KR100503991B1 - Heat-shrinkable polyester film and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a polyester heat-shrinkable film, the polyester heat-shrinkable film of the present invention is 10 to 30 mol% repeating units of trimethylene terephthalate, 2,2-dimethyl (-1,3-propylene) Terephthalate repeating unit containing 5 to 20 mol% and the remaining amount of ethylene terephthalate, characterized in that it comprises 5 to 25% by weight of a white inorganic pigment based on the total weight. The heat-shrinkable polyester film according to the present invention is not only excellent in basic properties such as heat resistance, chemical resistance, mechanical properties, printing properties, but also excellent in whiteness and heat shrinkage properties, and is useful for labeling or coating of containers.

Description

Heat-shrinkable polyester film and method for manufacturing the same

The present invention relates to a heat-shrinkable polyester film, and more particularly, not only excellent basic properties such as heat resistance, chemical resistance, mechanical properties, printing characteristics, but also excellent in whiteness and heat shrinkage characteristics, and thus, can be used for labeling or The present invention relates to a heat-shrinkable polyester film useful for taking doses and a method for producing the same.

Heat-shrinkable films are used not only for labeling plastics, glass bottles, batteries or electrolytic capacitors, but also for the overall coating of packaging containers, and are used for various purposes such as packing or tightly packing stationery or several containers. As such heat-shrinkable films, not only films such as polyvinyl chloride and polystyrene, but also polyester films have been used in recent years.

In order to use the heat-shrinkable film for various packaging materials or labels, not only basic properties such as heat resistance, chemical resistance, weather resistance, and printing characteristics, but also excellent heat shrinkage properties such as sealing property and shrinkage uniformity are required.

However, in the case of polyvinyl chloride or polystyrene heat-shrinkable film, which is widely used as a conventional heat-shrink film material, there is a problem that heat resistance, chemical resistance, weather resistance, and heat shrinkage characteristics are not sufficient. In particular, the polyvinyl chloride heat-shrinkable film contains a chlorine component, so the environmental friendliness of the incineration waste is very poor. Since polystyrene film is poor in printability, it is impossible to use ink for general plastic film, so it is necessary to use special ink, and it is difficult to store because of its high natural shrinkage rate, and it causes problems such as poor printing in the printing process. have.

Heat-shrinkable polyester film generally used is polyethylene terephthalate, which has excellent heat resistance, chemical resistance, weather resistance, and sufficient shrinkage.However, due to its high shrinkage stress and shrinkage rate, various problems occur when directly labeling the container or overall coating. do. In other words, if the shrinkage rate of the heat shrinkable film is too large, shrinkage unevenness occurs due to temperature irregularity in the shrinking tunnel or temperature deviation of the surface of the container, which causes distortion of the printed image and lowers the value of the product.

In addition, in recent years, a quadrilateral container has been used a lot to reduce the storage space. When a conventional polyester-based heat shrinkable film is used as the shrink label of the quadrangular container, the shrinkage stress in the vertical direction with respect to the main shrinkage direction and Since the shrinkage rate is high, end shrinkage phenomenon in which the edge of the label 11 is bowed due to the difference in shrinkage rate at the angled and flat portions after shrink labeling in the quadrangular container 10 as shown in FIG. ) Will cause the printed image to be distorted and the appearance will be poor.

In addition, it is sufficient to have a shrinkage of 30% or more in hot water at 80 ° C. for partial labeling, but high heat shrinkage is required at low temperatures, especially when the contents may deteriorate at high temperatures such as the entire coating of draft beer bottles. It is difficult to obtain sufficient low temperature heat shrinkage rate with the conventional polyester type heat shrinkable film.

In Japanese Patent Laid-Open Nos. 63-139725, 7-53416, 7-53737, 7-216107, 7-216109, 9-254257 and the like, polyethylene terephthalate or polybutylene terephthalate is blended at a constant ratio. In addition, it has been proposed that copolymerization of dicarboxylic acid components of terephthalic acid and isophthalic acid with diol components of ethylene glycol and 1,4-cyclohexanedimethanol can improve shrinkage uniformity by controlling the shrinkage rate. However, according to the above document, although it is effective in improving the shrinkage uniformity, the shrinkage in the main contraction direction is not sufficient to be used for the overall coating of the container, and the contraction rate in the vertical direction with respect to the main contraction direction is large, so that When labeling, there is a problem in that the appearance of the label is poor because the end action is severe.

In addition, in order to improve end play, Japanese Patent Laid-Open Nos. 9-239834 and 10-77335 use copolyesters such as neopentyl glycol [2,2-dimethyl (-1,3-propane) diol] as raw materials. As a method of controlling the shrinkage speed or heat treatment while stretching after stretching, it is proposed to improve the end slid phenomenon in the vertical direction. However, according to the above document, it is difficult to obtain a sufficient improvement effect in the end sliding phenomenon because the shrinkage stress in the vertical direction to the main contraction direction is too large, and the thermal contraction rate in the main contraction direction to be used for the entire coating of the container Not enough Therefore, referring to FIG. 2, since the adhesion of the shrink film 21 to the bottle cap portion 22 of the glass bottle 20 is not sufficient, not only the appearance is poor, but the sealing is not perfect, and contaminants from the outside are prevented. There is a problem of inflow.

Therefore, the technical problem to be solved by the present invention is to solve the above problems, not only excellent basic properties such as heat resistance, chemical resistance, mechanical properties, printing characteristics, but also excellent in whiteness and heat shrinkage characteristics, especially for labeling or whole skin of various containers It is to provide a heat shrinkable polyester film useful as a dose.

Another object of the present invention is to provide a method for producing the heat-shrinkable polyester film.

In order to achieve the above technical problem, the present invention provides 10 to 30 mol% of trimethylene terephthalate repeating units and 2 to 2-dimethyl (-1,3-propylene) terephthalate repeating units based on the total constituents. And it contains a residual amount of ethylene terephthalate, and provides a heat shrinkable polyester film comprising 5 to 25% by weight of a white inorganic pigment based on the total weight.

The heat-shrinkable polyester film has a sulfonic acid metal salt derivative represented by R1-SO ₃ Me (wherein R1 is an alkyl group having 5 to 20 carbon atoms and Me is an alkaline earth metal or an alkali metal) in order to improve the antistatic property, 0.02 relative to the film. It is preferable to further comprise from 0.8% by weight.

In order to achieve the above technical problem, the present invention provides a) polyethylene terephthalate, polytrimethylene terephthalate and dicarboxylic acid as terephthalic acid or dimethyl terephthalate and diol as ethylene glycol and 2,2-dimethyl (-1,3). Blending 2,2-dimethyl (-1,3-propane) diol copolymerized polyester obtained by copolymerizing -propane) diol to obtain a polyester resin mixture; b) mixing a white inorganic pigment into the polyester resin mixture; c) manufacturing a melt sheet by extrusion molding the polyester resin mixture mixed with the white inorganic pigment; d) cooling and solidifying the melt sheet to produce a cooled and solidified sheet; And e) stretching the cooled and solidified sheet, and 10 to 30 mole% of trimethylene terephthalate repeating units, 2,2-dimethyl (-1,3-propylene), based on the total constituents. Provided is a method for producing a heat-shrinkable polyester film containing 5 to 20 mol% of terephthalate repeating units and a residual amount of ethylene terephthalate and 5 to 25 weight% of a white inorganic pigment based on the total weight of the film.

Hereinafter, a heat shrinkable polyester film and a method of manufacturing the same according to the present invention will be described in more detail.

The present invention, 10 to 30 mol% of trimethylene terephthalate repeating units represented by the following formula (1), 2,2-dimethyl (-1,3-propylene) terephthalate repeating units represented by the formula (2) It provides 5 to 20 mol% and the remaining amount of ethylene terephthalate represented by the following formula (3), and provides a heat-shrinkable polyester film comprising 5 to 25% by weight of a white inorganic pigment based on the total weight of the film do.

In Formula 1, n is a positive integer.

In Formula 2, n is a positive integer.

In Formula 3, n is a positive integer.

In general, the heat shrinkage characteristic of the polyester film is caused by the amorphousness of the polyester molecular chain itself, the 2,2-dimethyl (-1,3-propylene) terephthalate repeating unit of the polyester film according to the present invention is a polyester molecule By contributing to increasing the amorphousness of the whole chain, it gives the film sufficient heat shrinkability. In addition, since the 2,2-dimethyl (-1,3-propylene) terephthalate repeating unit has a branched molecular structure, the 2,2-dimethyl (-1,3-propylene) terephthalate repeating unit has a branched molecular structure, thereby increasing the mechanical properties in the stretching direction and the vertical direction of the uniaxially stretched polyester film. It is possible to prevent the layer cracking phenomenon appearing in the uniaxial polyester film. Therefore, uniaxial stretching of sufficient magnification is possible. In addition, the trimethylene terephthalate repeating unit improves the printability by increasing the surface adhesion of the film and improves the stretching characteristics during the film manufacturing process.

In order to impart all of the above desirable properties to the film, the content of 2,2-dimethyl (-1,3-propylene) terephthalate repeating unit and trimethylene terephthalate repeating unit is 5-20 mol% and 10, respectively, based on the total constituents. It is preferable that it is to 30 mol%. When the content of the 2,2-dimethyl (-1,3-propylene) terephthalate repeating unit and the trimethylene terephthalate repeating unit is less than 5 mol% and 10 mol%, respectively, the above characteristics cannot be sufficiently imparted to the film. When the content of, 2-dimethyl (-1,3-propylene) terephthalate repeating unit and trimethylene terephthalate repeating unit exceeds 20 mol% and 30 mol%, respectively, the relatively low content of ethylene terephthalate repeating unit is reduced. Not only does the cost increase, but there is a problem that the mechanical properties and heat resistance are lowered.

In the present invention, in addition to the components described above, other components may be included within a range that does not affect the polyester-based heat shrink film properties of the present invention. For example, an isophthalate component may be included instead of the terephthalate component of the present invention. In addition, isophthalic acid or its esterified product, 2,6-naphthalenedicarboxylic acid or its esterified product, as an acid component of polyester, Diethylene glycol as a dicarboxylic acid and diol component such as sebacic acid, adipic acid, 5-sodium sulfisoisophthalic acid, trimellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, pimeric acid, azelaic acid and pyromellitic acid Polyhydric alcohol components such as diol, xylene glycol, butanediol, 1,4-cyclohexanedimethanol, triethylene glycol and polytetramethylene glycol of hexanediol and 2,2 (4-oxyphenol) propane derivatives can be used. Do.

In addition, the heat-shrinkable polyester film according to the present invention comprises 5 to 25% by weight of a white inorganic pigment based on the total weight of the film. If the inorganic pigment content is less than 5% by weight, the whiteness and hiding power of the polyester film is not sufficient, and if it exceeds 25% by weight, the mechanical properties of the polyester film are lowered and the film manufacturing process, especially the stretching process, becomes unstable. Production of film of one thickness becomes difficult. The white inorganic pigment is preferably at least one inorganic pigment selected from the group consisting of titanium oxide, barium sulfide and calcium carbonate.

The heat-shrinkable polyester film of the present invention has a sulfonic acid metal salt derivative represented by R 1 -SO ₃ Me (wherein R 1 is an alkyl group having 5 to 20 carbon atoms and Me is an alkaline earth metal or an alkali metal) relative to the polyester film. To 0.8% by weight may be further included. Since the surface resistance of a conventional polyester film is 1 × 10 ¹⁵ kPa or more, products shrink-wrapped with such a film are easily contaminated with dust or foreign matters, resulting in deterioration of product value. Coating the antistatic agent on the film as a method for preventing the contamination of the film is not preferable because the shrinkage of the film in advance during the heat treatment process during the coating process is poor heat shrinkage characteristics. Therefore, in the present invention, the sulfonic acid metal salt derivative is mixed with the polyester film so as not to affect the heat shrinkage characteristic of the film.

The content of the sulfonic acid metal salt derivative contained in the polyester film of the present invention is preferably 0.01% to 0.8% by weight relative to the polyester film, by adding a sulfonic acid metal salt derivative in this range of the decomposition and mechanical properties of the polyester film The antistatic property of a polyester film can be improved so that the specific resistance of a polyester film surface may be 2x10 <^13> Pa or less, without deterioration. The sulfonic acid metal salt derivative may be an acid value of 1.0 mgKOH / g or less, and may be used, such as sodium olylbenzenesulfonate, potassium nonylbenzenesulfonate, potassium undecylbenzenesulfonate, and the like. It is preferred that it is a metal selected from the group consisting of magnesium.

The heat-shrinkable polyester film of the present invention has a whiteness of 80% or more based on ASTM E313, a light transmittance of 40 μm thick film of 40% or less based on ASTM D1003, and a surface of the film for nitrocellulose-based ink. Adhesiveness is at least 5B based on ASTM D3359. Shrinkage in the main shrinkage direction is 40% or more in 80 ℃ hot water, and shrinkage in the vertical direction to the main shrinkage direction is less than 5%. Since it is a white opaque film, it can have a beautiful appearance by a simple printing process of 1 to 3 degrees without going through complicated gravure printing of 5 degrees or more. Ink adhesion is good and it has excellent printability. In addition, the end shrinkage phenomenon is minimized because the shrinkage in the main contraction direction is greater than 40% and the shrinkage in the vertical direction is small in hot water at 80 ° C.

In order to achieve the above technical problem, the present invention provides a) polyethylene terephthalate, polytrimethylene terephthalate and dicarboxylic acid as terephthalic acid or dimethyl terephthalate and diol as ethylene glycol and 2,2-dimethyl (-1,3). Blending 2,2-dimethyl (-1,3-propane) diol copolymerized polyester obtained by copolymerizing -propane) diol to obtain a polyester resin mixture; b) mixing a white inorganic pigment into the polyester resin mixture; c) manufacturing a melt sheet by extrusion molding the polyester resin mixture mixed with the white inorganic pigment; d) cooling and solidifying the melt sheet to produce a cooled and solidified sheet; And e) stretching the cooled and solidified sheet, and 10 to 30 mole% of trimethylene terephthalate repeating units, 2,2-dimethyl (-1,3-propylene), based on the total constituents. Provided is a method for producing a heat-shrinkable polyester film containing 5 to 20 mol% of terephthalate repeating units and a residual amount of ethylene terephthalate and 5 to 25 weight% of a white inorganic pigment based on the total weight of the film.

In order to introduce the 2,2-dimethyl (-1,3-propylene) terephthalate repeating unit of the above content into the heat-shrinkable polyester film according to the present invention, terephthalic acid or dimethyl terephthalate as a dicarboxylic acid component, and a diol component It is preferable to blend 2,2-dimethyl (-1,3-propane) diol copolymerized polyester having a structure of formula (4) obtained by copolymerizing ethylene glycol and 2,2-dimethyl (-1,3-propane) diol. Do.

In Formula 4, n and m are positive integers.

The intrinsic viscosity of the 2,2-dimethyl (-1,3-propane) diol copolymerized polyester is 0.5 to 0.8. The content of the dimethyl (-1,3-propylene) terephthalate repeating unit of the 2,2-dimethyl (-1,3-propane) diol copolymerized polyester is preferably 7 to 30 mol%. If it is less than 7 mol%, a film having sufficient heat shrinkage characteristics cannot be obtained. If it is more than 30 mol%, it is difficult to increase the degree of polymerization, and the copolymerization degree is excessively high, resulting in excessively high amorphousness, thereby preventing fusion problems during drying. It is difficult to precrystallize to make it, and to dry for a long time at low temperature. In addition, the melt-extruder also has a problem that must be used equipment specially designed for amorphous polymers.

In addition, in the method for producing a heat-shrinkable polyester film according to the present invention, the intrinsic viscosity of polyethylene terephthalate and polytrimethylene terephthalate is preferably 0.5 to 0.8 and 0.6 to 1.0, respectively.

On the other hand, when terephthalic acid and dimethyl terephthalate as dicarboxylic acid components and ethylene glycol, 1,3-propanediol and 2,2-dimethyl (-1,3-propane) diol are copolymerized together, trimethylene terephthalate is repeated. Since the properties of the unit and the dimethyl (-1,3-propylene) terephthalate repeating unit cannot be sufficiently utilized, the heat shrinkage properties aimed at in the present invention cannot be sufficiently obtained, and the degree of copolymerization becomes large and the amorphousness becomes excessively high. In order to prevent the fusion problem during drying, it is difficult to pre-crystallize and to dry for a long time at low temperature, and the melt extruder also has to use a device specially designed for the amorphous polymer.

Various polyesters constituting the heat-shrinkable polyester film can be synthesized through a known method, for example, a direct ester method or a transesterification reaction method.

The heat shrinkable polyester-based mixture constituting the film of the present invention may include various additives necessary for the production of the polyester film. For example, spherical silica, gel-type silica, alumina, kaolin, calcium carbonate, or the like may be added to improve the running property of the film in preparing the polymers.

In the present invention, the heat-shrinkable polyester film is a mixture of a white inorganic pigment in a mixture consisting of the 1,3-propanediol copolymer polyester and dimethyl (-1,3-propylene) terephthalate copolymer polyester, According to a conventional method is prepared by the extrusion molding → cooling solidification → monoaxial or biaxial stretching step, and if necessary, the final heat setting step is completed, which will be described in detail.

First, the mixture and the white inorganic pigment are kneaded well, and then extruded to form a melt sheet. In the extrusion molding, the hot melt of the mixture is usually carried out using an extrusion molding machine, but in some cases, the molding may be carried out in a softened state without heating the melt. The extruder used herein may be a single screw extruder, a biaxial coaxial or two-way extruder, but it is preferable to use a single screw extruder having a high kneading property for uniformity of physical properties. In such an extruder, a melt sheet obtained by melting and kneading the mixture is extruded through a die to obtain a melt sheet. Examples of dies used are T-dies and circular rings.

Subsequently, a solidified sheet is prepared by rapid cooling the melt sheet extruded from the die. Such cooling and solidification is preferably performed using a metal roll using a refrigerant such as gas or liquid. In the case of using a metal roll, it is possible to obtain an effect of making the sheet thickness uniform and improving surface characteristics. It is preferable to perform cooling solidification in the state with comparatively little orientation.

Subsequently, the cooling-solidified sheet is simultaneously or sequentially stretched on at least one axis, and in order to increase the uniformity of the thickness, it is preferable to perform the successive stretching.

According to one embodiment of the present invention, the film primarily drawn in the longitudinal direction is stretched in the transverse direction, that is, in a 90 ° direction with respect to the film running direction, if necessary. The stretching method is not particularly limited as long as it is a method commonly used in the art. Among them, tenter transverse stretching is the most typical stretching method. Specifically, both ends of the film being driven are fixed with clips running continuously, and the fixed state is gradually increased by increasing the distance between the clips at both ends in a suitable temperature atmosphere. It is a stretching method to perform.

Since the heat-shrinkable polyester film according to the present invention has good stretching properties, such a tenter method can be applied as it is, and thus a film having excellent stretch uniformity and thickness uniformity can be produced. Therefore, when it is used as a packaging material or label of various containers, it has a beautiful appearance due to the uniform shrinkage property.

In addition, the stretching method to be used is various, such as a method using gas pressure, a method by rolling, etc., and these may be appropriately selected or combined.

Heat-setting is performed as needed in order to adjust the thermal contraction rate with respect to the film obtained by extending | stretching on such conditions. For example, it is preferable to carry out for 10 to 30 seconds at 80 to 100 ° C. in the stretched state, relaxed state or limited shrinkage state of the stretched film after stretching. The heat setting temperature most suitable for the film may vary depending on the speed of the film passing through the heat treatment section, that is, the treatment time.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, it is a matter of course that the scope of the present invention is not limited to the following examples.

Production Example

100 mole parts of dimethyl terephthalate and 180 mole parts of ethylene glycol were added to an autoclave equipped with a distillation machine. At 150 ° C., manganese acetate was added 0.05% by weight of dimethyl terephthalate as a transesterification catalyst, and then methanol was removed. Reaction was advanced, heating up to 220 degreeC for minutes. After the transesterification reaction, 0.045% by weight of trimethyl phosphate was added to dimethyl terephthalate as a stabilizer, and 0.03% by weight of antimony trioxide was added to the polymerization catalyst after 10 minutes. Subsequently, after 5 minutes, the mixture was transferred to a second reactor equipped with a vacuum equipment, and then polymerized at 280 ° C. for about 140 minutes to obtain a homopolymer (A) of polyethylene terephthalate having an intrinsic viscosity of 0.62.

Polymerization was carried out in the same manner as the homopolymer (A) of polyethylene terephthalate, except that trimethylene glycol was used instead of ethylene glycol as a diol component, thereby obtaining a polytrimethylene terephthalate homopolymer (B) having an intrinsic viscosity of 0.85. Got it.

In addition, 90 mol parts of ethylene glycol instead of 180 mol parts of ethylene glycol as the diol component, and 2,

Polymerization was carried out in the same manner as the homopolymer (A) of polyethylene terephthalate, except that 90 mol part of 2-dimethyl (-1,3-propane) diol) was used, and an intrinsic viscosity of 0.64 was 2,2-dimethyl. (-1,3-propane) diol copolymer polyester (C) was obtained.

In addition, a titanium oxide master chip (D) was prepared by mixing the homopolymer (A) of the polyethylene terephthalate prepared above and titanium oxide (average particle diameter: 0.5 μm) having an anatase crystal structure in a weight ratio of 1: 1.

Examples 1-9 and Comparative Examples 1-6

Polyethylene terephthalate homopolymer (A), polytrimethylene terephthalate homopolymer (B), 2,2-dimethyl (-1,3-propane) diol copolymerized polyester (C) and titanium oxide produced by the above method After drying the master chip (D) to a moisture content of 0.05% by weight or less using a vacuum dryer, A, B, C and D were mixed in the composition ratio as shown in Table 1. Ethylene terephthalate repeating unit (A '), trimethylene terephthalate repeating unit (B') and dimethyl (-1,3-propylene) terephthalate repeating unit constituting the mixed polyester according to the examples and comparative examples of Table 1 The content of (C ′) is analyzed and shown in Table 2.

Subsequently, the mixed polyester was melt-extruded at 280 ° C. and cooled on a casting roll maintained at 30 ° C. to obtain an amorphous sheet. The amorphous sheet thus obtained was continuously stretched 3.5 times in a tenter to obtain a uniaxially stretched heat shrinkable polyester film having a thickness of 40 µm.

Examples 10-12 and Comparative Examples 7-8

Potassium oltylbenzenesulfonate master chip (E) was prepared by mixing 3 wt% of potassium olylbenzenesulfonate powder in the homopolymer (A) of the polyethylene terephthalate prepared above.

A homopolymer (A), a polytrimethylene terephthalate homopolymer (B), and 2,2-dimethyl (-1,3) of the thus-produced olylbenzenesulfonate master chip (E) and the polyethylene terephthalate prepared from the preparation examples. -Propane) diol copolymerized polyester (C) and titanium oxide master chip (D) was dried to a moisture content of 0.05% by weight or less using a vacuum dryer, and then A, B, C, D and the composition ratio as shown in Table 1 E was mixed. The mixed polyesters according to Examples 10 to 12 and Comparative Examples 3 and 4 of Table 1 are shown in Table 2 by analyzing the content of the components.

In Table 1, A, B, C, D and E are polyethylene terephthalate, polytrimethylene terephthalate, 2,2-dimethyl (-1,3-propane) diol copolyester, homopolymer of polyethylene terephthalate, respectively. Titanium oxide master chip containing (A) and titanium oxide in a weight ratio of 1: 1 and a homopolymer of polyethylene terephthalate (A). Is ethylene glycol and DMPG refers to 2,2-dimethyl (-1,3-propane) diol.

In Table 2, the repeating units A ', B' and C 'refer to ethylene terephthalate, trimethylene terephthalate and dimethyl (-1,3-propylene) terephthalate repeating units, respectively, OBSK refers to potassium ylbenzenesulfonate , TiO2 and OBSK content is based on the total weight of the film.

 Various performance evaluations of the films prepared according to the Examples and Comparative Examples were carried out as follows, and the results are shown in Table 3.

(1) whiteness

It was measured according to ASTM E313-96.

(2) light transmittance

It measured according to ASTM D1003 (diameter 25MM, scattering angle 2.5 degree).

(3) adhesion to nitrocellulose inks

It was measured according to ASTM D3359-83.

(4) breaking strength

For samples prepared with the film having a length of 10 cm and a width of 15 mm, the breaking strength in the main shrinkage direction and the vertical direction of the film was measured using UTM at room temperature.

(5) heat shrinkage

The prepared film was cut into a width of 15 mm and a length of 200 mm and then heat treated for 10 seconds in hot water maintained at 80 ° C., and then the length before and after the heat treatment was measured and calculated by the following equation.

Thermal Shrinkage (%) = [(L- ) / L] × 100

Where L is the length of the film before heat treatment, Is the length of the film after heat treatment.

(6) natural shrinkage

After the prepared film was cut into a width of 15 mm and a length of 200 mm and left for 7 days in an oven maintained at 40 ° C., the length before and after standing was measured, and the natural shrinkage was calculated by the same formula as the thermal shrinkage.

(7) surface resistivity

The surface resistivity of the surface was measured using an insulation resistance measuring device of the US Hewlett, at a temperature of 20 ° C., RH 65% and an applied voltage of 500V.

(8) appearance of film

The appearance of the film shrink | contracted 30% in the vertical direction of the main contraction direction in 80 degreeC warm water was visually judged.

◎: Good appearance (no wrinkles or cloudy appearance)

×: Poor appearance (wrinkles and turbidity)

In Table 3, MD and TD refer to shrinkage in the main shrinkage direction (transverse direction) and its vertical direction (longitudinal direction) of the film in 80 ° C. hot water, respectively, and NC refers to nitrocellulose-based ink.

Referring to Table 3, it can be seen that the heat-shrinkable polyester film of Examples 1 to 9 prepared according to the present invention has all good properties such as whiteness, light transmittance, ink adhesion, mechanical properties, shrinkage properties, and appearance. have.

On the other hand, in the heat-shrinkable polyester film of the present invention, when the content of the trimethylene terephthalate repeating unit is less than 10 mol%, ink adhesion is lowered (Comparative Example 1), and when it exceeds 30 mol%, the breaking strength of the film Was lowered (Comparative Example 2). In addition, when the content of the dimethyl (-1,3-propylene) terephthalate repeating unit is less than 5 mol%, the heat shrinkage property of the film is greatly lowered, and when it exceeds 20 mol%, the breaking strength of the film is lowered.

In addition, it can be seen that the film mixed with a white inorganic pigment such as titanium oxide in an amount according to the scope of the present invention has good whiteness and hiding power. If the content of titanium oxide is less than 5% by weight relative to the total amount of the film, the whiteness falls and the hiding power is poor (Comparative Example 5). If the content exceeds 25% by weight, the thermal shrinkage is lowered and the appearance of the film is also poor.

On the other hand, it can be seen that the film having the sulfonic acid metal salt derivative mixed according to the scope of the present invention has improved the antistatic property of the film without deteriorating the film properties such as breaking strength (Comparative Example 7 and Comparative Example 8) (Examples 10 to 12 ).

As described above, the heat-shrinkable polyester film according to the present invention is not only excellent in basic properties such as heat resistance, chemical resistance, mechanical properties, printing characteristics, but also excellent in whiteness, hiding power and heat shrinkage characteristics, and good antistatic properties. It is useful for the labeling of the various containers or for the entire coating, and especially when used for the labeling of the quadrangular container, it is possible to minimize the end sliding phenomenon in the vertical direction to the main contraction direction.

Figure 1 shows the end action phenomenon of the heat-shrinkable film used for the label of the square container,

2 is a cross-sectional view of a glass bottle entirely covered with a heat shrinkable film.

Claims (11)

10 to 30 mol% of trimethylene terephthalate repeating units, 5 to 20 mol% of 2,2-dimethyl (-1,3-propylene) terephthalate repeating units and the remaining amount of ethylene terephthalate relative to the total components, A heat shrinkable polyester film comprising 5 to 25% by weight of a white inorganic pigment based on the total weight of the film. The heat-shrinkable polyester film of claim 1, wherein the white inorganic pigment is at least one inorganic pigment selected from the group consisting of titanium oxide, barium sulfide, and calcium carbonate. According to claim 1, wherein the sulfonic acid metal salt derivative represented by R1-SO ₃ Me (wherein R1 is an alkyl group having 5 to 20 carbon atoms, Me is an alkaline earth metal or an alkali metal) 0.02 to 0.8% by weight based on the total weight of the film Heat-shrinkable polyester film characterized in that it further comprises. The heat-shrinkable polyester film of claim 3, wherein Me is a metal selected from the group consisting of lithium, sodium, potassium, and magnesium. 4. The heat-shrinkable polyester film of claim 3, wherein the sulfonic acid metal salt derivative is at least one sulfonic acid metal salt derivative selected from the group consisting of sodium olylbenzenesulfonate, potassium nonylbenzenesulfonate and potassium undecylbenzenesulfonate. The heat-shrinkable polyester film according to claim 3, wherein the resistivity of the polyester film surface is 2 x 10 ¹³ Pa or less. The method of claim 1, wherein the polyester film has a whiteness of 80% or more based on ASTM E313, the light transmittance for a film having a thickness of 40㎛ 40% or less based on ASTM D1003, the film for the nitrocellulose-based ink The surface adhesiveness of is over 5B grade based on ASTM D3359. The shrinkage in the main shrinkage direction of 40% or more in 80 ℃ hot water, the shrinkage in the vertical direction relative to the main shrinkage direction is less than 5%. a) 2,2- obtained by copolymerizing terephthalic acid or dimethyl terephthalate as the diethylene component and ethylene glycol and 2,2-dimethyl (-1,3-propane) diol as the polyethylene terephthalate, polytrimethylene terephthalate and dicarboxylic acid components Blending dimethyl (-1,3-propane) diol copolyester to obtain a polyester resin mixture; b) mixing a white inorganic pigment into the polyester resin mixture; c) manufacturing a melt sheet by extrusion molding the polyester resin mixture mixed with the white inorganic pigment; d) cooling and solidifying the melt sheet to produce a cooled and solidified sheet; And e) stretching the cold-solidified sheet. The method of manufacturing a heat-shrinkable polyester film according to claim 8, wherein the intrinsic viscosity of the polytrimethylene terephthalate is 0.6 to 1.0. The method of claim 8, wherein the intrinsic viscosity of the 2,2-dimethyl (-1,3-propane) diol copolymer polyester is 0.5 to 0.8. The method of claim 8, wherein the 2,2-dimethyl (-1,3-propane) diol copolymer polyester is 70 to 93 mol% ethylene terephthalate repeat unit and dimethyl (-1,3-propylene) terephthalate repeat unit 7 A heat shrinkable polyester film production method characterized by containing from 30 to 30% by mole.