JPH02274757A - Polyester resin composition, its preparation, and its use - Google Patents

Abstract

PURPOSE:To prepare a polyester resin compsn. useful for producing a stretched bottle excellent in the transparency, heat resistance, and gas barrier properties by compounding polyethylene terephthalate, polyethylene naphthalate, and a premixture of polyethylene terephthalate with polyethylene naphthalate, each in a specified amt. CONSTITUTION:100 pts.wt. in total of 10 to 90 pts.wt. polyethylene terephthalate and 90 to 10 pts.wt. polyethylene naphthalate is compounded with 1 to 20 pts.wt. premixture of 20 to 80wt.% polyethylene terephthalate with 80 to 20wt.% polyethylene naphthalate.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a polyester resin composition, a method for producing the same, and uses of this composition, and more particularly, to a molded article such as a stretched bottle having excellent transparency, heat resistance, etc. The present invention relates to a polyester resin composition, a method for producing the same, and uses of the composition.

Technical Background of the Invention and Problems Thereto Conventionally, glass has been widely used as a material for containers for seasonings, oils, juices, carbonated drinks, beer, Japanese sake, cosmetics, detergents, and the like. However, since glass containers are expensive to manufacture, a method is generally adopted in which empty containers are collected after use and reused. In addition, glass containers are heavy, which increases shipping costs, and they also have drawbacks such as being easily damaged and inconvenient to handle.

In an attempt to overcome these drawbacks of glass containers, there has recently been a rapid shift from glass containers to various plastic containers. Various plastics are used as materials depending on the type of filling contents and the purpose of use. Among these plastic materials, saturated crystalline polyester resins such as polyethylene terephthalate have excellent mechanical strength, heat resistance, Because it has excellent transparency and gas barrier properties, it is used as a material for containers for juices, soft drinks, carbonated drinks, seasonings, detergents, cosmetics, etc. Among these uses, juices, soft drinks,
Blow-molded containers for filling carbonated beverages are required to be sterilized and filled at high temperatures, and therefore the blow-molded containers are required to be made of heat-resistant resin that can withstand high-temperature filling. All of these blow-molded containers for filling are required to have excellent transparency.

However, although saturated crystalline polyester resins such as polyethylene terephthalate are plastics with excellent transparency, further improvement in the aforementioned heat resistance has been desired.

Therefore, the present inventors conducted intensive research to improve the heat resistance of saturated crystalline polyester resins such as polyethylene terephthalate, and found that heat resistance could be improved by blending polyethylene naphthalate with polyethylene terephthalate. Ta.

However, polyethylene terephthalate and polyethylene naphthalate have poor compatibility, and simply blending the two results in whitening of the resulting blend.
There were problems in that it became opaque and did not have good stretchability.

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

Purpose of the Invention The present invention aims to solve the problems associated with the prior art as described above, and provides a polyester resin composition and its polyester resin composition that can be used to form stretched bottles with excellent transparency, heat resistance, etc. The purpose is to provide a manufacturing method.

Another object of the present invention is to provide films, preforms, and containers made of the above-mentioned polyester resin compositions.

Summary of the Invention The polyester resin composition according to the present invention contains a total of 100 parts by weight of (A) 10 to 90 parts by weight of polyethylene terephthalate and (B) 90 to 10 parts by weight of polyethylene naphthalate.
It is characterized in that (C) polyethylene terephthalate weighs 20 to 80% by weight and polyethylene naphthalate weighs 80 to 20% by weight.

The method for producing a polyester resin composition according to the present invention includes (
A) polyethylene terephthalate, (B) polyethylene naphthalate, and (C) polyethylene terephthalate are characterized by mixing a pre-kneaded product obtained by melt-kneading polyethylene naphthalate.

Furthermore, the polyester film, polyester preform, and polyester container according to the present invention are characterized by being made of the above-mentioned polyester resin composition.

The polyester resin composition according to the present invention is composed of specific amounts of polyethylene terephthalate and polyethylene naphthalate, and a pre-kneaded product thereof, as described above, so that it has excellent transparency, and has heat resistance such as hot water resistance. It also has excellent properties such as properties and gas barrier properties.

In addition, in the present invention, since the polyester resin composition is produced by the method described above, a polyester resin composition can be obtained which has extremely excellent transparency, and also has excellent heat resistance such as hot water resistance, gas barrier properties, etc. It will be done.

Moreover, since the polyester film, polyester preform, and polyester container according to the present invention are formed from the above-mentioned polyester resin composition,
It has excellent transparency, and also has excellent heat resistance such as hot water resistance and gas barrier properties.

DETAILED DESCRIPTION OF THE INVENTION The polyester resin composition of the present invention, its manufacturing method, and the uses of this composition will be specifically described below.

The polyester resin composition according to the present invention comprises polyethylene terephthalate (A) and polyethylene naphthalate (A).
In addition to B), it includes a pre-kneaded product (C) obtained by melt-kneading polyethylene terephthalate (A) and polyethylene naphthalate (B), but first, regarding polyethylene terephthalate (A) used as a raw material. explain.

Polyethylene terephthalate The polyethylene terephthalate used in the present invention is produced using terephthalic acid or its ester-forming derivative and ethylene glycol or its ester-forming derivative as raw materials. Acids and/or other glycols may also be copolymerized.

Examples of dicarboxylic acids used in copolymerization other than terephthalic acid include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, and diphenoxyethane dicarboxylic acid, adipic acid, sepacic acid, Examples include aliphatic dicarboxylic acids such as azelaic acid and decanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

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

Polyethylene terephthalate particularly preferably used in the present invention has the general formula [I] -(OOC-◇→ C00CII C1l →-
... [The content of the ethylene terephthalate component unit (a) represented by [■] is 95.0 to 98.6 mol%,
97.0 to 98.5 mol%, particularly preferably 97.3 to 98.5 mol%
The content of the dioxyethylene terephthalate component unit (b) represented by the general formula [] % formula % [] is in the range of 98.3 mol %, preferably 1.4 to 5.0 mol %.
．． It is desirable that the amount is in the range of 5 to 3.1 mol%, particularly preferably 1.7 to 2.6 mol%.

Polyethylene terephthalate has ethylene terephthalate component units (a) represented by the general formula [I] and dioxyethylene terephthalate component units (b) represented by the general formula [I] arranged randomly to form ester bonds. This forms a substantially linear polyester.

The fact that the polyethylene terephthalate is substantially linear is confirmed by dissolving the polyethylene terephthalate in 0-chlorophenol.

Polyethylene terephthalate (A) used in the present invention
The intrinsic viscosity [η] measured in 0-chlorophenol at 25°C is 0.60 to 1.00 dn/g, preferably 0.60 to 1.00 dn/g.
70 to 0.87 dA/g, particularly preferably 0.72 to 0
．． It is in the range of 85 dl 7g. If the intrinsic viscosity [η] is smaller than 0.60617 g, a blow-molded container with excellent heat resistance, transparency and mechanical strength cannot be obtained, and if it is larger than 1,00617 g, the moldability and stretching of the preform will be impaired. Blow moldability becomes poor. In addition, the intrinsic viscosity of polyethylene terephthalate [η]
is measured by the following method. That is, 1 g of sample polyethylene terephthalate was added to 0-chlorophenol.
/100ml, measure the solution viscosity at room temperature using an Ubbelohde capillary viscometer, then gradually add 0-chlorophenol, measure the solution viscosity on the low concentration side, and reduce the concentration to 0%. Extrapolate to find the limiting viscosity ([η]).

Further, the crystallization temperature (Tel) of polyethylene terephthalate when heated at a rate of 10°C/min using a differential scanning calorimeter (D SC) is 155.0°C or higher, preferably 167.0°C. 0 to 185°C, particularly preferably 16
It is desirable that the temperature is in the range of 8.0 to 180.0°C. In addition, the elevated temperature crystallization temperature (Tel) of this polyethylene terephthalate is in the range of the following formula % in relation to the intrinsic viscosity [η], and more preferably, 67,5 [77] +122.5≦ Tel≦67.5
[η]+128. )5 is desirable.

Elevated crystallization temperature of polyethylene terephthalate (Tcl
) is lower than 165.0°C, the transparency of the resulting blow-molded container decreases, the heat resistance also decreases, and thermal deformation occurs when filling soft drinks such as juice or cola at high temperature.

Furthermore, if the elevated temperature crystallization temperature (Tel) is lower than the lower limit value of the above formula, thermal deformation is likely to occur similarly when filling a soft drink such as juice or cola at a high temperature.

In addition, the elevated crystallization temperature of polyethylene terephthalate (
Tcl) is measured by the following method. That is,
A thin section of about 10 mm g of a sample from the center of a polyethylene terephthalate chip was dried using a PerkinElmer DS (Model 2 differential scanning calorimeter) at about 140 °C under a pressure of about 5 mm Hg for about 5 hours or more. is sealed in a nitrogen atmosphere in an aluminum pan for liquids.Measurement conditions are as follows: First, the temperature is rapidly raised from room temperature, melted and held at 290°C for 10 minutes, then rapidly cooled to room temperature, and then heated at 10°C/
The apex temperature of the exothermic peak detected when the temperature is raised at a heating rate of 10 minutes is determined.

The melting point (Tm) of polyethylene terephthalate is
It is indicated by the peak temperature of the endothermic peak when measured under the same conditions as the elevated temperature crystallization temperature (Tcl).

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

The polyethylene terephthalate used in the present invention can be produced, for example, by a direct polymerization method. Specifically, a mixture of terephthalic acid and ethylene glycol is continuously reacted in at least two esterification reaction steps to obtain a lower-order condensate, which is then continuously reacted in at least two liquid phase polycondensation steps. obtaining a polyester by polycondensation under reduced pressure; forming polyester chips from the polyester by melt extrusion; polycondensing the polyester chips in at least one solid phase polymerization step in an inert gas atmosphere; A method of increasing the limiting viscosity [η] is adopted.

Next, each step and its conditions will be explained.

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 polyethylene terephthalate fall within desired ranges.

Specifically, first, terephthalic acid and 1.02 to 1.4 mol, preferably 1.03 to 1 mol, per 1 mol of terephthalic acid.
．． An ethylene glycol slurry of terephthalic acid is formed from a mixture of 3 moles of ethylene glycol. The slurry is continuously fed to the esterification reaction step. The esterification reaction is carried out using an apparatus in which at least two esterification reactors are connected in series, under conditions where ethylene glycol is refluxed, and water produced by the reaction is removed from the system in a rectification column. . The reaction conditions for carrying out the esterification reaction are that the temperature of the first stage esterification reaction is usually 240 to 270°C, preferably 245 to 265°C, and the pressure is usually 0, 2 to 3 kg/cnfG, preferably 0. , 5-2 kg/cr1G, and the temperature of the final stage esterification reaction is usually 250-280°C.
Preferably the temperature is 255-275°C, and the pressure is usually 0-1
．． 5kg/crlG preferably O~1.3kg/cnf
It is G. Therefore, when the esterification reaction is carried out in two stages, the esterification reaction conditions in the first stage and the second stage are within the above-mentioned ranges, and when the esterification reaction is carried out in three or more stages, the esterification reaction conditions in the second stage are The reaction conditions for the esterification reaction from the second stage to one stage before the final stage are between the reaction conditions for the first stage and the reaction conditions for the final stage.

For example, when the esterification reaction is carried out in three stages, the reaction temperature of the second stage esterification reaction is usually 245
-275°C, preferably 250-270°C, and the pressure is usually 0-2kg/crlG, preferably 0.2-1.
, 5 kg/cnfG. The reaction rate of these esterification reactions is not particularly limited in each stage, but it is preferable that the increase and degree of esterification reaction rate in each stage is smoothly distributed, and furthermore, in the final stage of esterification. In the reaction product, it is usually desirable to reach 90% or more, preferably 93% or more. A lower condensate is obtained by these esterification steps, and the number average molecular weight of the lower condensate is usually 500 to 5,000.

The low-order condensate thus obtained is continuously supplied to a polycondensation reactor for the next liquid phase polycondensation step. Regarding the reaction conditions of the polycondensation reaction, the reaction temperature of the first stage polycondensation is usually
260-290°C, preferably 265-290°C, more preferably 270-285°C, and the pressure is usually 500°C.
-20 Torr, preferably 200-30 Torr, and the temperature of the final stage polycondensation reaction is usually 270-300 Torr.
℃ Preferably 275 to 295℃, and the pressure is usually 1
0 to 0.1 Tor+preferably 5 to 0.5 To+r.

When the polycondensation reaction is carried out in two stages, the polycondensation reaction conditions for the first stage and the second stage are within the above ranges, and when the polycondensation reaction is carried out in three or more stages, from the second stage The reaction conditions for the polycondensation reaction up to one stage before the final stage are between the reaction conditions for the first stage and the reaction conditions for the final stage. For example, if the polycondensation reaction is carried out in three stages, the second
The reaction temperature of the polycondensation reaction in the second step is usually 265-295°C, preferably 270-290°C, more preferably 270-295°C.
The temperature is 85° C. and the pressure is usually in the range of 50 to 2 Torr, preferably 40 to 5 Torr.

There is no particular limit to the intrinsic viscosity [η] reached in each of these polycondensation reaction steps, but it is preferable that the degree of increase in the intrinsic viscosity in each stage is distributed smoothly, and that The intrinsic viscosity [η] of polyethylene terephthalate obtained from the reactor is usually 0.55 to
0. 72 dA 7g preferably 0.57-0.68
It is in the range of dI/g. The polyethylene terephthalate thus obtained from the final polycondensation reactor is usually formed into chips by melt extrusion.

Furthermore, the polyethylene terephthalate chips are fed to a solid state polycondensation process. The solid phase polycondensation step consists of 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.
/cnfG ~10To++ preferably normal pressure to 10
The solid phase polycondensation reaction is carried out under the condition of 0To+r in an atmosphere of an inert gas such as nitrogen gas, argon gas, carbon dioxide gas, etc. 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 also be carried out in the coexistence of the polycondensation catalyst described below. , Tori n
- Tertiary amines such as butylamine, benzyldimethylamine, quaternary ammonium hydroxides such as tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, acetic acid When carried out by adding a small amount of a basic compound such as sodium,
This is preferred because the proportion of dioxyethylene terephthalate component units in the main chain of polyethylene terephthalate can be maintained at a relatively low level.

There are no particular restrictions on the method of adding these base component unit compounds, and they may be added to all of the esterification reactors, or they may be added to a specific reactor in the first stage or second stage or later. good. Further, the polycondensation reaction is preferably carried out in the presence of a catalyst and a stabilizer. Germanium compounds such as germanium dioxide, germanium tetraethoxide, germanium tetra n-butoxide as a catalyst,
Antimony catalysts such as antimony trioxide and titanium catalysts such as titanium tetrabutoxide can be used. Among these catalysts, germanium dioxide compounds are preferred because the produced polyethylene terephthalate has excellent hue and transparency. In addition, as stabilizers, phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, triphenyl phosphite, trisdodecyl phosphite, trisnonylphenyl Phosphite esters such as phosphite, acidic phosphate esters such as methyl arashido phosphate, isoprobil arashido phosphate, butyl arashido phosphate, dibutyl phosphate, monobutyl phosphate, dioctyl phosphate, phosphoric acid, polyphosphorus Phosphorus compounds such as acids are used. The proportion of these catalysts or stabilizers to be used is usually preferably 0.0005 to 0.2% by weight based on the weight of the metal in the catalyst, based on the weight of the mixture of terephthalic acid and ethylene glycol. is in the range of 0.001 to 0.05% by weight, and in the case of a stabilizer, it is usually 0.001 to 0.1% by weight, preferably 0.01% by weight, based on the weight of phosphorus atoms in the stabilizer.
The range is from 0.002 to 0.02% by weight. These catalysts and stabilizers can be supplied at the stage of the esterification reaction process, or can be supplied at the first stage of the polycondensation reaction process.
It can also be supplied to a stage reactor.

Polyethylene terephthalate as such a raw material is used in the form of pellets, and these pellets can take the form of strands, sheets, lumps, powders, and the like.

Pellets as such raw materials may be freshly prepared, or may be obtained by pulverizing pellets that have been formed into a parison or container, or a mixture thereof. It may be.

Polyethylene naphthalate The polyethylene naphthalate used in the present invention is 26
- It is desirable to contain ethylene-2,6-naphthalate units derived from naphthalene dicarboxylic acid and ethylene glycol in an amount of 60 mol% or more, preferably 80% or more, more preferably 90 mol% or more; , 6-naphthalate in an amount of less than 40 mol%.

Constituent units other than ethylene-26-naphthalate include terephthalic acid, isophthalic acid, 2,7-naphthalene dicarboxylic acid, 25-naphthalene dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, and 4,4'-diphenyl ether dicarboxylic acid. , 4,4'-diphenylsulfonedicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, aromatic dicarboxylic acids such as dibromoterephthalic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sepatic acid, decanedicarboxylic acid, etc. , alicyclic dicarboxylic acids such as 14-cyclopropanedicarboxylic acid, cyclopropanedicarboxylic acid, and hexahydroterephthalic acid; hydroxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid, and p-hydroxyethoxybenzoic acid; propylene glycol; Methylene glycol, diethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, neopentylene gelicol, p-xylene glycol, 14-cyclohexane dimetatool, bisphenol Asl', p-diphenoxysulfone, 1. 4-
Examples include structural units derived from bis(β-hydroxyethoxy)benzene, 2,2-bis(pβ-hydroxyethoxyphenyl)propane, polyalkylene glycol, p-phenylenebis(dimethylsiloxane), glycerin, and the like.

Furthermore, the polyethylene naphthalate used in the present invention contains a small amount, for example, 2 mol% or less, of a structural unit derived from a polyfunctional compound such as trimesic acid, trimethylolethane, trimethylolpropane, trimethylolmethane, or pentaerythritol. It's okay to stay.

Furthermore, the polyethylene naphthalate used in the present invention contains a small amount of a constituent unit derived from a monofunctional compound such as benzoylbenzoic acid, diphenylsulfone monocarboxylic acid, stearic acid, methoxypolyethylene glycol, or phenoxypolyethylene glycol, for example, in an amount of 2 mol% or less. may be included.

Such polyethylene naphthalate is substantially linear, which is confirmed by its dissolution in O-chlorophenol.

The intrinsic viscosity [η] of polyethylene naphthalate measured in 0-chlorophenol at 25°C is 0.2 to 1.1.
dA 7g, preferably in the range of 0.3 to 0.9 dI/g, particularly preferably in the range of 0.4 to 0.8 dl/g.

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

Additionally, a polyethylene naphthalate differential scanning calorimeter (
The temperature-raising crystallization temperature (Tc) when the temperature is raised at a rate of 10 °C/min with DSC) is 150 °C or higher, preferably 160 to 230 °C, particularly preferably 170 to 22 °C.
It is desirable that the temperature is in the range of 0°C.

In addition, the temperature-elevated crystallization temperature (T
c) is measured in the same way as for polyethylene terephthalate.

Note that polyethylene naphthalate as described above can be manufactured by a conventionally known manufacturing method.

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

As described above, the polyester resin composition according to the present invention contains not only polyethylene terephthalate (A) and polyethylene naphthalate (B) but also a pre-kneaded product (C
), it contains polyethylene terephthalate (A
) and polyethylene naphthalate (B), a polyester resin composition with excellent transparency and stretchability can be obtained.

To obtain such a pre-kneaded product, various known methods can be used. For example, polyethylene terephthalate (A) and polyethylene naphthalate (B) are mixed using a Henschel mixer, ■-blender, ribbon blender, tumbler blender, etc. After mixing, a method of melting and kneading with a screw extruder, twin screw extruder, Nigu, Banbury mixer, etc. can be mentioned. Further examples include methods of subsequent granulation or pulverization.

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

When obtaining such a pre-kneaded product, polyethylene terephthalate is used in the pre-kneaded product 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 60-40
Used in amounts of % by weight.

When polyethylene terephthalate and polyethylene naphthalate are used within the ranges described above, a polyester resin composition etc. can be obtained which has extremely excellent transparency, and is also excellent in heat resistance such as hot water resistance, gas barrier properties, etc.

Production of polyester resin composition The polyester resin composition according to the present invention can be obtained by mixing the above-mentioned polyethylene terephthalate (A), polyethylene naphthalate (B), and their pre-kneaded product (C). In this case, various known methods can be used. For example, polyethylene terephthalate (A), polyethylene naphthalate (B), and a pre-kneaded product (C) of these are mixed using a Henschel mixer, V-blender, ribbon blender, tumbler blender, etc. A method of mixing can be mentioned. Furthermore, after mixing in this way, - a screw extruder, a twin screw extruder, a kneader,
Examples include a method in which the mixture is melt-kneaded using a Banbury mixer or the like, and then granulated or pulverized.

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

When 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 8
in an amount of 0 to 20 parts by weight, and the sum of these (A+B
) 100 parts by weight, 20-80% by weight of polyethylene terephthalate and 80-2% by weight of polyethylene naphthalate
The pre-kneaded product (C) with 0% by weight is used in an amount of ~20 parts by weight, preferably 3 to 10 parts by weight.

When polyethylene terephthalate (A) is used in an amount of 1-0 to 90 parts by weight, moldability is excellent and the effect of improving gas barrier properties tends to be large.

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

Furthermore, when the pre-kneaded product (C) is used in an amount of 1 to 20 parts by weight with respect to the total of 100 parts by weight of the above (A) and (B), the effect of improving transparency is large and the molding There is a tendency for the quality to be excellent.

The polyester resin composition according to the present invention includes various compounding agents that are usually added to polyester, such as heat stabilizers, weather stabilizers, antistatic agents, lubricants, mold release agents, pigment dispersants, pigments, or dyes. can be added within a range that does not impair the purpose of the present invention. These compounding agents may be added when preparing the pre-kneaded material (C), or may be added when producing the polyester resin composition according to the present invention.

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

The polyester film according to the present invention is produced from the above-mentioned polyester resin composition by a normal molding method. Even if this polyester film is unstretched,
It may be a stretched product.

In the case of an unstretched product, the thickness of this polyester film is usually 50 to 900 μm, preferably 200 to 60 μm.
It is desirable that the thickness be 0 μm.

In the case of stretched products, there are -axially stretched films and biaxially stretched films. - In the case of an axially stretched film, it is desirable that the stretching ratio is usually in the range of 1.1 to 10 times, preferably 1.2 to 8 times, particularly preferably 1.5 to 7 times.

In addition, in a biaxially stretched film, the stretching ratio is usually in the range of 1.1 to 8 times in the vertical axis direction, preferably 1.2 to 7 times, particularly preferably 14.5 to 6 times, and in the horizontal direction. It is desirable that the amount is usually 1.1 to 8 times, preferably 1.2 to 7 times, particularly preferably 1.5 to 6 times.

In order to manufacture the polyester film according to the present invention, any conventionally known method can be employed. In general, a film-like product formed from the polyester resin composition or a polyester resin composition containing the additives as required is either left as it is or is solidified by cooling to a temperature below the glass transition point. Afterwards, the original molded product may be reheated and then stretched at a temperature ranging from the glass transition point to the melting point, preferably from the glass transition point to about 80° C. higher than the glass transition point. In order to heat set the stretched film, it may be heat-treated for an appropriate short time at the stretching temperature or a higher temperature.

To produce such polyester stretched film,
Specifically, when the original molded product is a film-like product,
A method of stretching an unstretched film-like material in the uniaxial direction (-axial stretching), a method of stretching in the vertical axis direction and then further stretching in the horizontal axis direction (biaxial stretching), a method of stretching in the vertical axis direction and the horizontal axis direction simultaneously Stretching method (biaxial stretching), method of repeating sequential stretching in any one direction after biaxial stretching, method of further stretching in both directions after biaxial stretching, space between film-like object and mold An example of this is the so-called vacuum forming method in which stretch forming is performed by reducing the pressure.

Note that the polyester resin composition according to the present invention can also be processed into a sheet shape according to the method for producing the polyester film described above.

The polyester preform according to the present invention is manufactured using the above 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 stretch-blow-molding the polyester preform.

As a stretch blow molding method, the above preform is stretched in the longitudinal direction within the stretching temperature range of the composition, and then further blow molded to stretch it in the transverse direction (biaxial stretch blow molding). law), etc.

For example, in order to manufacture the polyester container of the present invention using a biaxial stretch blow molding method, one end of a parison molded with a bottom is molded with a normal injection molding machine, or a parison molded with an extrusion molding machine is formed with a bottom. The obtained parison was stretched at a temperature of 90 to 1, which is the stretching temperature of the polyester resin composition.
At 40℃, the rod moving in the vertical direction within the blow molding mold and the blowing of pressurized gas are used to increase the temperature by 1.5 to 3.5 times in the vertical direction.
Examples include a method of stretching preferably 2 to 3 times and 2 to 5 times in the transverse direction, preferably 3 to 4.5 times. In addition, as a molding method using injection molding, cold
Either a two-stage method using a parison or a one-stage method using a hot parison may be used.

In addition, 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 has particularly excellent transparency and heat resistance, so it can be used for various purposes, for example, it can be used as a container for seasonings, oils, alcoholic beverages, cosmetics, detergents, etc. .

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

Moreover, since the polyester film, polyester preform, and polyester container according to the present invention are formed from the above-mentioned polyester resin composition,
It has excellent transparency, and also has excellent heat resistance such as hot water resistance and gas barrier properties.

[Examples] The present invention will be explained below using Examples, but the present invention is not limited to these Examples.

Measuring method: To measure carbon dioxide gas permeability, dry ice was filled in a stretched blow-molded bottle at 23°C with the amount adjusted so that the internal pressure was approximately 5 kg/crl, and then the bottle was placed at 23°C.
The weight was left in a constant temperature room at 50% RH to measure the change in weight over time, and the average amount of carbon dioxide gas permeated per day from 7 days to 21 days after sealing (the volume of carbon dioxide converted to 1 atm, 23°C) was calculated. Internal pressure (aim) immediately after filling CC)) with dry ice
Calculated by dividing by The number of test bottles was three for each sample, and the average value was determined.

In addition, the gas barrier property with thickness correction is evaluated using the carbon dioxide permeability coefficient.
Carbon dioxide permeation tester PERMATRA manufactured by OL (USA)
Using the RI-IV type, the thickness is 300 to 450 using the PERMATRAN method at a temperature of 23°C and relative humidity of 0%.
The carbon dioxide gas permeability coefficient of a sample consisting of a section at the center of the bottle body of μm was measured.

In addition, the transparency is achieved by cutting the body of the bottle, making it a Japanese heavy color.
manufactured by ASTM, using a haze meter NDH-20D.
The haze value of the test piece was measured three times using a method similar to D 1G03, and the average value was used for evaluation.

Hot water resistance measurement method The heat-resistant water was measured by the following method.

First, the basis weight and filling of the bottle are measured at 23° C. and 50% RH. Next, support the hot water controlled at 95℃.
Put it under the ring, leave it for 10 minutes, then put it in cold water, cool it thoroughly in water (for at least 1 hour), drain the water, leave it for at least 1 day, then measure the hole again, and then put it in cold water. The shrinkage rate (%) with respect to the volume was determined. Measurements were performed three times under each condition, and the average value was taken as the average value.

Example 1 Preparation of pre-kneaded product (C) Polyethylene terephthalate [[η] measured at 25°C in 0-chlorophenol is 0.80 (the same applies hereinafter), Jl
, 35 Mitsui Pet Resin ■] and 50 parts by weight of a polyethylene naphthalate resin obtained from 26-naphthalene dicarboxylic acid and ethylene glycol and having the following physical properties were mixed in a Henschel mixer, and then
The mixture was melt-kneaded using an extruder at 280°C to obtain pellets.

Polyethylene naphthalate resin: Intrinsic viscosity [η: 0.6 dl/g Elevated crystallization temperature (Tc): 180°C Production of polyester resin composition, preform and container Next, during the preparation of the above-mentioned pre-kneaded product 80 parts by weight of polyethylene terephthalate, 20 parts by weight of polyethylene naphthalate, and 0.0 parts by weight of lithium stearate were used.
After mixing with 5 parts by weight using a Henschel mixer, the mixture was melt-kneaded using an extruder at 280°C to obtain pellets.

This pellet was molded using a molding machine M100A manufactured by Meiki Manufacturing Co., Ltd. to obtain a preform for forming a bottle. The molding temperature at this time was 270 to 290°C.

Next, the preform obtained as described above is CoRP
A biaxially stretched bottle was obtained by molding using a B-01 molding machine manufactured by OPLAST. The stretching temperature at this time was 90 to 140°C. In addition, the stretching ratio in the longitudinal direction is 3.1 times,
The horizontal direction was 4.4 times. Table 1 shows the physical properties of the obtained bottle.

Examples 2 to 3 and Comparative Examples 1 to 4 In Example 1, the blending amounts of polyethylene terephthalate, polyethylene naphthalate, and pre-kneaded material (Mu) used in the production of the polyester resin composition were as shown in Table 1. Pellets of a polyester resin composition were obtained in the same manner as in Example 1 except for the following changes. Using the obtained pellets, a preform was prepared 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)

[Claims] (1) For a total of 100 parts by weight of (A) 10 to 90 parts by weight of polyethylene terephthalate and (B) 90 to 10 parts by weight of polyethylene naphthalate, (C) 20 to 80 parts by weight of polyethylene terephthalate and polyethylene naphthalate. A polyester resin composition comprising 1 to 20 parts by weight of a pre-kneaded material with 80 to 20% by weight. (2) A polyester resin composition characterized by mixing a pre-kneaded product obtained by melt-kneading (A) polyethylene terephthalate, (B) polyethylene naphthalate, and (C) polyethylene terephthalate and polyethylene naphthalate. Production method. (3) For a total of 100 parts by weight of (A) 10 to 90 parts by weight of polyethylene terephthalate and (B) 90 to 10 parts by weight of polyethylene naphthalate, (C) 20 to 80 parts by weight of polyethylene terephthalate and polyethylene naphthalate. A film comprising a polyester resin composition comprising 1 to 20 parts by weight of a pre-kneaded material with 80 to 20% by weight. (4) (A) 10 to 90 parts by weight of polyethylene terephthalate and (B) 90 to 10 parts by weight of polyethylene naphthalate (C) 20 to 80 parts by weight of polyethylene terephthalate and polyethylene naphthalate A preform comprising a polyester resin composition comprising 1 to 20 parts by weight of a pre-kneaded material with 80 to 20% by weight. (5) For a total of 100 parts by weight of (A) 10 to 90 parts by weight of polyethylene terephthalate and (B) 90 to 10 parts by weight of polyethylene naphthalate, (C) 80 to 20 parts by weight of polyethylene terephthalate and polyethylene naphthalate. A container comprising a polyester resin composition comprising 1 to 20 parts by weight of a pre-kneaded material with 20 to 80% by weight.