KR100932289B1 - Twistable Polyester Films - Google Patents

Abstract

The present invention relates to a polyester film for excellent twist packaging that can be used for individual packaging such as candy, chocolate, caramel and the like, as well as for flowers or other gift packaging, wherein the elongation value (MD) in the elongation value of the film is in the transverse direction (TD). Small compared to the elongation value and the difference is within 10-30%; Fold holding angle obtained by calculating the angle (θ) of the folded part in half under the condition of pressure 0.2MPa, pressurization time 1 sec. And 60 ° or less in transverse direction; Using a twist gauge, apply tension to both ends of the film under a load of 270 g, then twist 20 laps, remove the grip, and let it stand at room temperature for 24 hours. The kink retention rate derived by is 65% or more; It is characterized by a density of 1.30 to 1.37 g / cm3 measured by a 25 ° C thermostat density tube, and such a polyester film inherently has excellent mechanical properties, printability, transparency, thickness uniformity, and cutting. It is useful as a packaging material such as candy, caramel or chocolate packaging material with excellent kinkability and kink retention rate while having sex and harmlessness.

Equation 1

θ = 2sin ^-1 (F / 2L)

Where F is the length of the imaginary line between the two ends of the film folded in half, and 2L is the total length of the film folded.

Equation 2

Twist Retention Rate (%) = (X / 20) × 100

Description

Twistable Polyester Films

The present invention relates to a polyester film for twist packaging having excellent twistability and twist holding performance, which can be used for individual packaging such as candy, chocolate, caramel, and flowers or other gift packaging.

Polyethylene terephthalate (PET) molded articles, which are currently produced industrially, are widely used in fibers, films and other molded articles. In particular, polyethylene terephthalate films obtained from aromatic dicarboxylic acids and glycols have excellent heat resistance, tensile strength, elongation, Young's modulus, elastic recovery, impact resistance, and the like. Its mechanical properties, dimensional stability, and electrical insulation make it widely used for industrial and agricultural materials such as magnetic recording tapes, photographic films, insulating materials, and films to be deposited. In addition, it is excellent in chemical properties such as chemical resistance, weather resistance, water resistance, transparency, supplementary property, water resistance, gas barrier property, etc. The use of materials is also increasing significantly.

Usually, the industrial production method of a polyethylene terephthalate film melt-extruded a polyethylene terephthalate polymer and cooled in a cooling drum to prepare an amorphous sheet, and then stretched and heat set to obtain a biaxially stretched film. In this case, as an industrial production method of polyethylene terephthalate polymer used in the production of polyethylene terephthalate film, a direct ester which is usually heated to a reaction temperature of 200 to 280 ° C. under atmospheric pressure or pressure using dicarboxylic acid such as terephthalic acid and ethylene glycol as main components. The main component obtained by bis (beta-hydroxyethyl) is obtained by the polymerization reaction or by a transesterification reaction in which a dimethyl carboxylate such as dimethyl terephthalate and glycol such as ethylene glycol are used as a main component and heated to a reaction temperature of 140 to 240 ° C. in the presence of a catalyst. ) The terephthalate and its low molecular weight condensate (esterified product) are obtained, and it is manufactured by the method of carrying out the polycondensation continuously by heating at the reaction temperature of 260-300 degreeC with a polycondensation catalyst under high vacuum.

Polyethylene terephthalate is well known to be of great industrial value due to such excellent properties. However, in some applications, there are some areas where use is restricted.

In particular, packaging films (twisted film) such as candy, caramel, chocolate, etc., which are wrapped by twisting the film, should have characteristics such as excellent twistability and maintainability, high rigidity, printability, harmlessness to human body, and cutting property. However, polyethylene terephthalate has almost no kinkability due to the high crystallinity and resilience of the existing film forming technology.

As a conventional twist film, cellophane, OPS, PVC film and the like have been mainly used because of excellent twisting characteristics.

However, these conventional twisted films have their disadvantages for each type of polymer.

For example, PVC film is subject to environmental regulations by country / region due to environmental hormones caused by plasticizers and dioxin generation when incinerated, and is designated as a regulated item in some food packaging applications in Korea. It is a situation. In the case of OPS film, it is difficult to produce products with uniform thickness, and the defect rate in twisted packaging is large and its use is limited due to problems of thermal stability (dimension stability), mechanical toughness and processability.

In the case of cellophane, it has excellent kinkability but strong hygroscopicity, which makes a big difference in the physical properties due to the surrounding environment. In addition, the manufacturing process of cellophane polymer is a problem a lot of pollution industry. In particular, its price is high, so its use is limited.

Recently, some co-extruded polypropylene films have been developed and used, but some packaging companies are discontinuing their use due to problems such as printability, contamination of food contents due to layer separation of the coextrusion layer, and thermal stability. It is a state.

Therefore, if twisting property can be given to polyester film, it can be used for twisted packing while satisfying the properties required for various packing applications such as mechanical properties, printability, transparency, thickness uniformity, cutting property, food hygiene stability, etc. It can have advantages.

However, due to the characteristics of the existing polyester film manufacturing method, crystal structure growth due to orientation and heat is inevitable due to stretching and heat treatment at high temperature during the film manufacturing process and relaxation rate for dimensional stabilization. Due to the recovery properties, polyethylene terephthalate films having excellent kinkability have been difficult to date.

Accordingly, the present invention is to have a twistability and twist retention suitable for the twist packaging to the conventional polyester film having no twisting characteristics, using a polyester resin with a copolymerization component as a raw material, film production By controlling the conditions, crystallization caused by the orientation and heat progressed in the film forming process is suppressed, thereby providing a twisting property and producing a polyester film exhibiting long-term twist retention.

Accordingly, it is an object of the present invention to provide a polyester film which is endowed with twisting property and can maintain twisting for a long time.

In the polyester film of the present invention for achieving the above object, the longitudinal direction (MD) elongation value of the film is smaller than the transverse direction (TD) elongation value and the difference in value is within 10-30%; Using Heat Gradient, the film was pressurized at a pressure of 0.2Mpa and pressurization time of 1 second at room temperature, folded in half, and the folding holding angle obtained by calculating the angle (θ) of the folded portion after 30 minutes through the following equation (1) 60 ° or less in both longitudinal and transverse directions; Using a twist gauge, apply tension to both ends of the film with a load of 270g, twist the 20 wheels on the grip, and let it stand at room temperature for 24 hours after removing the grip. The kink retention rate derived by is more than 65%; And the density measured by the density gradient pipe method is 1.30 to 1.37 g / cm 3.

Equation 1

θ = 2sin ^-1 (F / 2L)

Where F is the length of the imaginary line between the two ends of the film folded in half, and 2L is the total length of the film folded.

Equation 2

Twist Retention Rate (%) = (X / 20) × 100

The polyester film according to the present invention inherently has excellent mechanical properties, printability, transparency, thickness uniformity, cutting property and harmlessness, and has excellent twistability and retention rate, such as candy, caramel or chocolate packaging material. It is useful as a packaging material.

The present invention will be described in more detail as follows.

In the polyester film according to the present invention, the longitudinal elongation value is smaller than the transverse elongation value in the elongation value of the film, and the difference in value is within 10 to 30%.

In the case of twisted packaging machines such as candy packaging, twisting is performed at both ends of the transverse direction (TD) at the same time as cutting in the direction perpendicular to the roll running direction of the film (TD), where the distance between the grips is fixed. In the state of twisting, a strong stretching force is applied in the transverse direction of the film, and a fold line of the film is generated in the transverse direction. Therefore, it was found that the holding property and the elongation (%) in the transverse direction to the longitudinal direction were moderately large and balanced to produce an effective twisting property for twist packaging such as candy. The elongation must be greater in the transverse direction (TD) than in the longitudinal (machine direction, MD) value for effective twisting in the transverse direction, and the elongation difference (E _TD -E _MD ) is 5 to 50%, preferably 10 It is ~ 30% days. In addition to providing excellent twisting property in the transverse direction (TD) like candy packaging, it can be easily adjusted by adjusting the relative stretching ratio in the longitudinal direction and the transverse direction in order to give uniform twisting property in the transverse direction or all directions for special purposes. Do.

In addition, when the folding holding angle (θ) indicating the folding performance of the film is measured and evaluated, it is excellent in the twisting property not to be opened by 60 ° or more. If the kink holding angle exceeds 60 °, the kink is not sufficient, so that the contents are exposed, and there is a problem that the kink is released during the long time transportation storage and heating aging process of caramels at room temperature.

As another assessment of twisting, the twist holding rate needs to be maintained at 65% or higher. This ensures long-term twist retention.

Twist retention rate is to take a specimen of polyester film in the longitudinal direction and the transverse direction at a constant size (width 10mm x length 80mm) at room temperature, and then use a twist machine (Twist Machine, Maker: United States Testing Co, Inc., Model: 8000). Using a constant tension under the condition of 270g load was twisted 20 wheels at a constant rpm in the grip and released from the grip for 24 hours at room temperature after the angle of twist was calculated by measuring the angle (wheels, X).

Such a polyester film is preferably obtained from a copolymer composition comprising a copolymerizing component. When using a copolymer composition, the basic crystal structure of the polyester is formed when the film is formed into a film through a sheet drawing process as compared with that obtained from polyethylene terephthalate alone. By hindering the crystallinity of the stretched film. In particular, the acid component or glycol component which can be used as a component of the copolymer composition is structurally linear diethylene glycol, triethylene glycol, neopentyl glycol, adipic acid and cyclic isophthalic acid, cyclohexane dimethanol, naphthalene Types such as dicarboxylate can be used. In particular, when these copolymerization components are used, crystallization is suppressed through the stretching process, the corresponding stretching temperature, and the heat treatment process during film formation, but in order to effectively increase the twist performance of the final film, folds generated when deformation (twist) is applied to the film at room temperature. And further inducing crystallization due to stress received during the kink to lower the strain recovery force of the film. Therefore, in the case of using the cyclic copolymer component, crystallization is suppressed during the film manufacturing process, but the crystallization of the deformable portion is difficult during the twisting deformation, so that permanent deformation is difficult and thus does not exhibit excellent twist retention. On the other hand, when using a copolymer of linear structure, the glass transition temperature (Tg) can be considerably lowered compared to the cyclic structure component, so that it can be stretched at a relatively low temperature, and thus the crystallization of the entire film can be suppressed by low temperature stretching. do. In addition, the twisted deformation of the film, due to the linear structure of the polymer chain is relatively easy to crystallization by deformation compared to the annular structure was found to significantly improve the twist retention of the film.

delete

With this in mind, in the present invention, dicarboxylic acid having a linear structure of HOOC- (CH ₂ ) _n -COOH (n = 4 to 12) is used as the aliphatic dicarboxylic acid.

In the use of the copolymer composition, the method may be used by adding one or more copolymerization components to copolymerize or blending polyethylene terephthalate and one or more polyester copolymers.

In addition, the content of the copolymerization component present in the film when the polyester film is added by adding such a component changes the glass transition temperature (Tg) of the extruded unstretched sheet for producing the film. Therefore, the content of the copolymerization component remaining in the film is added to the extent that the glass transition temperature of the unstretched sheet can be maintained at 60 ° C or higher. The glass transition temperature of less than 60 ℃ is a high risk of causing a change in the physical properties of the film at room temperature and is not desirable for maintaining long-term twisting. In view of such a point, it is preferable that the content of a preferable copolymerization component is 3-20 mol% in the whole copolymer composition.

The degree to which crystallization is suppressed can be judged by measuring the thermal properties of the extruded unoriented sheet and the film in the stretching step. The cooling crystallization temperature (Tc) and the heat crystallization temperature (Tcc), which show the possibility of crystallization progress during extrusion sheet quenching, stretching, and heat treatment, are measured by differential scanning thermal analyzer (DSC).

Polyethylene terephthalate film having a cooling crystallization temperature (Tc) of about 190 ° C promotes crystallization during the manufacturing process. For manufacturing a film having excellent twistability, Tc is preferably 170 ° C or lower, and preferably 160 ° C or lower. Do. This has the effect of relatively slow retardation of crystallization during the film manufacturing process. In addition, even at the heat crystallization temperature (Tcc), general polyethylene terephthalate exhibits a temperature of about 130 ° C, which promotes crystallization during the film manufacturing process. Requires slow thermal crystallization

The twisted packaging film of the present invention is produced by the step of extrusion, casting, cooling, preheating, uniaxially or biaxially stretching the polyethylene terephthalate or polyester copolymer composition according to a conventional method. Is the same as

First, the polyester-based resin mixture is kneaded well, and then melt-extruded at a melting point or higher temperature, followed by quenching at a temperature below Tg in a casting roll, and then an amorphous sheet is prepared first. At this time, the intrinsic viscosity (IV) of the resin is preferably 0.60 to 0.75 or less. If the intrinsic viscosity of the resin is lower or higher than this, breakage problems or deterioration of physical properties are caused during film formation, and it affects the filter pressure, making uniform sheet molding difficult and inevitably lowering the film formation speed.

When the film is manufactured using general polyethylene terephthalate, the sheet is stretched in the longitudinal direction and in the transverse direction. In general, the stretch in the longitudinal direction and the transverse direction is 3 to 5 times, respectively, and the heat treatment is performed at a high temperature of 200 ° C. or higher. By the way, in the present invention, according to the relative draw ratios in the longitudinal and transverse directions, the twisting characteristics in the longitudinal direction and the transverse direction may be different. Preferably, in the case of a candy wrapping paper, the longitudinal direction in the folding holding angle, In the case of the twist holding ratio, since the value in the transverse direction must be excellent, it is preferable to make the stretching ratio in the longitudinal direction larger than the transverse direction. If the folding holding angle and the twist holding ratio are required to be opposite to each other, the transverse stretching ratio may be kept larger than the longitudinal stretching ratio. In other words, by adjusting the relative draw ratio of the longitudinal draw ratio and the transverse draw ratio, it is possible to easily adjust the folding holding angle or the twist holding ratio in each of the longitudinal direction and the transverse direction.

On the other hand, it is preferable to extend | stretch longitudinal direction temperature between Tg + 30 degreeC more than Tg of the said composition sheet, It is preferable to suppress orientation crystallization progression through low-temperature extending | stretching near Tg preferably.

In the transverse stretching, the stretching is preferably carried out between the longitudinal stretching temperature Tsm and the longitudinal stretching temperature Tsm + 30 ° C.

In the heat treatment process, the heat treatment temperature is preferably at least Tg and the transverse stretching temperature (Tst) + 30 ° C. or less, and preferably at least Tg or less. After the film is manufactured, if it receives heat during the printing process, etc., the heat treatment should be performed at a temperature of at least Tg to minimize the shrinkage.

On the other hand, in the Relaxation section, the relaxation rate is suitably 3% or less, and preferably, the relaxation rate is 0%. Rather, it is possible to draw in the open section (Relax rate -3%). However, there may be some wrinkles in appearance when drawn.

The density of the polyester film thus prepared is preferably 1.30 to 1.37 g / cm 3. Density is a factor that greatly influences the folding retention angle and twist characteristics of the film. When the density is less than 1.30, the twist performance is greatly improved, but The shrinkage rate is very large, and the change over time such as dimensional change and wrinkles is large, and the storage stability of the product is also lowered, which reduces its value as a product. If the density is greater than 1.37, it means that the prepared crystallinity is large, which causes a problem in that the twist performance is deteriorated.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

(Measurement of physical properties)

1) folding holding angle

The higher the degree that the object deformed by the external force cannot recover, the better the foldability or twistability. Therefore, in the evaluation method of the twistability, the film was folded at the same temperature and pressure for the same time, and then the pressure was removed, and then the folding property (Deadfold property) was compared with the folding holding angle of the film. The direction of foldability was measured by taking the film in the longitudinal direction and the transverse direction here.

① Equipment used: Heat Gradient (Toyoseiki)

② Equipment condition: Pressure-0.2MPa, Pressurization time-1sec, Temperature-Room temperature (25 ℃)

③ Sample method: Size (width W = 10mm, length 2L = 20mm)

※ Sample is taken as MD D / F when measured in MD direction-Folded line in TD direction

④ Evaluation method of folding retention angle

After the constant pressure was applied to the film by the above method, the angle of the folded portion was calculated and compared after a predetermined time (30 minutes). See FIG. 1 for the calculation method.

Folding hold angle: θ = 2 sin ^-1 (F / 2L), L = 10 mm

Where W is the width of the film, L is the length of the film folded in half, and F is the length of the imaginary line between the two end points of the film folded in half.

2) Kink retention rate

Twisting retention rate is a certain size (10mm width × 80mm length) of the specimen of polyester film at room temperature and using both twist machine (Twist Machine, Maker: United States Testing Co, Inc., Model: 8000) both ends of the film After taking a constant tension with a weight of 270g, twisted 20 laps from the grip and released from the grip for 24 hours at room temperature, after calculating the number of wheels (X) remaining twist was calculated.

Twist Retention Rate (%) = (X / 20) × 100

3) Shinto

delete

delete

delete

delete

delete

① Measuring method: 10mm in width and 100mm in length for each MD, TD direction of the film

UTM (Universal Instrument Machine) at a speed of 300 mm / min

Measured.

② Equipment: Instron 1123 (England)

4) film density

① Measuring method: Float the sample in the density gradient pipe and measure it (25 ℃ constant temperature bath)

② Equipment: Densito Meter (SIBAYAMA, Japan)

Examples and Comparative Examples

After extruding the raw material resin, it was quenched to prepare an amorphous sheet, and then again biaxially stretched for each condition to prepare a 20 μm film. Specific raw material resin compositions and stretching methods are as shown in Table 1 below.

The glass transition temperature (Tg), the cooling crystallization temperature (Tc) and the heating crystallization temperature (Tcc) of the sheet were measured and the results are shown in Table 1 below. Elongation difference and density of was measured as described above and the results are shown in Table 1 below.

상기 표 1의 결과로부터, 본 발명에서와 같이 공중합 성분으로서 지방족 디카르본산을 사용하고, 종방향 연신온도, 횡방향연신온도 및 열처리온도 등을 조절한 결과 신도값의 차이가 10~30% 범주이면서 접힘유지각도가 종방향 및 횡방향 모두 60° 이하이며, 꼬임유지율도 65% 이상이며, 밀도가 1.37g/㎤ 이하인 필름을 얻을 수 있음을 알 수 있다. 특히, 실시예 1의 경우 종방향 연신비를 횡방향 연신비보다 크게 조절함으로써 종방향의 접힘유지각도, 그리고 꼬임유지율에 있어서는 횡방향의 꼬임유지율이 실시예 2에 비해서 사탕 싸개지 등의 공정에 적합한 값을 나타냄을 알 수 있다.

From the results of Table 1 above, the difference in elongation value is 10 to 30% by using aliphatic dicarboxylic acid as a copolymerization component as in the present invention and adjusting the longitudinal stretching temperature, the lateral stretching temperature and the heat treatment temperature. On the other hand, it can be seen that a film having a folding holding angle of 60 ° or less in both the longitudinal and transverse directions, having a twist holding ratio of 65% or more, and a density of 1.37 g / cm 3 or less can be obtained. In particular, in the case of Example 1, by adjusting the longitudinal draw ratio to be larger than the transverse draw ratio, in the longitudinal folding angle and the twist holding ratio, the twist holding ratio in the transverse direction is more suitable for a process such as candy wrapping than in Example 2. It can be seen that.

delete

On the other hand, Comparative Examples 1 and 2 are films obtained by the composition of polyethylene terephthalate alone, which does not contain a copolymerization component. In this case, the values are not satisfactory in the folding holding angle, the twist holding ratio, and the elongation difference. In the case of using an aliphatic dicarboxylic acid as a copolymerization component, but due to the deviation of the manufacturing conditions showed an unsatisfactory result in the fold holding angle or twist holding ratio. In the case of Comparative Example 4, the use of aromatic dicarboxylic acid as the copolymerization component showed unsatisfactory results in all of the folding holding angle, the twist holding ratio, and the elongation value.

In addition, it can be seen that the films according to the comparative examples all have a value of 1.37 g / cm 3 or more in density, which is not preferable in terms of twistability.

1 is a schematic diagram for illustrating a calculation method of the folding holding angle.

<Description of Drawing Major Symbols>

W- film width, L- half folded film length

F- length of imaginary line between two ends of film folded in half

θ- angle in half folded

Claims (3)

The longitudinal (MD) elongation value of the film is smaller than the transverse (TD) elongation value and the difference in value is within 10-30%; Using Heat Gradient, the film is pressurized at a pressure of 0.2 MPa at 1 ° C and pressurization time of 1 second, folded in half, and the folding holding angle obtained by calculating the angle (θ) of the folded portion after 30 minutes through the following equation (1) 60 ° or less in both longitudinal and transverse directions; Using a twist gauge, apply tension to both ends of the film with a load of 270g, twist the 20 wheels on the grip, and let it stand at room temperature for 24 hours after removing the grip. The kink retention rate derived by is more than 65%; And a density measured by the density gradient pipe method of 1.30 to 1.37 g / cm 3. Equation 1 θ = 2sin ^-1 (F / 2L) Where F is the length of the imaginary line between the two ends of the film folded in half, and 2L is the total length of the film folded. Equation 2 Twist Retention Rate (%) = (X / 20) × 100 delete The method according to claim 1, wherein the polyester film is obtained from a copolymer composition comprising at least one aliphatic dicarboxylic acid component as a copolymerization component, wherein the copolymerization component is contained in 3 to 20 mol% of the copolymer composition. Polyester film having a.

Images