JP2723140B2 - Polyester resin composition, method for producing the same, and use of the composition - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a polyester resin composition, a method for producing the same, and uses of the composition.
The present invention relates to a polyester resin composition capable of obtaining a molded article such as a stretched bottle having excellent transparency and heat resistance, a method for producing the same, and uses of the composition.

Technical Background of the Invention and Problems Thereof Conventionally, glass has been widely used as a material for containers such as seasonings, oils, juices, carbonated drinks, beer, sake, cosmetics, and detergents. However, since the production cost of the glass container is high, a method of collecting an empty container after normal use and circulating and reusing the container has been adopted. Further, since the glass container is heavy, the transportation cost is increased, and the glass container is liable to be broken and is inconvenient to handle.

In an effort to overcome these drawbacks of glass containers, the conversion from glass containers to various plastic containers has recently been rapidly progressing. As the material, various plastics are employed depending on the type of filling content and the purpose of use, and among these plastic materials, a saturated crystalline polyester resin such as polyethylene terephthalate has mechanical strength, heat resistance, Because of its excellent transparency and gas barrier properties, it is used as a container material for juices, soft drinks, carbonated drinks, seasonings, detergents, cosmetics, and the like. Among these uses, hollow molded containers for filling juices, soft drinks, and carbonated drinks are required to be sterilized and filled at a high temperature. Therefore, heat-resistant resins that can withstand high-temperature filling are required. It is required to form a hollow molded container, and it is required that all of these filled hollow molded containers have excellent transparency.

However, a saturated crystalline polyester resin such as polyethylene terephthalate is a plastic excellent in transparency, but further improvement in heat resistance has been desired.

Therefore, the present inventors have made intensive studies to improve the heat resistance of a saturated crystalline polyester resin such as polyethylene terephthalate, and found that the addition of polyethylene naphthalate to the polyethylene terephthalate can improve the heat resistance. Was.

However, polyethylene terephthalate and polyethylene naphthalate are inferior in compatibility, and the mere blending of both causes whitening and opacity of the resulting blend, and also has poor drawability. Was.

In order to solve such problems, the inventors of the present invention have conducted further intensive studies and found that if a specific pre-kneaded material is added to a composition comprising polyethylene terephthalate and polyethylene naphthalate, transparency and heat resistance can be improved. The present inventors have found that a polyester resin composition capable of forming a stretched bottle and the like excellent in such properties can be obtained, and have completed the present invention.

Object of the Invention The present invention is intended to solve the problems associated with the prior art as described above, transparency, a polyester resin composition capable of forming a stretched bottle and the like with excellent heat resistance and the like It is intended to provide a manufacturing method.

Another object of the present invention is to provide a film, a preform, and a container comprising the polyester resin composition as described above.

SUMMARY OF THE INVENTION The polyester resin composition according to the present invention comprises (A) 10 to 90 parts by weight of polyethylene terephthalate and (B) 90 to 10 parts by weight of polyethylene naphthalate.
(C) Pre-kneaded product of 20 to 80% by weight of polyethylene terephthalate and 80 to 20% by weight of polyethylene naphthalate with respect to 100 parts by weight.
It is characterized by consisting of 20 parts by weight.

The method for producing the polyester resin composition according to the present invention comprises: (A) 10 to 90 parts by weight of polyethylene terephthalate, (B) 90 to 10 parts by weight of polyethylene naphthalate, and (C) 20 to 80 parts by weight of polyethylene terephthalate and polyethylene naphthalate. A pre-kneaded product obtained by melt-kneading 80 to 20% by weight of phthalate is mixed in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the components (A) and (B) in total. And

Further, the polyester film, the polyester preform and the polyester container according to the present invention are characterized by comprising the polyester resin composition as described above.

Since the polyester resin composition according to the present invention is composed of a specific amount of polyethylene terephthalate, polyethylene naphthalate, and a pre-kneaded product thereof as described above, the polyester resin composition has remarkably excellent transparency and heat resistance such as hot water resistance. Also, it has excellent gas barrier properties.

Further, in the present invention, since the polyester resin composition is produced by the above method, a polyester resin composition having remarkably excellent transparency, heat resistance such as hot water resistance, and excellent gas barrier properties is obtained. Can be

Further, since the polyester film, polyester preform and polyester container according to the present invention are formed from the polyester resin composition as described above, they are remarkably excellent in transparency and heat resistance such as hot water resistance,
Excellent gas barrier properties.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the polyester resin composition according to the present invention, a method for producing the same, and uses of the composition will be specifically described.

The polyester resin composition according to the present invention comprises polyethylene terephthalate (A) in addition to polyethylene terephthalate (A) and polyethylene naphthalate (B).
And a pre-kneaded product (C) obtained by melt-kneading polyethylene naphthalate (B). First, polyethylene terephthalate (A) used as a raw material will be described.

Polyethylene terephthalate Polyethylene terephthalate used in the present invention,
Manufactured using terephthalic acid or an ester-forming derivative thereof and ethylene glycol or an ester-forming derivative thereof as raw materials, the polyethylene terephthalate is obtained by copolymerizing 20 mol% or less of another dicarboxylic acid and / or another glycol. May be.

As the dicarboxylic acid used for copolymerization other than terephthalic acid, specifically, phthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, aromatic dicarboxylic acids such as diphenoxyethane dicarboxylic acid, adipic acid, sebacic acid, Examples thereof include aliphatic dicarboxylic acids such as azelaic acid and decane dicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

As the glycol used for copolymerization other than ethylene glycol, specifically, trimethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, aliphatic glycols such as dodecamethylene glycol, cyclohexane dimethanol and the like Examples thereof include alicyclic glycols, bisphenols, hydroquinone, and aromatic diols such as 2,2-bis (4-β-hydroxyethoxyphenyl) propane.

The polyethylene terephthalate particularly preferably used in the present invention has a general formula [I] The content of the ethylene terephthalate component unit (a) represented by the following formula is in the range of 95.0 to 98.6 mol%, preferably 97.0 to 98.5 mol%, and more preferably 97.3 to 98.3 mol%.
I] The content of the dioxyethylene terephthalate component unit (b) represented by the formula is 1.4 to 5.0 mol%, preferably 1.5 to 3.1 mol%.
Mole% is particularly preferably in the range of 1.7 to 2.6 mol%.

In the polyethylene terephthalate, the ethylene terephthalate component unit (a) represented by the general formula [I] and the dioxyethylene terephthalate component unit (b) represented by the general formula [II] are randomly arranged to form an ester bond. This forms a substantially linear polyester. The fact that the polyethylene terephthalate is substantially linear is confirmed by the fact that the polyethylene terephthalate dissolves in o-chlorophenol.

The intrinsic viscosity [η] of the polyethylene terephthalate (A) used in the present invention measured at 25 ° C. in o-chlorophenol is 0.60 to 1.00 dl / g, preferably 0.70 to 0.87 dl.
/ g, particularly preferably in the range of 0.72 to 0.85 dl / g. If the intrinsic viscosity [η] is less than 0.60 dl / g, a hollow molded container excellent in heat resistance, transparency, and mechanical strength cannot be obtained. And the stretch blow moldability becomes inferior. The intrinsic viscosity [η] of polyethylene terephthalate is measured by the following method. That is, the sample polyethylene terephthalate in o-chlorophenol, 1g / 100ml
, And the solution viscosity was measured at room temperature using an Ubbelohde capillary viscometer. Thereafter, o-chlorophenol was gradually added, and the solution viscosity on the low concentration side was measured.
The intrinsic viscosity ([η]) is determined by extrapolating to the% concentration.

Further, the temperature-rising crystallization temperature (Tcl) when the polyethylene terephthalate is heated at a rate of 10 ° C./min with a differential scanning calorimeter (DSC) is 155.0 ° C. or higher, preferably 167.0 ° C.
To 185 ° C, particularly preferably 168.0 to 180.0 ° C. Further, the temperature rise crystallization temperature (Tcl) of the polyethylene terephthalate is in the range of the following formula 67.5 [η] + 119.0 ≦ Tcl ≦ 67.5 [η] +133.5 in relation to the intrinsic viscosity [η], More preferably, it is desirable to be in the range of 67.5 [η] + 122.5 ≦ Tcl ≦ 67.5 [η] +128.5.

Temperature rise crystallization temperature of polyethylene terephthalate (Tc
When l) is lower than 165.0 ° C., the transparency of the obtained hollow molded container is reduced, the heat resistance is also reduced, and thermal deformation occurs when a soft drink such as juice or cola is filled at a high temperature. Further, when the temperature-increase crystallization temperature (Tcl) is lower than the lower limit of the above equation, thermal deformation is likely to occur when a soft drink such as juice or cola is filled at a high temperature. In addition, the temperature rise crystallization temperature (Tcl) of polyethylene terephthalate is measured by the following method. That is, using a DSC-2 type differential scanning calorimeter manufactured by PerkinElmer, a sample of about 10 mmg from the center of a polyethylene terephthalate chip dried at about 140 ° C. under a pressure of about 5 mmHg for about 5 hours or more was used for liquid. The measurement is performed by enclosing in an aluminum pan under a nitrogen atmosphere. The measurement conditions were as follows: first, the temperature was rapidly raised from room temperature, melted and held at 290 ° C for 10 minutes, then rapidly cooled to room temperature, and then the peak temperature of the exothermic peak detected when the temperature was raised at a rate of 10 ° C / min. Ask.

Further, the melting point (Tm) of polyethylene terephthalate is indicated by the peak temperature of the endothermic peak measured under the same conditions as the temperature rise crystallization temperature (Tcl).

Next, a method for producing the above polyethylene terephthalate will be described.

Polyethylene terephthalate used in the present invention,
For example, it can be produced by a direct polymerization method.
Specifically, a low-order condensate is obtained by continuously reacting a mixture of terephthalic acid and ethylene glycol in at least two steps of esterification reaction steps, and further, this is continuously converted in at least two steps of liquid phase polycondensation steps. Polyester is obtained by subjecting it to polycondensation under reduced pressure to form a polyester chip by melt extrusion.
A method is employed in which the polyester chips are polycondensed in an inert gas atmosphere in at least one solid phase polymerization step to increase the intrinsic viscosity [η].

 Next, each step and its conditions will be described.

The polyethylene terephthalate as described above can be obtained by appropriately selecting the conditions of each step and controlling the polycondensation reaction so that the composition and intrinsic viscosity of the polyethylene terephthalate fall within desired ranges.

Specifically, first, an ethylene glycol slurry of terephthalic acid is formed from a mixture of terephthalic acid and 1.02 to 1.4 moles, preferably 1.03 to 1.3 moles of ethylene glycol per mole of terephthalic acid. The slurry is continuously supplied to the esterification reaction step. The esterification reaction is carried out using a device in which at least two esterification reactors are connected in series, under conditions where ethylene glycol is refluxed, while removing water generated by the reaction outside the system by a rectification column. . The reaction conditions for performing the esterification reaction are such that the temperature of the first-stage esterification reaction is usually 240 to 2
70 ° C, preferably 245-265 ° C, pressure is usually 0.2-3kg
/ cm ² G preferably 0.5 to ² kg / cm ² G, and the temperature of the final esterification reaction is usually 250 to 280 ° C., preferably 255
To 275 ° C., and the pressure is usually 0 to 1.5 kg / cm ² G, preferably 0 to 1.3 kg / cm ² G. Therefore, when the esterification reaction is carried out in two stages, the first-stage and second-stage esterification reaction conditions are respectively in the above ranges, and when the esterification reaction is carried out in three or more stages, the second stage The reaction conditions for the esterification reaction from the first stage to the stage immediately before the final stage are those between the above-mentioned first-stage reaction conditions and final-stage reaction conditions. For example, if the esterification reaction is performed in three steps,
The reaction temperature of the second stage esterification reaction is usually 245 to 275 ° C.
The temperature is preferably 250 to 270 ° C., and the pressure is usually 0 to ² kg / cm ² G
Preferably it is 0.2 to 1.5 kg / cm ² G. The reaction rates of these esterification reactions are not particularly limited in each stage, but it is preferable that the increase and the degree of the esterification reaction rate in each stage be distributed smoothly, and furthermore, the final stage of the esterification In the reaction product, it is usually desirable to reach 90% or more, preferably 93% or more. A low-order condensate is obtained by these esterification steps, and the number-average molecular weight of the low-order condensate is usually 500 to 5,000.

The low-order condensate thus obtained is continuously supplied to the polycondensation reactor in the next liquid phase polycondensation step. The reaction conditions of the polycondensation reaction are such that the reaction temperature of the first stage polycondensation is usually 260 to 290 ° C, preferably 265 to 290 ° C, more preferably
270-285 ° C, pressure is usually 500-20 Torr, preferably 2
The temperature is usually from 270 to 300 ° C, preferably from 275 to 295 ° C, and the pressure is usually from 10 to 0.1 Torr, preferably from 5 to 0.5 Torr.

When the polycondensation reaction is carried out in two stages, the first stage and second stage polycondensation reaction conditions are respectively in the above ranges, and when the polycondensation reaction is carried out in three or more stages, the second stage starts from the second stage. The reaction conditions for the polycondensation reaction up to one stage before the final stage are those between the above-mentioned first stage reaction conditions and the final stage reaction conditions. For example, when the polycondensation reaction is performed in three stages, the reaction temperature of the second stage polycondensation reaction is usually 265 to 295 ° C., preferably 270 to 290 ° C., and more preferably 270 to 285 ° C. Is typically in the range of 50-2 Torr, preferably 40-5 Torr. The intrinsic viscosity [η] 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 furthermore, the final stage polycondensation The intrinsic viscosity [η] of polyethylene terephthalate obtained from the reactor is usually 0.55 to
The range is 0.72 dl / g, preferably 0.57 to 0.68 dl / g. Thus, the polyethylene terephthalate obtained from the final polycondensation reactor is usually formed into chips by a melt extrusion molding method.

Further, the polyethylene terephthalate chips are supplied to a solid phase polycondensation step. The solid phase polycondensation step comprises at least one stage, the polycondensation temperature is usually 190 to 230 ° C., preferably 195 to 225 ° C., and the pressure is usually 1 kg / cm ² G to 10 Torr.
Nitrogen gas, preferably under normal pressure to 100 Torr,
The solid-phase polycondensation reaction is performed under an inert gas atmosphere such as an argon gas or a carbon dioxide gas. Among these inert gases, nitrogen gas is preferred.

The above-mentioned esterification reaction can be carried out without adding any additives other than terephthalic acid and ethylene glycol, and can be carried out in the presence of a polycondensation catalyst described later. Tertiary n-butylamine, benzyldimethylamine and the like
Quaternary ammonium hydroxide such as quaternary amine, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide and a small amount of a basic compound such as lithium carbonate, sodium carbonate, potassium carbonate and sodium acetate. To implement.
It is preferable because the ratio of the dioxyethylene terephthalate component unit in the main chain of polyethylene terephthalate can be maintained at a relatively low level.

The method of adding these base component unit compounds is not particularly limited, and they may be added to all of the esterification reactors or may be added to the first or second or subsequent specific reactors. Good. Further, the polycondensation reaction is preferably performed in the presence of a catalyst and a stabilizer. As a catalyst, a germanium compound such as germanium dioxide, germanium tetraethoxide, or germanium tetra n-butoxide, an antimony catalyst such as antimony trioxide, or a titanium catalyst such as titanium tetrabutoxide can be used. Among these catalysts, it is preferable to use a germanium dioxide compound because the resulting polyethylene terephthalate has excellent hue and transparency. Examples of the stabilizer include phosphates such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, triphenyl phosphite, trisdodecyl phosphite, and trisnonyl phenyl. Phosphites such as phosphites,
Acidic phosphates such as methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate and dioctyl phosphate, and phosphorus compounds such as phosphoric acid and polyphosphoric acid are used. The proportion of these catalysts or stabilizers used is usually 0.0005 to 0.2% by weight, preferably 0.001 to 0.05% by weight of the metal in the catalyst in the case of a catalyst, based on the weight of the mixture of terephthalic acid and ethylene glycol. %, And in the case of a stabilizer, usually 0.1% by weight of phosphorus atoms in the stabilizer.
It is in the range of 001 to 0.1% by weight, preferably 0.002 to 0.02% by weight. These catalysts and stabilizers can be supplied at the stage of the esterification reaction step,
It can also be supplied to the first stage reactor of the polycondensation reaction step.

Polyethylene terephthalate as such a raw material is used in the form of pellets, and the pellets can be in the form of a strand, a sheet, a block, a powder, or the like.

The pellets as such raw materials may be newly prepared ones, or may be obtained by pulverizing a molded product once molded into a parison or a container from the pellets, and further, a mixture thereof. It may be.

Polyethylene naphthalate Polyethylene naphthalate used in the present invention is 2,
It is desirable to contain ethylene-2,6-naphthalate units derived from 6-naphthalenedicarboxylic acid and ethylene glycol in an amount of 60 mol% or more, preferably 80% or more, and more preferably 90 mol% or more. 2,6
-It may contain structural units other than naphthalate in an amount of less than 40 mol%.

Structural units other than ethylene-2,6-naphthalate include terephthalic acid, isophthalic acid, 2,7-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, and 4,4 ' -Diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid, aromatic dicarboxylic acid such as dibromoterephthalic acid, adipic acid, azelaic acid, sebacic acid, decane dicarboxylic acid, etc. Aliphatic dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid, alicyclic dicarboxylic acid such as hexahydroterephthalic acid, glycolic acid,
hydroxycarboxylic acids such as p-hydroxybenzoic acid and p-hydroxyethoxybenzoic acid, propylene glycol, trimethylene glycol, diethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, neopentylene glycol, p
-Xylene glycol, 1,4-cyclohexanedimethanol, bisphenol A, p, p-diphenoxysulfone, 1,4-bis (β-hydroxyethoxy) benzene,
Examples include structural units derived from 2,2-bis (p-β-hydroxyethoxyphenyl) propane, polyalkylene glycol, p-phenylenebis (dimethylsiloxane), glycerin, and the like.

Further, the polyethylene naphthalate used in the present invention contains a small amount of a structural unit derived from a polyfunctional compound such as trimesic acid, trimethylolethane, trimethylolpropane, trimethylolmethane, pentaerythritol, for example, in an amount of 2 mol% or less. You may go out.

Further, the polyethylene naphthalate used in the present invention may contain a small amount of a structural unit derived from a monofunctional compound such as benzoylbenzoic acid, diphenylsulfonemonocarboxylic acid, stearic acid, methoxypolyethylene glycol, and phenoxypolyethylene glycol, for example, in an amount of 2 mol% or less. May be included.

Such polyethylene naphthalate is substantially linear, which means that the polyethylene naphthalate is o-
Confirmed by dissolving in chlorophenol.

The intrinsic viscosity [η] of polyethylene naphthalate measured in o-chlorophenol at 25 ° C. is in the range of 0.2 to 1.1 dl / g, preferably 0.3 to 0.9 dl / g, particularly preferably 0.4 to 0.8 dl / g. Is desirable.

The intrinsic viscosity [η] of polyethylene naphthalate is measured in the same manner as in the case of polyethylene terephthalate.

Further, the temperature-rising crystallization temperature (Tc) when the polyethylene nalephthalate is heated at a rate of 10 ° C./min with a differential scanning calorimeter (DSC) is 150 ° C. or higher, and preferably 160 to 230 ° C.
C, particularly preferably in the range of 170 to 220C.

The temperature-rise crystallization temperature (Tc) of polyethylene naphthalate is measured in the same manner as in the case of polyethylene terephthalate.

The above-mentioned polyethylene naphthalate can be produced by a conventionally known production method.

Pre-kneaded product In the present invention, a pre-kneaded product (master batch, MB) obtained by melt-kneading polyethylene terephthalate and polyethylene naphthalate in addition to polyethylene terephthalate and polyethylene naphthalate as described above is used.

Thus, the polyester resin composition according to the present invention,
In addition to the polyethylene terephthalate (A) and the polyethylene naphthalate (B), since these pre-kneaded materials (C) are included, the transparency and stretchability of the polyethylene terephthalate (A) and the polyethylene naphthalate (B) are increased. This gives a polyester resin composition having excellent properties.

In order to obtain such a pre-kneaded material, various known methods can be used. For example, a Henschel mixer, v-
A method in which polyethylene terephthalate (A) and polyethylene naphthalate (B) are mixed using a blender, ribbon blender, tumbler blender, or the like, and then melt-kneaded using a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like. Can be mentioned. Furthermore, a method of subsequently granulating or pulverizing can be mentioned.

Such melt kneading is usually at 260 to 300 ° C, preferably
It is performed at a temperature of 270-290 ° C.

In obtaining such a pre-kneaded product, polyethylene terephthalate is used in an amount of 20 to 80% by weight, preferably 40 to 60% by weight, and polyethylene naphthalate is used in an amount of 80 to 20% by weight, preferably Is used in an amount of 60 to 40% by weight.

When polyethylene terephthalate and polyethylene naphthalate are used in the above range, a polyester resin composition or the like having remarkably excellent transparency, heat resistance such as hot water resistance, gas barrier properties, and the like can be obtained.

Production of Polyester Resin Composition By mixing the above polyethylene terephthalate (A), polyethylene naphthalate (B) and their pre-kneaded product (C), the polyester resin composition according to the present invention is obtained. At this time, various known methods can be used. For example, using a Henschel mixer, v-blender, ribbon blender, tumbler blender, or the like, polyethylene terephthalate (A), polyethylene naphthalate (B), and a pre-kneaded product thereof (C ) Can be used. Furthermore, a method of mixing and kneading with a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like after mixing as described above, and then granulating or pulverizing can be exemplified.

Such melt kneading is usually performed at a temperature of 260 to 300 ° C, preferably 270 to 290 ° C.

In producing the polyester resin composition according to the present invention, polyethylene terephthalate (A) is used in an amount of 10 to 90 parts by weight, preferably 20 to 80 parts by weight, and polyethylene naphthalate (B) is used in an amount of 90 to 10 parts by weight. , Preferably in an amount of 80 to 20 parts by weight, and based on 100 parts by weight of the total (A + B), a prekneaded product of polyethylene terephthalate 20 to 80% by weight and polyethylene naphthalate 80 to 20% by weight (C ) Is used in an amount of 1 to 20 parts by weight, preferably 3 to 10 parts by weight.

When polyethylene terephthalate (A) is used in an amount of 10 to 90 parts by weight, the moldability is excellent and the effect of improving gas barrier properties tends to be large.

When the polyethylene naphthalate (B) is used in an amount of 10 to 90 parts by weight, an effect of improving heat resistance is observed, and a tendency for excellent moldability occurs.

When the pre-kneaded material (C) is used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total of (A) and (B), the effect of improving transparency is large, and A tendency to have excellent physical properties occurs.

The polyester resin composition according to the present invention includes heat stabilizers, weather stabilizers, antistatic agents, lubricants, mold release agents, pigment dispersants, pigments or dyes, and various compounding agents usually used by adding to polyester. Can be added in a range that does not impair the object of the present invention. These compounding agents may be added when preparing the preliminary kneaded material (C), or may be added when manufacturing the polyester resin composition according to the present invention.

The polyester resin composition according to the present invention, as it is,
Alternatively, it can be used in various shapes such as sheet, plate, tube, hollow, and container.

The polyester film according to the present invention is produced from the polyester resin composition by a usual molding method. This polyester film may be an unstretched product or a stretched product.

In the case of an unstretched product, it is desirable that the thickness of the polyester film is usually 50 to 900 μm, preferably 200 to 600 μm.

In the case of a stretched product, there are a uniaxially stretched film and a biaxially stretched film. In a uniaxially stretched film, the stretching ratio is usually in the range of 1.1 to 10 times, preferably 1.2 to 8 times, and particularly preferably 1.5 to 7 times.

In the biaxially stretched film, the stretching ratio is usually 1.1 to 8 times, preferably 1.2 to 7 times, particularly preferably 1.5 to 6 times in the vertical direction, and usually 1.1 to 8 times in the horizontal direction.
It is desirable that the ratio be in the range of 1.2 times, preferably 1.2 times to 7 times, particularly preferably 1.5 times to 6 times.

To produce the polyester film according to the present invention,
Any conventionally known method can be adopted.
Generally, the polyester resin composition or a film-like material formed from the polyester resin composition further containing the additive as necessary is used as it is, or once cooled and solidified to a temperature equal to or lower than the glass transition point. Then, the original molded product may be stretched at a glass transition point or a melting point, preferably at a temperature in the range of about 80 ° C. higher than the glass transition point or the glass transition point. In order to heat-set the stretched film, an appropriate short-time heat treatment may be performed at the stretching temperature or higher.

To produce such a polyester stretched film, specifically, when the original molded product is a film-like material, a method of uniaxially stretching an unstretched film-like material (uniaxial stretching), After stretching in the horizontal direction (biaxial stretching), simultaneously stretching in the vertical and horizontal directions (biaxial stretching), and further sequentially in any one direction after biaxial stretching Examples of the method include a method of repeating stretching, a method of performing biaxial stretching and further stretching in both directions, and a so-called vacuum forming method of performing stretch forming by reducing the pressure between a film and a mold.

In addition, the polyester resin composition according to the present invention can be processed into a sheet according to the method for producing the polyester film.

The polyester preform according to the present invention is manufactured using the above-mentioned polyester resin composition.

For example, the polyester preform of the present invention can be obtained by injection molding the polyester resin composition.

The polyester container according to the present invention can be manufactured, for example, by press-molding a sheet made of the polyester resin composition, or by, for example, stretch blow-molding the polyester preform.

As the stretch blow molding method, the above preform is stretched in the longitudinal direction within the range of the stretching temperature in the composition, and then further blow molded to stretch in the horizontal axis direction (biaxial stretch blow molding). Method).

For example, in order to produce the polyester container of the present invention by a biaxial stretch blow molding method, one end of a bottomed parison molded by a usual injection molding machine or one end of a parison molded by an extrusion molding machine is bottomed. The obtained parison is a stretching temperature of the polyester resin composition of 90 to 14
At 0 ° C., 1.5 to 3.5 times, preferably 2 to 3 times, and 2 to 5 times, and preferably 2 to 5 times, in the longitudinal direction by blowing the rod and pressurized gas moving in the longitudinal direction in the blow molding die. Is 3 ~
A method of stretching by 4.5 times can be exemplified. The molding method by injection molding may be either a two-stage method using a cold parison or a one-stage method using a hot parison.

In the present invention, in order to improve the rigidity of the polyester container, a layer made of polyethylene terephthalate (A) may be laminated on the inner layer and the outer layer of the polyester resin composition layer.

The polyester container according to the present invention is particularly excellent in transparency and heat resistance and can be used for various applications. For example, it can be used as a container for seasonings, oils, alcoholic beverages, cosmetics, detergents, and the like. .

Effect of the Invention Since the polyester resin composition according to the present invention is composed of polyethylene terephthalate, polyethylene terephthalate, and a pre-kneaded material thereof as described above, it is extremely excellent in transparency, and furthermore, heat resistance such as hot water resistance, gas Excellent barrier properties.

Further, since the polyester film, polyester preform and polyester container according to the present invention are formed from the polyester resin composition as described above, they are remarkably excellent in transparency and heat resistance such as hot water resistance,
Excellent gas barrier properties.

EXAMPLES Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

Measurement method When measuring the carbon dioxide gas permeability, dry ice was sealed in a stretched hollow molded bottle at 23 ° C with the filling amount adjusted to an internal pressure of about 5 kg / cm ² , and then the bottle was heated at 23 ° C and 50% RH. Of the weight was measured in a constant temperature chamber of 7
The average permeation amount of carbon dioxide gas per day from the day to 21 days later (the carbon dioxide gas volume (cc) converted to 1 atm and 23 ° C.) was divided by the internal pressure (atm) immediately after the dry ice was enclosed.
The number of test bottles was three for each sample, and the average value was determined.

In addition, the gas barrier properties with thickness correction shall be evaluated by the carbon dioxide gas permeability coefficient. Using a PERMATRARC-IV carbon dioxide gas permeation tester made by NODERN CONTROL (USA), at 23 ° C and the relative humidity by the PERMATRAN method. Under a condition of 0%, a carbon dioxide gas permeability coefficient of a sample formed of a section at the center of the bottle body having a thickness of 300 to 450 μm was measured.

Transparency was measured by cutting the body of the bottle and using a haze meter NDH-20D manufactured by Nippon Denshoku Co., Ltd.
The haze of the test piece was measured three times by a method according to 003, and the average value was evaluated.

Hot water measurement method The hot water was measured by the following method.

First, the basis weight and the insertion amount of the bottle are measured at 23 ° C. and 50% RH. Next, put hot water adjusted to 95 ° C under the support ring, leave it for 10 minutes, put it in cold water, cool it down sufficiently in water (at least 1 hour), drain it, and then 1 day After leaving as above, the score was measured again, and the shrinkage (%) with respect to the original volume was determined. The measurement was performed three times under each condition, and the average value was obtained.

Example 1 Preparation of Prekneaded Material (C) 50 parts by weight of polyethylene terephthalate [[η] measured in o-chlorophenol at 25 ° C. is 0.80 (the same applies hereinafter), J1,35 manufactured by Mitsui Pet Resin Co., Ltd.) Polyethylene naphthalate resin 50 having the following physical properties obtained from 2,6-naphthalenedicarboxylic acid and ethylene glycol 50
After mixing with a weight part by a Henschel mixer, the mixture was melt-kneaded at 280 ° C. by an extruder to obtain pellets.

Polyethylene naphthalate resin: Intrinsic viscosity [η]: 0.6 dl / g Heating crystallization temperature (Tc): 180 ° C. Production of polyester resin composition, preform and container Next, it is used in the preparation of the above-mentioned pre-kneaded material. After mixing 80 parts by weight of the obtained polyethylene terephthalate, 20 parts by weight of polyethylene naphthalate, and 0.5 part by weight of lithium stearate with a Henschel mixer, the mixture was melt-kneaded at 280 ° C. by an extruder to obtain pellets.

The pellets were molded with a molding machine M-100A manufactured by Meiki Seisakusho Co., Ltd. to obtain a preform for bottle formation. The molding temperature at this time was 270 to 290 ° C.

Next, the preform obtained as described above is CORPOP
It was molded with a LAST-01 LB-01 molding machine to obtain a biaxially stretched bottle. The stretching temperature at this time was 90 to 140 ° C. The stretching ratio was 3.1 times in the vertical direction and 4.4 times in the horizontal direction. Table 1 shows the physical properties of the obtained bottle.

Examples 2-3 and Comparative Examples 1-4 In Example 1, the amounts of polyethylene terephthalate, polyethylene naphthalate and the pre-kneaded material (MB) used in the production of the polyester resin composition were as shown in Table 1. Except having changed, it carried out similarly to Example 1, and obtained the pellet of the polyester resin composition. Using the obtained pellets, a preform in the same manner as in Example 1,
A biaxially stretched bottle was obtained. Table 1 shows the physical properties of the obtained bottle (container).

Claims (5)

(57) [Claims] (1) Polyethylene terephthalate (A) 10 to 90
Parts by weight and (B) 90 to 10 parts by weight of polyethylene naphthalate
(C) Pre-kneaded product of 20 to 80% by weight of polyethylene terephthalate and 80 to 20% by weight of polyethylene naphthalate with respect to 100 parts by weight.
A polyester resin composition comprising 20 parts by weight. (2) Polyethylene terephthalate (A) 10 to 90
Parts by weight, (B) 90 to 10 parts by weight of polyethylene naphthalate, and (C) 20 to 80% by weight of polyethylene terephthalate and 80 to 20% by weight of polyethylene naphthalate are melt-kneaded with the pre-kneaded material described in (A) above. A) A method for producing a polyester resin composition, which comprises mixing 1 to 20 parts by weight with respect to 100 parts by weight of the total of component (B) and component (B). (3) Polyethylene terephthalate (A) 10 to 90
Parts by weight and (B) 90 to 10 parts by weight of polyethylene naphthalate
(C) Pre-kneaded product of 20 to 80% by weight of polyethylene terephthalate and 80 to 20% by weight of polyethylene naphthalate with respect to 100 parts by weight.
A film comprising a polyester resin composition comprising 20 parts by weight. (A) Polyethylene terephthalate 10-90
Parts by weight and (B) 90 to 10 parts by weight of polyethylene naphthalate
(C) Pre-kneaded product of 20 to 80% by weight of polyethylene terephthalate and 80 to 20% by weight of polyethylene naphthalate with respect to 100 parts by weight.
A preform comprising a polyester resin composition comprising 20 parts by weight. (5) Polyethylene terephthalate (A) 10 to 90
Parts by weight and (B) 90 to 10 parts by weight of polyethylene naphthalate
(C) Pre-kneaded product of 20 to 80% by weight of polyethylene terephthalate and 80 to 20% by weight of polyethylene naphthalate with respect to 100 parts by weight.
A container comprising a polyester resin composition comprising 20 parts by weight.