KR20160079449A - Laminated polyester film and preparation method thereof - Google Patents

Abstract

The present invention relates to a stacked polyester film, and a manufacturing method thereof. The polyester film of the present invention comprises: a first layer including a first polyester resin manufactured by a first catalyst; and a second layer in a stacked form, which includes a second polyester resin manufactured by a second catalyst, wherein the second catalyst is different from the first catalyst. The polyester film according to the present invention has improved brightness and low oligomer leaching characteristics, thereby being useful as a substrate of a prism for an ITO substrate, a silver nanowire substrate, a metal mesh substrate, and an LED backlight unit.

Description

TECHNICAL FIELD [0001] The present invention relates to a laminated polyester film,

Examples relate to a laminated polyester film and a method for producing the same.

In general, polyester films are excellent in dimensional stability, thickness uniformity and optical transparency, and are used not only for display devices but also for various kinds of industrial materials such as beverage filling containers, medical supplies, packaging materials, sheets, and automobile molded products. Plasma Display Panel (PDP) and LCD (Liquid Crystal Display), which occupy the most part of the display industry, use plastic films as component parts of devices. When optical transparency is required, polyester films are used And a polyimide film is mainly used when durability and heat resistance are required. In particular, the biaxially stretched polyester film is excellent in dimensional stability, thickness uniformity and optical transparency, and is used in various industrial fields as described above.

The base film used in such a display field is required to have various characteristics such as process running stability, transparency, scratch resistance, planarity and light transmittance. The reason why so many requirements are required is that the purpose of the base film used in the display field must satisfy the optical specificity.

If the flatness of the film is poor, flatness, which is one of the characteristics required for the base film, causes a slipping phenomenon due to uneven tension in the production process of the base film, resulting in scratch defects on the surface of the film, It may cause partial coating defects in the coating process, which causes the value of the product to deteriorate.

One of the other characteristics required for the base film is scratch resistance. When scratches are generated in the base film, black spots, which are electrical defects due to unevenness in coating, occur in the defect portions. In addition, hard coating, Which is a characteristic required for a base film. And cause optical defects, which adversely affects the quality and yield of the product.

These properties required in the base film are ultimately necessary characteristics for increasing the luminance of the film, the thermal stability, and the processing characteristics. Therefore, the lowering of transparency, scratch resistance, planarity, and total light transmittance causes a problem in lowering of brightness and reliability and a decrease in yield. Such a decrease in luminance requires a higher light source in order to obtain a necessary amount of light, and it requires a higher cost and a higher power consumption of a material in order to obtain a higher light source, which is a fatal defect in the base film used in the display field .

Therefore, various studies have been made on the base film for improving the luminance. For example, Japanese Patent No. 4288607 discloses a biaxially stretched polyester film which is a light diffusion layer having a base film and a coating amount and containing a binder and particles, and Japanese Patent No. 5023471 discloses a bubble- And a coating layer containing a light stabilizer and an antioxidant on the surface of the film.

However, the above-mentioned conventional techniques have a problem that voids are generated in stretching the films.

Japanese Patent No. 4288607 Japanese Patent No. 5023471

An embodiment of the present invention provides a laminated polyester film and a method of manufacturing the laminated polyester film which are excellent in properties such as transparency and low oligomer by solving the problems of the prior art as described above.

According to one embodiment,

A first layer comprising a first polyester resin made from a first catalyst; And

And a second layer comprising a second polyester resin made from a second catalyst different from the first catalyst.

According to one embodiment,

(a) preparing a first polyester resin using a germanium compound as a catalyst; (b) preparing a second polyester resin using an antimony compound as a catalyst; (c) simultaneously extruding the polyester resins to produce a laminated undrawn sheet; And (d) stretching the unstretched sheet. The present invention also provides a method for producing a laminated polyester film.

The laminated polyester film according to the embodiment is formed by proper combination of the first polyester layer prepared by using the germanium compound as a catalyst and the second polyester layer produced by using the antimony compound as a catalyst, , And has low oligomer elution characteristics. Therefore, on the basis of these properties, it can be usefully used as a substrate for an ITO substrate, a silver nanowire substrate, a metal mesh substrate, and a prism for a LCD backlight unit, which are recently used in touch panels.

A laminated polyester film according to one embodiment comprises two or more layers. Said laminated polyester film comprising: a first layer comprising a first polyester resin made from a first catalyst; And a second layer comprising a second polyester resin made from a second catalyst different from the first catalyst. The laminated polyester film may further comprise a third layer comprising a third polyester resin made from the first catalyst, wherein the second layer may be located between the first and third layers have.

In one embodiment, the laminated polyester film may have a structure in which the first layer and the second layer are sequentially laminated.

In one embodiment, the laminated polyester film may have a structure in which the first layer, the second layer and the third layer are sequentially laminated.

The first layer comprises a first polyester resin. More specifically, the first layer contains the first polyester resin as a main component. The first layer may include about 85 wt% or more of the first polyester resin. More specifically, the first layer may comprise at least about 95 wt% of the first polyester resin. More specifically, the first layer may comprise at least about 99 wt% of the first polyester resin.

And the second layer comprises a second polyester resin. More specifically, the second layer contains the second polyester resin as a main component. The second layer may comprise about 85 wt% or more of the second polyester resin. More specifically, the second layer may comprise at least about 95 wt% of the second polyester resin. More specifically, the second layer may comprise about 99 wt% or more of the second polyester resin.

And the third layer comprises a third polyester resin. More specifically, the third layer contains the third polyester resin as a main component. The third layer may include about 85 wt% or more of the third polyester resin. More specifically, the third layer may comprise at least about 95 wt% of the third polyester resin. More specifically, the third layer may comprise about 99 wt% or more of the third polyester resin.

The first polyester resin includes a diol component and a dicarboxylic acid component. More specifically, the first polyester resin may consist entirely of the diol component and the dicarboxylic acid component. More specifically, the first polyester resin may contain at least 95 mol% of the diol component and the dicarboxylic acid.

The first polyester resin may be formed by a first catalyst. That is, the first catalyst may be used, and the diol component and the dicarboxylic acid component may be polymerized after the transesterification reaction to form the first polyester resin.

Specific examples of the diol component include ethylene glycol, 1,4-cyclohexanedimethanol, 1,3-propanediol, 1,2-octanediol, 1,3-octanediol, 2,3 Butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol) 1,3-propanediol, 2,2-diethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 3- 1,5-pentanediol, and mixtures thereof. The diol component may comprise about 80 mole% or more of ethylene glycol. More specifically, the diol component may comprise at least about 90 mole% ethylene glycol. More specifically, the diol component may comprise at least about 95 mole% ethylene glycol. More specifically, the diol component may comprise at least about 99 mole% ethylene glycol.

The dicarboxylic acid component may be an aromatic dicarboxylic acid such as terephthalic acid, dimethylterephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and orthophthalic acid; Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid; Alicyclic dicarboxylic acid; And their esterified products can be used alone or in combination of two or more. More specifically, the dicarboxylic acid component may comprise at least about 80 mole% aromatic dicarboxylic acid. More specifically, the dicarboxylic acid component may comprise at least about 80 mole percent terephthalic acid. More specifically, the dicarboxylic acid component may comprise at least about 90 mole percent terephthalic acid. More specifically, the dicarboxylic acid component may comprise at least about 95 mole percent terephthalic acid. More specifically, the dicarboxylic acid component may comprise at least about 99 mole% terephthalic acid.

The first polyester resin may be polyethylene terephthalate.

The IV viscosity of the first polyester resin may range from about 0.65 dl / g to about 0.75 dl / g. More specifically, the IV viscosity of the first polyester resin may be from about 0.67 dl / g to about 0.73 dl / g. More specifically, the IV viscosity of the first polyester resin may be from about 0.68 dl / g to about 0.72 dl / g.

The first catalyst may be a germanium compound and / or a titanium compound.

Examples of the germanium compound include (a) amorphous germanium oxide, (b) fine crystalline germanium oxide, (c) a solution in which germanium oxide is dissolved in glycol in the presence of an alkali metal or alkaline earth metal or a compound thereof, (d) Is dissolved in water, and the like. The germanium-based catalyst may be used in an amount of 10 to 10,000 ppm, preferably 10 to 20,000 ppm, more preferably 10 to 20,000 ppm, per 100 g of the polyethylene terephthalate resin constituting the polyester film. The germanium- 1,000 ppm. Here, when the amount of the catalyst is too small, the polycondensation reaction of the polyester resin is not effectively carried out, or when the color of the polyester resin is poor and the amount of the catalyst is too large, no additional catalytic effect is obtained, Or may act as an impurity of the polyester resin.

Examples of the titanium compound include titanium oxide, titanium chelate compound, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate and butyl-isopropyl titanate It is preferable that the content of the titanium element is 1 to 50 ppm based on the polymer weight in order to control the side reaction causing discoloration.

The first catalyst may remain in the first polyester resin in an amount of from about 10 ppm to about 200 ppm, more specifically from about 20 ppm to about 150 ppm.

In addition, the second polyester resin includes the diol component and the dicarboxylic acid component. More specifically, the second polyester resin may consist entirely of the diol component and the dicarboxylic acid component. More specifically, the second polyester resin may contain at least about 95 mol% of the diol component and the dicarboxylic acid.

The second polyester resin may be formed by a second catalyst. That is, the second catalyst may be used, and the diol component and the dicarboxylic acid component may be polymerized after the ester exchange reaction to form the second polyester resin.

The second polyester resin may be polyethylene terephthalate. The IV viscosity of the second polyester resin may be from about 0.55 dl / g to about 0.65 dl / g. More specifically, the IV viscosity of the second polyester resin may be about 0.57 dl / g to about 0.63 dl / g. More specifically, the IV viscosity of the second polyester resin may be from about 0.58 dl / g to about 0.62 dl / g.

The second catalyst is different from the first catalyst. More specifically, the second catalyst may be an antimony compound.

Examples of the antimony compound include antimony oxide (Sb ₂ O ₃ ) and antimony acetate (Sb (CH ₃ COO) ₃ ).

The second catalyst may remain in the second polyester resin in an amount of from about 40 ppm to about 250 ppm, more specifically from about 50 ppm to about 180 ppm.

The third polyester resin includes the diol component and the dicarboxylic acid component. More specifically, the third polyester resin may consist entirely of the diol component and the dicarboxylic acid component. More specifically, the third polyester resin may contain at least about 95 mol% of the diol component and the dicarboxylic acid.

The third polyester resin may be formed by the first catalyst. More specifically, the first catalyst may be a germanium compound and / or a titanium compound.

 That is, the first catalyst may be used, and the diol component and the dicarboxylic acid component may be polymerized after the transesterification reaction to form the third polyester resin.

The third polyester resin may be polyethylene terephthalate. In this case, the IV viscosity of the third polyester resin may be about 0.65 dl / g to about 0.75 dl / g. More specifically, the IV viscosity of the third polyester resin may be from about 0.67 dl / g to about 0.73 dl / g. More specifically, the IV viscosity of the third polyester resin may be from about 0.68 dl / g to about 0.72 dl / g.

The third polyester resin may be substantially the same as the first polyester resin.

The viscosity of the first polyester resin is higher than that of the second polyester resin. The difference between the viscosity of the first polyester resin and the viscosity of the second polyester resin may be about 0.05 dl / g to about 0.15 dl / g.

The viscosity of the third polyester resin is higher than the viscosity of the second polyester resin. The difference between the viscosity of the third polyester resin and the viscosity of the second polyester resin may be about 0.05 dl / g to about 0.15 dl / g.

With respect to the same direction, the refractive index of the first layer may be smaller than the refractive index of the second layer. The difference between the refractive index of the first layer and the refractive index of the second layer may be from about 0.001 to about 0.01.

With respect to the same direction, the refractive index of the third layer may be smaller than the refractive index of the second layer. The difference between the refractive index of the third layer and the refractive index of the second layer may be between about 0.001 and about 0.01.

The refractive index in the width direction of the first layer may be about 1.670 to about 1.680.

The width direction refractive index of the second layer may be about 1.671 to about 1.690.

The width direction refractive index of the third layer may be about 1.670 to about 1.680.

The ratio of the thickness of the first layer and the thickness of the second layer may be from about 1:20 to about 1: 3. More specifically, the ratio of the thickness of the first layer and the thickness of the second layer may be from about 1:15 to about 1: 5. More specifically, the ratio of the thickness of the first layer and the thickness of the second layer may be from about 1:13 to about 1: 8.

The ratio of the thickness of the third layer and the thickness of the second layer may be from about 1:20 to about 1: 3. More specifically, the ratio of the thickness of the third layer and the thickness of the second layer may be from about 1:15 to about 1: 5. More specifically, the ratio of the thickness of the third layer and the thickness of the second layer may be from about 1:13 to about 1: 8.

The thickness of the laminated polyester film according to the embodiment, in particular, the sum of the thicknesses of the first layer, second layer and third layer may be about 100 탆 to about 300 탆. More specifically, the sum of the thicknesses of the first layer, the second layer and the third layer may be about 120 탆 to about 270 탆.

The transparency of the laminated polyester film according to an embodiment may be from about 85% to about 95%. More specifically, the transparency of the laminated polyester film according to an embodiment may be from about 88% to about 93%.

The haze of the laminated polyester film according to the embodiment may be about 2% or less. More specifically, the haze of the laminated polyester film according to an embodiment may be about 1.5% or less. More specifically, the haze of the laminated polyester film according to the embodiment may be about 1.1% or less. More specifically, the haze of the laminated polyester film according to the embodiment may be about 0.7% or less.

The laminated polyester film according to the embodiment has low oligomer elution properties. That is, the amount of the oligomer eluted from the laminated polyester film according to the embodiment is small.

Thus, after the laminated polyester film according to the embodiment was left at the temperature of about 130 캜 for about 5 minutes, the haze of the laminated polyester film according to the embodiment can be raised to about 3% or less as compared with that before the heat treatment have. More specifically, the haze of the laminated polyester film according to the embodiment can be raised to about 2% or less under the above conditions, as compared with that before the heat treatment. More specifically, the haze of the laminated polyester film according to the examples can be raised to about 1% or less under the above conditions, as compared with before the heat treatment.

The laminated polyester film according to the embodiment may further include a primer layer on both outermost sides. The primer layer may contain an inorganic particle having a diameter of about 100 nm to about 150 nm as a slip agent. The primer layer may include urethane-based, acrylic-based, and polyester-based resins.

The laminated polyester film according to the embodiment can be produced by the following process.

(a) preparing a first polyester resin using a germanium compound as a catalyst; (b) preparing a second polyester resin using an antimony compound as a catalyst; (c) simultaneously extruding the polyester resins to produce a laminated undrawn sheet; And (d) stretching the unstretched sheet. Further, after the step (b), the step of preparing the third polyester resin using the germanium compound as a catalyst may be further included.

More specifically, first, the first polyester resin is produced. The first polyester resin is prepared by the esterification reaction of the diol and the dicarboxylic acid. At this time, the first polyester resin is produced using the first catalyst.

The first polyester resin can be produced by a solid phase polymerization process. For example, a first polyester resin such as polyethylene terephthalate having a number average molecular weight of about 20,000 or so is subjected to melt polymerization. Thus, the first polyester resin melt-polymerized is made into a pellet shape, and the first polyester resin in the form of pellets is further crystallized at 150-200 deg. C and then polymerized at 200-230 deg.

Then, the second polyester resin is prepared. The second polyester resin is prepared by the esterification reaction of the diol and the dicarboxylic acid. At this time, the second polyester resin is prepared using the second catalyst.

After this step, a third polyester resin may be further prepared. The third polyester resin is prepared by the esterification reaction of the diol and the dicarboxylic acid. At this time, the third polyester resin is prepared using the first catalyst.

The third polyester resin can be produced by the solid phase polymerization process as described above and can be substantially the same as the first polyester resin.

At least two or more of the first polyester resin, the second polyester resin and the third polyester resin are melt-extruded to produce an unoriented sheet. The polyester resin is co-extruded into different layers. Accordingly, the unstretched sheet includes two or more layers. More specifically, the unstretched sheet comprises a first layer mainly comprising the first polyester resin, a second layer mainly comprising the second polyester resin, and a third layer mainly comprising the third polyester resin And may have a stacked structure in order.

Thereafter, the unstretched sheet is stretched in the longitudinal direction (machine direction) and the width direction (tenter direction), and is heat-set so that the polyester film can be produced.

The melt extrusion is preferably performed at a temperature of Tm + 30 to Tm + 60 占 폚. If the temperature of the extruder is lower than Tm + 30 占 폚 in the melt extrusion process, the melt will not be smoothly melted and the viscosity of the extrudate will increase to lower the productivity. Conversely, if the temperature exceeds Tm + 60 占 폚, the molecular weight of the resin decreases due to depolymerization due to thermal decomposition, A problem may arise. The cooling is preferably carried out at a temperature of 30 ° C or lower, more preferably 15 to 30 ° C.

The unstretched sheet can be stretched by uniaxial stretching or biaxial stretching.

The non-stretched sheet can be stretched by a suitable stretching ratio in the longitudinal direction and the width direction. For example, the unstretched sheet may be stretched about 2.5 to about 6 times in the longitudinal direction and about 2.5 to about 6 times in the width direction. More specifically, the unstretched sheet may be stretched from about 2.7 times to about 4 times in the longitudinal direction, and from about 2.7 times to about 4 times in the width direction. The longitudinal direction and the width direction may be perpendicular to each other.

The stretching temperature is preferably in the range of Tg + 5 to Tg + 50 deg. C, and the lower the Tg, the better the stretchability, but the breakage may occur. In particular, in order to improve the brittleness, a stretching temperature range of Tg + 10 to Tg + 40 deg. C is preferable.

After initiating the heat setting, the film is relaxed in the longitudinal and transverse directions, and the heat setting temperature range of the stretched sheet is preferably 120 to 260 ° C.

The laminated polyester film according to an embodiment may be formed using two or more polyester resins formed with different catalysts. In particular, each layer of the laminated polyester film according to the embodiment contains different polyester resins.

At this time, the first layer may include a first polyester resin prepared by using a germanium compound as a catalyst, and the second layer may include a second polyester resin prepared by using an antimony compound as a catalyst.

Accordingly, the first layer and the second layer have different characteristics. The first polyester resin has a high viscosity and can have a low refractive index. Further, the second polyester resin may have a low viscosity and a high refractive index.

Thus, the first layer and the second layer having different characteristics are stacked on each other. Particularly, in the laminated polyester film having three or more layers, the first polyester resin constitutes a skin layer and the second polyester resin constitutes a core layer. That is, the second polyester resin of the laminated unoriented sheet may be positioned between the first polyester resin and the third polyester resin.

Thus, the first layer and the second layer are appropriately combined so that the laminated polyester film according to the embodiment has improved brightness and low oligomer elution properties.

Accordingly, the laminated polyester film according to the embodiment can be used as a substrate for ITO, a substrate for prism for LCD backlight unit, a substrate for silver nanowire, and a substrate for metal mesh.

Hereinafter, the present invention will be described in more detail by way of examples. The following examples are illustrative of the present invention, but the present invention is not limited to the following examples.

Examples and Comparative Examples

Polyethylene terephthalate 1 (manufactured by using a germanium oxide catalyst, IV 0.7 dl / g, Tg 82.5 ° C, Tm 253 ° C, residual germanium content 30 pp in the chip) and polyethylene terephthalate 2 (manufactured by SKC product using antimony oxide catalyst , IV 0.615 dl / g). Thereafter, a polyester film was produced by the following process in a layer configuration as shown in Table 1 below.

Each polyethylene terephthalate (PET) was melt-extruded through an extruder at about 280 DEG C and then cooled in a casting roll at about 20 DEG C to prepare an unoriented sheet. The unoriented sheet thus obtained was immediately heated to 60 ° C and then stretched at about 110 ° C, about three times in the longitudinal direction and about three times in the width direction. Thereafter, the stretched sheet was heat set at about 120 DEG C for about 30 seconds. Thus, a polyethylene terephthalate film was produced.

division Floor composition Thickness (μm) Thickness ratio Example 1 PET1 / PET2 / PET1 250 10/230/10 Example 2 PET1 / PET2 / PET1 250 20/210/20 Comparative Example 1 PET2 250 250

Test Example  One: Hayes  change

In order to examine the haze change of the film, the films obtained in Examples and Comparative Examples were left in an oven at 130 캜 for about 3 minutes, and the rate of change of haze was measured. The results are shown in Table 2 below.

Test Example  2: heat Contraction ratio  change

In order to examine the thermal shrinkage change of the film, the films obtained in the above Examples and Comparative Examples were allowed to stand in an oven at 150 캜 for about 30 minutes, and the heat shrinkage ratio in the longitudinal direction and the width direction was measured. The results are shown in Table 2 below.

division Heat shrinkage (MD) Heat shrinkage (TD) Width direction refractive index Transmittance Haze (%) Change in Haze (%) Example 1 0.75 0.1 1.681 90.5 0.20 0.8 Example 2 0.70 0.05 1.680 90.6 0.15 0.7 Comparative Example 1 0.75 0.1 1.684 90.5 0.25 19

As shown in Table 2, it was confirmed that the three-layer laminated films of Examples 1 and 2 had a large difference in refractive index compared to Comparative Example 1 having a single layer structure, and had excellent heat shrinkage characteristics and moldability, A substrate for a prism of a unit, a substrate for a silver nanowire, and a substrate for a metal mesh.

Claims (16)

A first layer comprising a first polyester resin made from a first catalyst; And
A second layer comprising a second polyester resin made from a second catalyst different from the first catalyst;
≪ / RTI >
The method according to claim 1,
Wherein the first catalyst is selected from a germanium compound or a titanium compound, and the second catalyst is an antimony compound.
The method according to claim 1,
Wherein the laminated polyester film further comprises a third layer comprising a third polyester resin made from the first catalyst and the second layer is located between the first and third layers, Ester film.
The method according to claim 1,
Wherein a viscosity of the first polyester resin is higher than a viscosity of the second polyester resin.
The method according to claim 1,
Wherein the refractive index of the first layer is smaller than the refractive index of the second layer.
The method according to claim 1,
Wherein the first polyester resin has an intrinsic viscosity (IV viscosity) of 0.65 to 0.75 dl / g and an intrinsic viscosity (IV viscosity) of the second polyester resin is 0.55 to 0.65 dl / g.
The method of claim 3,
Wherein the third polyester resin is produced by catalyzing a germanium or titanium compound.
The method of claim 3,
Wherein the first polyester resin, the second polyester resin and the third polyester resin are polyethylene terephthalate.
The method of claim 3,
The ratio of the thickness of the first layer and the thickness of the second layer is 1: 20 to 1: 3,
Wherein the ratio of the thickness of the third layer and the thickness of the second layer is from 1:20 to 1: 3.
The method of claim 3,
Wherein the sum of the thicknesses of the first layer, the second layer and the third layer is 100 mu m to 300 mu m.
11. The method according to any one of claims 1 to 10,
Wherein the film is used as a substrate for ITO, a substrate of a prism for an LCD backlight unit, a substrate for silver nanowires, and a substrate for a metal mesh.
(a) preparing a first polyester resin using a germanium compound as a catalyst;
(b) preparing a second polyester resin using an antimony compound as a catalyst;
(c) simultaneously extruding the polyester resins to produce a laminated undrawn sheet; And
(d) stretching the unstretched sheet.
13. The method of claim 12,
Further comprising, after the step (b), a step of producing a third polyester resin by using a germanium compound as a catalyst.
14. The method of claim 13,
And the second polyester resin of the laminated unstretched sheet is positioned between the first polyester resin and the third polyester resin.
13. The method of claim 12,
Wherein the unstretched sheet is stretched 2.5 to 6 times in the longitudinal direction and 2.5 to 6 times in the width direction.
16. The method of claim 15,
Wherein the stretched sheet is thermally fixed at a temperature of 120 ° C to 260 ° C in the step (d).