according to claim 1, wherein the discharge of the treated water from the treatment tank and the return of the discharged treated water to the treatment tank are intermittent. . 8. The method for producing a polyester according to claim 1, wherein fresh treated water supplied to the treatment tank is subjected to ion exchange treatment and then supplied to the treatment tank. 9. The polyester has an intrinsic viscosity of 0.55 to 0.55.
9. The method for producing a polyester according to claim 1, wherein the main repeating unit of 1.30 deciliter / gram is a polyester composed of ethylene terephthalate.