KR102589138B1 - High transparent polyester film - Google Patents

Abstract

The present invention relates to a highly transparent polyester film, and relates to a polyester film with excellent antistatic properties, water resistance, and optical properties.

Description

Highly transparent polyester film {HIGH TRANSPARENT POLYESTER FILM}

The present invention relates to a highly transparent polyester film, and relates to a polyester film with excellent antistatic properties, water resistance, and optical properties.

Polyester film is used as a support for semiconductor materials and films for dry film resist (DFR).

Recently, the circuits to be formed have become very complex, the lines have become thinner, and the gaps between them have become narrower, and in line with the trend of high-resolution products, highly transparent and thin polyester films are required. If the transparency of the polyester film used as a support is low, the photoresist layer is not sufficiently exposed during the exposure process, and if the haze of the film is high and the surface roughness is rough, the photoresist layer is damaged by scattering of light on the film surface and inside. In the process, light scattering occurs, the resist surface becomes uneven, and resolution deteriorates.

In addition, polyester films that are transparent and have a low surface roughness may cause defects and electrical charges during the film manufacturing and winding process. A method of imparting antistatic performance to a film is to form a coating layer on the film using an aqueous coating composition containing a surfactant. The antistatic performance of the surfactant type is greatly affected by moisture, so the antistatic performance is excellent in high humidity conditions, but the antistatic performance is significantly reduced in dry conditions. When stored for a long time, the antistatic agent of the surfactant type migrates and the film deteriorates. There is a problem in which the haze of the film increases as a factor that reduces the transparency of the film.

Therefore, there has been a demand for a polyester film with low haze, excellent light transmittance, and excellent antistatic performance.

Japanese Patent Publication No. 2000-221688 (2000.08.11)

The purpose of the present invention is to provide a highly transparent polyester film that has no migration of antistatic agents, can maintain antistatic properties and high transparency of the film for a long period of time, and can maintain antistatic properties even when in direct contact with moisture. There is.

In addition, the purpose is to provide a polyester film with excellent light transmittance and antistatic properties that can form a high-resolution pattern when applied as a support for dry film resist.

In addition, the purpose is to provide a polyester film that can satisfy running characteristics and winding characteristics without using an anti-blocking agent inside the film when manufacturing the polyester film.

One aspect of the present invention includes a polyester base layer containing no inorganic particles and an antistatic coating layer laminated on one or both sides of the polyester base layer,

The antistatic coating layer is a polyester film formed by applying and stretching a water-dispersible antistatic composition containing a conductive polymer, a polyurethane-based water-dispersible binder, inorganic particles, and water.

The polyester film of the present invention has antistatic properties and has excellent transmittance, so it can be used as various optical members for displays.

More specifically, the polyester film of the present invention can be used as a support for a high-resolution dry film resist or as a window film.

Figure 1 is an 800x enlarged photograph to show an example of being evaluated as ○ when evaluating a side wall.
Figure 2 is an 800x enlarged photograph to show an example of being evaluated as × when evaluating a side wall.

Hereinafter, the present invention will be described in more detail through the accompanying specific examples or examples. However, the following specific examples or examples are only a reference for explaining the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Additionally, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The terminology used in the description herein is merely to effectively describe specific embodiments and is not intended to limit the invention.

Additionally, as used in the specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to also include the plural forms, unless the context clearly dictates otherwise.

One aspect of the present invention includes a polyester base layer made of particle-free polyester resin and an antistatic coating layer laminated on one or both sides of the polyester base layer,

The antistatic coating layer is a polyester film formed by applying and stretching a water-dispersible antistatic composition containing a conductive polymer, a polyurethane-based water-dispersible binder, inorganic particles, and water.

In one aspect of the present invention, the polyester film may have a b* of less than 0 as measured by a colorimeter.

In one aspect of the present invention, the polyester film may have a total light transmittance of 90% or more, an initial haze of less than 0.5%, and a haze change amount ΔH according to Equation 1 below of 0.1% or less.

[Equation 1]

△H = Hf - Hi

(In Equation 1 above, Hf is the haze of the polyester film measured after being left at 25°C and RH 50% for 180 days, Hi is the haze of the initial polyester film before leaving, and the unit is %.)

In one aspect of the present invention, the polyester film has an initial surface resistance SRf of 10 ¹³ Ω/sq or less, is immersed in water for 45 minutes, dried at 60°C for 10 minutes, and left at 25°C and RH 60% for 30 minutes. The surface resistance SRi measured after is 10 ¹³ Ω/sq or less, and the surface resistance change amount △SR according to Equation 2 below may be 10 ¹ Ω/sq or less.

[Equation 2]

△SR = SRf - SRi

(In Equation 2 above, SRf is the surface resistance of the polyester film measured after being immersed in water for 45 minutes, dried at 60°C for 10 minutes, and left at 25°C and RH 60% for 30 minutes, and SRi is the initial polyester film. is the surface resistance, and the unit is Ω/sq.)

In one aspect of the present invention, the conductive polymer is a conductive polymer solution in which one or more conductive polymers selected from the group consisting of polyaniline-based polymers, polypyrrole-based polymers, polythiophene-based polymers, and derivatives thereof are doped with a dopant. It may be.

In one aspect of the present invention, the inorganic particles may be colloidal silica with an average particle diameter of 50 to 500 nm.

In one aspect of the present invention, the water-dispersible antistatic composition may further include any one or more selected from organic solvents, wetting agents, emulsifiers, and cross-linking agents.

In one aspect of the present invention, the solid content of the inorganic particles may be 10% by weight or less among the total solid content of the water-dispersible antistatic composition.

In one aspect of the present invention, the polyester base layer may have a thickness of 10 to 250 ㎛, and the antistatic coating layer may have a thickness of 10 to 150 nm.

In one aspect of the present invention, the polyester base layer does not contain inorganic particles and may be a biaxially oriented polyethylene terephthalate film.

In one aspect of the present invention, the polyester film may be a polyester film for high-resolution dry film resist.

Another aspect of the present invention is a high-resolution dry film resist comprising the polyester film. More specifically, it is a high-resolution dry film resist including the polyester film and the photoresist layer.

The inventors of the present invention have developed a polyester film that has excellent light transmittance and low haze, can maintain antistatic properties and transparency of the film for a long period of time, and can be applied as a support to form high-resolution fine patterns when applied to dry film resist. The study was conducted to provide. As a result, runability and film forming stability can be achieved by applying the particles using an in-line coating method instead of adding inorganic particles, which are usually added in consideration of runability and winding characteristics during polyester film production. The present invention was completed by discovering that all of the above objectives can be achieved by forming a coating layer using an in-line coating method by applying a water-dispersible antistatic composition of a specific composition.

Hereinafter, the configuration of the present invention will be described in more detail.

(1) Polyester base layer

In one aspect of the present invention, the polyester base layer is characterized in that it does not contain particles, more specifically, inorganic particles. In other words, it may be a biaxially oriented polyester film produced by melting and extruding particle-free polyester resin chips into a sheet and then biaxially stretching them.

More specifically, the polyester resin used in the polyester base layer is preferably polyethylene terephthalate because it has excellent mechanical properties and transparency, but is not limited thereto.

More specifically, the polyethylene terephthalate resin used in the polyester base layer can have an intrinsic viscosity of 0.5 to 1.0, and more preferably 0.60 to 0.80 because it has excellent heat resistance and excellent film processability.

In one aspect of the present invention, the polyester base layer may be one layer or two or more layers laminated, and all layers may not contain inorganic particles.

In one aspect of the present invention, the thickness of the polyester base layer may be 10 to 250 ㎛, more specifically 10 to 150 ㎛, and in order to be used as a support for a high-resolution dry film resist, it may be 10 to 20 ㎛. , but is not limited to this.

(2) Anti-static coating layer

In one aspect of the present invention, the antistatic coating layer may be formed on one or both sides of the polyester base layer, and an antistatic composition containing a conductive polymer, a polyurethane-based water-dispersible binder, and inorganic particles may be applied using an in-line application method. It can be applied to improve runability, film forming stability, and winding ability when forming a film of a polyester base layer that does not contain the above particles, and can provide a film with excellent antistatic properties and optical properties.

That is, when manufacturing the polyester film used as the polyester base layer, the polyester resin is melt-extruded and stretched in the machine direction, and then a water-dispersible antistatic composition to form an antistatic coating layer is applied, and then stretched in the width direction. An antistatic coating layer may be formed by stretching and heat treatment.

In one aspect of the present invention, the thickness of the antistatic coating layer may be 10 to 150 nm, more specifically 15 to 100 nm, and more specifically 20 to 60 nm.

In one aspect of the present invention, the antistatic coating layer is formed by applying the water-dispersible antistatic composition, comprising 1 to 30% by weight of a conductive polymer, 60 to 90% by weight of a polyurethane-based water-dispersible binder, based on 100% by weight of solid content, It may contain 1 to 10% by weight of inorganic particles.

In one aspect of the present invention, the water-dispersible antistatic composition used to form the antistatic coating layer may include a conductive polymer, a polyurethane-based water-dispersible binder, inorganic particles, and water. Additionally, if necessary, it may further include one or more selected from organic solvents, wetting agents, emulsifiers, and cross-linking agents.

More specifically, in one aspect of the present invention, the water-dispersible antistatic composition used to form the antistatic coating layer may include a conductive polymer, a polyurethane-based water-dispersible binder, inorganic particles, a wetting agent, an organic solvent, and water. there is.

In one aspect of the present invention, the water-dispersible antistatic composition includes 5 to 50% by weight of a conductive polymer solution with a solids content of 1 to 3% by weight, and a polyurethane-based water-dispersible binder solution with a solids content of 30 to 40% by weight 1 to 20%. % by weight, it may contain 3 to 50 wt% of organic solvent, 0.01 to 5 wt% of colloidal silica with a solid content of 10 to 40 wt%, and a residual amount of water.

In addition, if necessary, it further contains one or more additives selected from silicone-based wetting agents, fluorine-based wetting agents, slip agents, anti-foaming agents, wetting agents, surfactants, thickeners, plasticizers, antioxidants, ultraviolet absorbers, preservatives, cross-linking agents, etc. You can.

In one aspect of the present invention, the conductive polymer may be a conductive polymer solution doped with a dopant, such as a polycyphene-based, polypyrrole-based, or polyaniline-based polymer resin, but is not limited thereto. Even better, it is better to use a polythiophene-based conductive polymer resin, and most preferably, it is to use a conductive polymer solution in which poly(3,4-ethylenedioxythiophene) is doped with polystyrene sulfonic acid (PEDOT:PSS). It has excellent water dispersibility, so an antistatic coating layer can be formed through an in-line application process. Transparency does not deteriorate even after going through a stretching process after the in-line application process, and this is desirable from the viewpoint of heat resistance and desired surface resistance. The conductive polymer has a surface resistance of 10 ¹³ Ω/sq or less. More specifically, it is preferably used in a range that satisfies the physical properties of 10 ⁵ to 10 ¹³ Ω/sq, but is not limited thereto. Additionally, from the viewpoint of minimizing the width-to-width deviation of antistatic properties when biaxially stretching the polyester film, the conductive polymer may be used with an average particle diameter of 50 to 100 nm.

The conductive polymer may be used as a conductive polymer solution mixed in a solvent to achieve optimal dispersibility. Specifically, for example, when using PEDOT:PSS, it can be used in water, alcohol, solvents with a high dielectric constant, etc. It may be used in combination. Commercial examples include Clevios P (solid content 1.2 to 1.4 wt%) from Heraeus, but are not limited thereto.

The content of the conductive polymer solution in the water-dispersible antistatic composition may be 5 to 50% by weight, more preferably 6 to 20% by weight, within the above range sufficient to achieve the desired physical properties. It is not limited to content or this.

In one aspect of the present invention, by using the water-based polyurethane binder mixed with a conductive polymer, miscibility is excellent, surface resistance performance is improved, adhesion to the polyester base film is excellent, and physical properties change under high temperature and high humidity conditions. It is possible to form an antistatic layer with less yellowing phenomenon.

In one aspect, the polyurethane-based water-dispersible binder is not particularly limited, but includes at least one functional group selected from the group consisting of a hydroxyl group, an amine group, an alkyl group, and a carboxyl group to improve moisture resistance and film adhesion. It may be an anionic polyether-based urethane dispersion. At this time, the dispersion may be particles with an average particle diameter of 10 to 200 nm dispersed in a colloidal state using water as a dispersion medium. Specifically, it may be used as an aqueous dispersion with a solid content of 30 to 40% by weight.

The polyurethane-based water-dispersible binder can achieve excellent heat resistance and low surface resistance change rate by using a polyurethane binder made by reacting polycarbonate-based polyol with diisocyanate. More preferably, the use of hexamethylene diisocyanate as a specific example of the diisocyanate is good from the viewpoint of improving heat resistance and forming a coating film with less yellowing phenomenon, but is not limited thereto.

In addition, the polyurethane-based water-dispersible binder may be dispersed in a solvent, and the solvent is not limited to one or two or more selected from the group consisting of amide-based organic solvents and aprotic highly polar (AHD) organic solvents. A mixed solvent may be used, but is not limited thereto. Commercialized examples include, but are not limited to, Neo Resins' Neo Rez R-860, R-960, and R-972.

The content of the polyurethane-based water-dispersible binder in the water-dispersible antistatic composition may be 1 to 20% by weight, more preferably 2 to 10% by weight, and the content within the above range is sufficient to achieve the desired physical properties, but is limited thereto. It doesn't work.

In one aspect of the present invention, it is preferable to use colloidal silica having a solid content of 10 to 40% by weight as the inorganic particle because it has excellent dispersibility in the composition and can provide a film with excellent optical properties, and has an average particle diameter of Using colloidal silica of 50 to 500 nm, more specifically 80 to 450 nm, can achieve the desired optical properties such as light transmittance and haze, and when used as a support for DFR, high-resolution fine patterns can be achieved. It is preferable because it can form.

In the water-dispersible antistatic composition, the content of colloidal silica having a solid content of 10 to 40 wt% may be 0.01 to 5 wt%, more preferably 0.2 to 2 wt%, and the desired physical properties may be achieved within the above range. The amount is sufficient to achieve this, but is not limited thereto.

In one aspect of the present invention, the organic solvent used in the water-dispersible antistatic composition is any one or two or more selected from alcohol-based organic solvents, aprotic highly polar (AHD) organic solvents, and amide-based organic solvents. It may be a mixed solvent.

The content of the organic solvent may be 3 to 50% by weight, more specifically 5 to 40% by weight, and more specifically 10 to 30% by weight of the water-dispersible antistatic composition, and within the above range, the conductive polymer and polyurethane-based moisture The content is suitable for improving the dispersibility of the acidic binder, but is not limited thereto.

Even better, by using one or two or more mixed solvents selected from aprotic highly polar organic solvents and amide-based organic solvents along with alcohol-based organic solvents, the dispersibility of the conductive polymer is improved, and doping is activated to increase surface resistance. This can result in further improved performance.

More specifically, 1 to 30% by weight of an alcohol-based organic solvent, more specifically 5 to 20% by weight and 2 to 20% by weight of any one or two or more mixed solvents selected from aprotic highly polar organic solvents and amide-based organic solvents. Specifically, 5 to 10% by weight may be used.

The alcohol-based organic solvent is not limited, but specific examples include methanol, ethanol, propanol, isopropanol, butanol, and 2-amino-2-methyl-1-propanol, and may be used alone or in a mixture of two or more. You can use it. By using an alcohol-based organic solvent, the miscibility and dispersibility between the conductive polymer and the water-based polyurethane resin can be further improved.

The aprotic highly polar organic solvent is not limited, but specifically, for example, dimethyl sulfoxide, propylene carbonate, etc. may be used, and may be used alone or in a mixture of two or more. The conductivity of the conductive polymer can be further improved by using an aprotic, highly polar organic solvent. When an aprotic highly polar organic solvent is used alone, a dispersion stabilizer such as ethylene glycol, glycerin, and sorbitol may be further included, but is not limited thereto.

The amide-based organic solvent is not limited, but specifically includes, for example, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N-dimethylacetamide, N- Methylpyrrolidone and 2-amino-2-methyl-1-propanol may be used, and may be used alone or in combination of two or more. The conductivity of the conductive polymer can be further improved by using an amide-based organic solvent.

In one aspect of the present invention, the water-dispersible antistatic composition may further include a wetting agent to further improve coating properties. Although not limited, specific examples include modified silicone-based wetting agents such as Dow Corning's Q2-5212, ENBODIC's TEGO WET 250, BYK CHEMIE's BYK 348, and fluorine-based wetting agents such as Zonyl's FSH. It is not limited. The wetting agent is preferably used in an amount of 0.1 to 2% by weight, and the desired coating property improvement can be achieved within the above range, but is not limited thereto.

In one aspect of the present invention, the water-dispersible antistatic composition may further include a curing agent, and any curing agent commonly used for polyurethane-based water-dispersible binders may be used without limitation.

In one aspect of the present invention, the thickness of the antistatic coating layer may be 10 to 150 nm when applied dry. The above range is preferable because it forms a coating layer that has excellent surface resistance and does not cause blocking.

(3) Physical properties of polyester film

The polyester film according to one aspect of the present invention may have a blue color with b* measured with a colorimeter being less than 0. More specifically, b* may be a real number selected from -10 to -1, and more specifically, a real number selected from -2 to -8. The b* refers to the value measured by the measurement method described later.

Additionally, the polyester film according to one aspect of the present invention may have a total light transmittance of 90% or more, an initial haze of less than 0.5%, and a haze change amount ΔH according to Equation 1 below of 0.1% or less.

[Equation 1]

△H = Hf - Hi

(In Equation 1 above, Hf is the haze of the polyester film measured after being left at 25°C and RH 50% for 180 days, Hi is the haze of the initial polyester film before leaving, and the unit is %.)

In addition, the polyester film according to one aspect of the present invention has an initial surface resistance SRf of 10 ¹³ Ω/sq or less, is immersed in water for 45 minutes, dried at 60 ° C. for 10 minutes, and left at 25 ° C. and RH 60% for 30 minutes. The surface resistance SRi measured after treatment may be 10 ¹³ Ω/sq or less, and the surface resistance change amount △SR according to Equation 2 below may be 10 ¹ Ω/sq or less.

[Equation 2]

△SR = SRf - SRi

(In Equation 2 above, SRf is the surface resistance of the polyester film measured after being immersed in water for 45 minutes, dried at 60°C for 10 minutes, and left at 25°C and RH 60% for 30 minutes, and SRi is the initial polyester film. is the surface resistance, and the unit is Ω/sq.)

(4) Manufacturing method of polyester film

In one aspect of the present invention, the water-dispersible antistatic composition may be applied by an in-line application method during the polyester film manufacturing process. That is, when manufacturing a polyester base film, it can be manufactured by applying it using an in-line coating method before stretching or after primary stretching and before secondary stretching, and then stretching. During the secondary stretching and heat setting, water evaporates by heating and becomes charged. An anti-inflammatory coating layer may be formed. The application method is not limited as long as it is a known application method.

More specifically, for example, a polyester resin chip containing no particles is melt-extruded to produce an unstretched sheet, uniaxially stretched in the machine direction, then the water-dispersible antistatic composition is applied, and then stretched again in the width direction. It may be manufactured by stretching, followed by heat treatment and relaxation. The stretching is not limited, but may be stretched 1.5 to 6 times, more specifically 2 to 4 times. The heat treatment may be performed at 220 to 250°C, more specifically, 230 to 240°C, but is not limited thereto. The relaxation may be 5 to 20%, more specifically 10 to 15%, in the machine and transverse directions, but is not limited thereto.

The present invention will be described in more detail below based on examples and comparative examples. However, the following Examples and Comparative Examples are only one example to explain the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

The physical properties of the films prepared in Examples and Comparative Examples were evaluated as follows.

1) Haze and total light transmittance

A specimen of the deposited film was measured using a HAZE METER (Model name: Nipon denshoku, Model NDH 5000).

2) Haze change rate (△H)

The film was placed in a box with an open top of 3cm in height, 21cm in width, and 27cm in length, heat treated at 85°C, 85%, 72Hr and 60°C, 95%, 120Hr, respectively, and left for 5 minutes. Afterwards, the haze change rate (△H) was measured using a HAZE METER (Nipon denshoku, Model NDH 5000) according to the JIS K 715 standard.

The haze change rate was calculated according to Equation 1 below, and the light transmittance change rate was calculated according to Equation 2 below.

[Calculation Formula 1]

△H = H _f - H _i

In the above formula, H _f is the haze of the film after being maintained at 85°C and 85% for 72 hours or 60°C and 95% for 120 hours, and Hi is the haze of the film before heating.

3) Color meter

The film color was confirmed using a color meter. The measurement method was using Konica Minolta (CM-512m3) equipment, measuring 30 sheets (480㎛) of 16㎛ film overlapping and comparing the film color with b*, which indicates the color of the film.

The color (b*) of the film measured at this time was measured by forming an antistatic layer using an in-line coating method and then stretching it.

4) Surface resistance

The surface resistance of the antistatic layer of the present invention was evaluated. The measurement method is Mitsubishi Chemical Corp. Surface resistance was measured using Hiresta-Up MCP-HP450 equipment under the conditions of 25℃, 50%RH, 100V, and 10 seconds.

The surface resistance of the film measured at this time was measured by forming an antistatic coating layer using an in-line coating method and then stretching it.

In the measurement results, Over means a state where more than 10 ¹⁴ Ω/sq is measured when measuring surface resistance and no electricity flows.

5) Water resistance

The water resistance and surface resistance of the antistatic layer of the present invention were evaluated.

Measure the initial surface resistance of the coating film (100 x 100mm).

Soak the coating film in 500ml water for 45 minutes.

After washing the surface of the film with water three times, remove moisture to avoid damaging the surface.

Leave in the oven at 60℃ for 10 minutes.

Leave it at 25℃ and 60%RH for 30 minutes.

Measure surface resistance using the surface resistance measurement method in 4) above.

6) Transferability: Surface resistance after transfer evaluation

After transfer evaluation of the antistatic layer, surface resistance was evaluated. For the transfer evaluation, a weight of 50 g/cm2 was placed on top of the film with the antistatic side of the film and the coating back side in contact, and the surface resistance of the coated back side was measured after leaving it at 40°C for 3 days. The surface resistance measurement method behind the coating was described by Mitsubishi Chemical Corp. Surface resistance was measured using Hiresta-Up MCP-HP450 equipment under the conditions of 25℃, 50%RH, 100V, and 10 seconds.

OK is Over (above 10 ¹⁴ Ω/sq) where surface resistance is not measured, and NG is below 10 ¹³ Ω/sq where surface resistance is measured.

7) Side Wall Evaluation Method

Dry film resist properties were evaluated by applying it as a support for dry film resist (DFR). A photoresist layer was formed on the antistatic coating layer of the film prepared in Examples and Preparation Examples, and a polyolefin film was laminated thereon as a protective layer. A printed circuit was produced using the obtained dry film resist.

That is, the photoresist layer surface of the dry film resist from which the protective layer was peeled was brought into close contact with a copper plate prepared on an epoxy resin plate containing glass fiber. Next, the glass plate on which the circuit was printed was brought into close contact with the dry film resist, and exposure to ultraviolet rays was performed from the side of the glass plate. This circuit was a high-end circuit with a line thickness of 14 ㎛ and a space spacing of 14 ㎛.

Afterwards, the dry film resist was peeled off and a series of development operations such as washing and etching were performed to fabricate the circuit. The side wall of the circuit obtained in this way was observed using a microscope.

○: As shown in Figure 1, the surface of the side wall is formed very smooth, and no protrusions are observed at all.

△: Some protrusions are formed on the surface of the side wall, and the surface appears to be smooth.

×: As shown in Figure 2, the surface of the side wall is not smooth and is very uneven.

[Production Example 1]

Preparation of water-dispersible antistatic composition (1)

60% by weight of conductive polymer aqueous dispersion (Heraeus, Clevios P solid content 1.3% by weight), 6% by weight of water, and 5% by weight of isopropyl alcohol were placed in a mixing vessel, stirred for 1 hour, and 2-amino-2-methyl-1 -Additionally 2% by weight of propanol (Alfa aesar, 95%) was added to the mixing container and stirred for another hour, then 20% by weight of water-based polyurethane binder resin (Neo rez R-960, manufactured by Neo Resins, solid content 31% by weight) was added. After stirring again for 30 minutes, 5% by weight of dimethyl sulfoxide and 2% by weight of silicone-based wetting agent (BYK 348) were added to the mixing container and stirred for an additional hour to prepare a primary antistatic coating composition. Then, the primary antistatic coating composition is prepared by secondary dilution. At this time, 30% by weight of the primary antistatic coating composition, 69.2% by weight of water, 0.4% by weight of colloidal silica (0.3㎛, solid content 20% by weight), and 0.4% by weight of fluorine-based wetting agent (Zonyl FSH) were mixed to form a water-dispersible antistatic agent. Composition (1) was prepared.

[Production Example 2]

Preparation of water-dispersible antistatic composition (2)

60% by weight of conductive polymer aqueous dispersion (Heraeus, Clevios P solid content 1.3% by weight), 6% by weight of water, and 5% by weight of isopropyl alcohol were placed in a mixing vessel, stirred for 1 hour, and 2-amino-2-methyl-1 -Additionally 2% by weight of propanol (Alfa aesar, 95%) was added to the mixing container and stirred for another hour, and then 20% by weight of water-based polyurethane binder resin (Neo rez R-960 from Neo resins, solid content 31% by weight) was added. After stirring again for 30 minutes, 5% by weight of dimethyl sulfoxide and 2% by weight of silicone-based wetting agent (BYK 348) were added to the mixing container and stirred for an additional hour to prepare a primary antistatic coating composition. Then, the primary antistatic coating composition is prepared by secondary dilution. At this time, 20% by weight of the primary antistatic coating composition, 79.2% by weight of water, 0.4% by weight of colloidal silica (0.3㎛ solid content 20% by weight), and 0.4% by weight of fluorine-based wetting agent (Zonyl FSH) were mixed to form a water-dispersible antistatic composition. (2) was prepared.

[Production Example 3]

Preparation of water-dispersible antistatic composition (3)

60% by weight of conductive polymer aqueous dispersion (Heraeus, Clevios P solid content 1.3% by weight), 6% by weight of water, and 5% by weight of isopropyl alcohol were placed in a mixing vessel, stirred for 1 hour, and 2-amino-2-methyl-1 -Additionally 2% by weight of propanol (Alfa aesar, 95%) was added to the mixing container and stirred for another hour, and then 20% by weight of water-based polyurethane binder resin (Neo rez R-960 from Neo resins, solid content 31% by weight) was added. After stirring again for 30 minutes, 5% by weight of dimethyl sulfoxide and 2% by weight of silicone-based wetting agent (BYK 348) were added to the mixing container and stirred for an additional hour to prepare a primary antistatic coating composition. Then, the primary antistatic coating composition is prepared by secondary dilution. At this time, 10% by weight of the primary antistatic coating composition, 89.2% by weight of water, 0.4% by weight of colloidal silica (0.3㎛ solid content 20% by weight), and 0.4% by weight of fluorine-based wetting agent (Zonyl FSH) were mixed to form a water-dispersible antistatic composition. (3) was prepared.

[Production Example 4]

Preparation of water-dispersible antistatic composition (4)

Acrylic water dispersion (ATX-014 from Takamatsu, Japan, solid content 40% by weight) 5.18% by weight, anionic polymer antistatic agent (Jinbo Co., Ltd., ICP-323, molecular weight 100,000 or more, solid content 25.5% by weight) 9.0% by weight, colloidal A water-dispersible antistatic composition (4) was prepared by mixing 0.4% by weight of silica (0.3㎛ solid content, 20% by weight), 2% by weight of a silicone-based wetting agent (BYK 348), and 83.42% by weight of water.

[Production Example 5]

Preparation of water-dispersible antistatic composition (5)

Acrylic water dispersion (Primal-3208 from Rohm & Haas, solid content 44% by weight) 2.27% by weight, amphoteric antistatic agent (SY Chem, UNISTA 3PN, molecular weight 2,000-3,000, solid content 18.5% by weight) 5.41% by weight, colloidal silica ( A water-dispersible antistatic composition (5) was prepared by mixing 0.4% by weight of 0.3㎛ solid content (20% by weight), 2% by weight of silicone-based wetting agent (BYK 348), and 89.92% by weight of water.

[Production Example 6]

Preparation of water-dispersible antistatic composition (6)

60% by weight of conductive polymer aqueous dispersion (Heraeus, Clevios P solid content 1.3% by weight), 6% by weight of water, and 5% by weight of isopropyl alcohol were placed in a mixing vessel, stirred for 1 hour, and 2-amino-2-methyl-1 -Additionally 2% by weight of propanol (Alfa aesar, 95%) was added to the mixing container and stirred for another hour, and then 20% by weight of water-based polyurethane binder resin (Neo rez R-960 from Neo resins, solid content 31% by weight) was added. After stirring again for 30 minutes, 5% by weight of dimethyl sulfoxide and 2% by weight of silicone-based wetting agent (BYK 348) were added to the mixing container and stirred for an additional hour to prepare a primary antistatic coating composition. Then, the primary antistatic coating composition is prepared by secondary dilution. At this time, 20% by weight of the primary antistatic coating composition, 79.2% by weight of water, 0.27% by weight of colloidal silica (0.08㎛ solid content 40% by weight), and 0.4% by weight of fluorine-based wetting agent (Zonyl FSH) were mixed to form a water-dispersible antistatic composition. (6) was prepared.

[Production Example 7]

Preparation of water-dispersible antistatic composition (7)

60% by weight of conductive polymer aqueous dispersion (Heraeus, Clevios P solid content 1.3% by weight), 6% by weight of water, and 5% by weight of isopropyl alcohol were placed in a mixing vessel, stirred for 1 hour, and 2-amino-2-methyl-1 -Additionally 2% by weight of propanol (Alfa aesar, 95%) was added to the mixing container and stirred for another hour, and then 20% by weight of water-based polyurethane binder resin (Neo rez R-960 from Neo resins, solid content 31% by weight) was added. After stirring again for 30 minutes, 5% by weight of dimethyl sulfoxide and 2% by weight of silicone-based wetting agent (BYK 348) were added to the mixing container and stirred for an additional hour to prepare a primary antistatic coating composition. Then, the primary antistatic coating composition is prepared by secondary dilution. At this time, 20% by weight of the primary antistatic coating composition, 79.2% by weight of water, 0.16% by weight of colloidal silica (0.45㎛ solid content 40% by weight), and 0.4% by weight of fluorine-based wetting agent (Zonyl FSH) were mixed to form a water-dispersible antistatic composition. (7) was prepared.

[Production Example 8]

Preparation of water-dispersible antistatic composition (8)

60% by weight of conductive polymer aqueous dispersion (Heraeus, Clevios P solid content 1.3% by weight), 6% by weight of water, and 5% by weight of isopropyl alcohol were placed in a mixing vessel, stirred for 1 hour, and 2-amino-2-methyl-1 -Additionally 2% by weight of propanol (Alfa aesar, 95%) was added to the mixing container and stirred for another hour, and then 20% by weight of water-based polyurethane binder resin (Neo rez R-960 from Neo resins, solid content 31% by weight) was added. After stirring again for 30 minutes, 5% by weight of dimethyl sulfoxide and 2% by weight of silicone-based wetting agent (BYK 348) were added to the mixing container and stirred for an additional hour to prepare a primary antistatic coating composition. Then, the primary antistatic coating composition is prepared by secondary dilution. At this time, 20% by weight of the primary antistatic coating composition, 79.2% by weight of water, 0.2% by weight of water-dispersed silica (20% by weight of 0.8㎛ solid content), and 0.4% by weight of fluorine-based wetting agent (Zonyl FSH) were mixed to form a water-dispersible antistatic composition. (7) was prepared.

[Production Example 9]

Preparation of water-dispersible antistatic composition (9)

60% by weight of conductive polymer aqueous dispersion (Heraeus, Clevios P solid content 1.3% by weight), 6% by weight of water, and 5% by weight of isopropyl alcohol were placed in a mixing vessel, stirred for 1 hour, and 2-amino-2-methyl-1 -Additionally 2% by weight of propanol (Alfa aesar, 95%) was added to the mixing container and stirred for another hour, and then 20% by weight of water-based polyurethane binder resin (Neo rez R-960 from Neo resins, solid content 31% by weight) was added. After stirring again for 30 minutes, 5% by weight of dimethyl sulfoxide and 2% by weight of silicone-based wetting agent (BYK 348) were added to the mixing container and stirred for an additional hour to prepare a primary antistatic coating composition. Then, the primary antistatic coating composition is prepared by secondary dilution. At this time, 20% by weight of the primary antistatic coating composition, 79.2% by weight of water, 0.3% by weight of water-dispersed PMMA (1.5㎛ solid content 20% by weight), and 0.4% by weight of fluorine-based wetting agent (Zonyl FSH) were mixed to form a water-dispersible antistatic composition. (7) was prepared.

[Production Example 10]

Preparation of water-dispersible antistatic composition (10)

60% by weight of conductive polymer aqueous dispersion (Heraeus, Clevios P solid content 1.3% by weight), 6% by weight of water, and 5% by weight of isopropyl alcohol were placed in a mixing vessel, stirred for 1 hour, and 2-amino-2-methyl-1 -Additionally 2% by weight of propanol (Alfa aesar, 95%) was added to the mixing container and stirred for another hour, then 20% by weight of water-based polyurethane binder resin (Neo rez R-960, manufactured by Neo Resins, solid content 31% by weight) was added. After stirring again for 30 minutes, 5% by weight of dimethyl sulfoxide and 2% by weight of silicone-based wetting agent (BYK 348) were added to the mixing container and stirred for an additional hour to prepare a primary antistatic coating composition. Then, the primary antistatic coating composition is prepared by secondary dilution. At this time, a water-dispersible antistatic composition (10) was prepared by mixing 30% by weight of the primary antistatic coating composition, 69.6% by weight of water, and 0.4% by weight of a fluorine-based wetting agent (Zonyl FSH).

[Example 1]

Polyethylene terephthalate chips with moisture removed below 100ppm were melted by injecting them into a melt extruder, and then extruded through a T-die, rapidly cooled and solidified using a casting drum with a surface temperature of 20°C to produce a polyethylene terephthalate sheet with a thickness of 250㎛. .

The prepared polyethylene terephthalate sheet was stretched 3.5 times in the machine direction (MD) at 110°C and then cooled to room temperature. On one side of the uniaxially stretched film, the water-dispersible antistatic composition (1) prepared in Preparation Example 1 was applied using gravure to a thickness of 50 nm after final drying, and then preheated at 140 ° C., dried, and applied in the transverse direction (TD). ) and stretched 4 times. Afterwards, heat treatment was performed at 235°C in a tenter, and the film was relaxed by 10% in the machine and transverse directions at 200°C and heat set to produce a 16㎛ biaxially stretched film with an antistatic coating layer formed on one side.

The physical properties of the produced film were evaluated and are shown in Table 1 below.

[Example 2]

In Example 1, a film was prepared in the same manner as Example 1, except that the water-dispersible antistatic composition (2) prepared in Preparation Example 2 was used instead of the water-dispersible antistatic composition (1).

The physical properties of the produced film were evaluated and are shown in Table 1 below.

[Example 3]

In Example 1, a film was prepared in the same manner as Example 1, except that the water-dispersible antistatic composition (3) prepared in Preparation Example 3 was used instead of the water-dispersible antistatic composition (1).

The physical properties of the produced film were evaluated and are shown in Table 1 below.

[Example 4]

In Example 1, a film was prepared in the same manner as Example 1, except that the water-dispersible antistatic composition (6) prepared in Preparation Example 3 was used instead of the water-dispersible antistatic composition (1).

The physical properties of the produced film were evaluated and are shown in Table 1 below.

[Example 5]

In Example 1, a film was prepared in the same manner as Example 1, except that the water-dispersible antistatic composition (7) prepared in Preparation Example 3 was used instead of the water-dispersible antistatic composition (1).

The physical properties of the produced film were evaluated and are shown in Table 1 below.

[Example 6]

In Example 1, a film was prepared in the same manner as Example 1, except that the water-dispersible antistatic composition (8) prepared in Preparation Example 8 was used instead of the water-dispersible antistatic composition (1).

The physical properties of the produced film were evaluated and are shown in Table 1 below.

[Example 7]

In Example 1, a film was prepared in the same manner as Example 1, except that the water-dispersible antistatic composition (9) prepared in Preparation Example 9 was used instead of the water-dispersible antistatic composition (1).

The physical properties of the produced film were evaluated and are shown in Table 1 below.

[Comparative Example 1]

In Example 1, a film was prepared in the same manner as Example 1, except that the water-dispersible antistatic composition (4) prepared in Preparation Example 4 was used instead of the water-dispersible antistatic composition (1).

The physical properties of the manufactured film were evaluated and are shown in Table 2 below.

[Comparative Example 2]

In Example 1, a film was prepared in the same manner as Example 1, except that the water-dispersible antistatic composition (5) prepared in Preparation Example 5 was used instead of the water-dispersible antistatic composition (1).

The physical properties of the manufactured film were evaluated and are shown in Table 2 below.

[Comparative Example 3]

Polyethylene terephthalate chips containing 300ppm of silica particles with an average particle diameter (D50) of 0.7㎛ and D90 of 2.5㎛, and with moisture removed to less than 100ppm, are injected into a melt extruder and melted, and then extruded through a T-die, with a surface temperature of 20%. A polyethylene terephthalate sheet with a thickness of 250㎛ was manufactured by rapid cooling and solidification using a casting drum at ℃.

The prepared polyethylene terephthalate sheet was stretched 3.5 times in the machine direction (MD) at 110°C and then cooled to room temperature. On one side of the uniaxially stretched film, the water-dispersible antistatic composition (1) prepared in Preparation Example 1 was applied using gravure to a thickness of 50 nm after final drying, and then preheated at 140 ° C., dried, and applied in the transverse direction (TD). ) and stretched 4 times. Afterwards, heat treatment was performed at 235°C in a tenter, and the film was relaxed by 10% in the machine and transverse directions at 200°C and heat set to produce a 16㎛ biaxially stretched film with an antistatic coating layer formed on one side.

The physical properties of the manufactured film were evaluated and are shown in Table 2 below.

[Comparative Example 4]

Polyethylene terephthalate chips containing 300ppm of silica particles with an average particle diameter (D50) of 0.7㎛ and D90 of 2.5㎛, and with moisture removed to less than 100ppm, are injected into a melt extruder and melted, and then extruded through a T-die, with a surface temperature of 20%. A polyethylene terephthalate sheet with a thickness of 250㎛ was manufactured by rapid cooling and solidification using a casting drum at ℃.

The prepared polyethylene terephthalate sheet was stretched 3.5 times in the machine direction (MD) at 110°C and then cooled to room temperature. The uniaxially stretched film was preheated at 140°C and stretched 4 times in the transverse direction (TD). Afterwards, heat treatment was performed at 235°C in a tenter, and the film was relaxed by 10% in the machine and transverse directions at 200°C and heat set to produce a 16㎛ biaxially stretched film.

The physical properties of the manufactured film were evaluated and are shown in Table 2 below.

[Comparative Example 5]

Polyethylene terephthalate chips containing 300ppm of silica particles with an average particle diameter (D50) of 0.7㎛ and D90 of 2.5㎛, and with moisture removed to less than 100ppm, are injected into a melt extruder and melted, and then extruded through a T-die, with a surface temperature of 20%. A polyethylene terephthalate sheet with a thickness of 250㎛ was manufactured by rapid cooling and solidification using a casting drum at ℃.

The prepared polyethylene terephthalate sheet was stretched 3.5 times in the machine direction (MD) at 110°C and then cooled to room temperature. On one side of the uniaxially stretched film, the water-dispersible antistatic composition (10) prepared in Preparation Example 10 was applied using gravure to a thickness of 50 nm after final drying, followed by preheating and drying at 140°C and applying it in the transverse direction (TD). ) and stretched 4 times. Afterwards, heat treatment was performed at 235°C in a tenter, and the film was relaxed by 10% in the machine and transverse directions at 200°C and heat set to produce a 16㎛ biaxially stretched film with an antistatic coating layer formed on one side.

The physical properties of the manufactured film were evaluated and are shown in Table 2 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Water-dispersible antistatic composition (One) (2) (3) (6) (7) (8) (9) Optical properties Haze
(%) 0.33 0.34 0.33 0.3 0.45 0.5 0.45 Total light transmittance (%) 90.45 90.42 90.4 90.5 90.46 90.5 90.5 Optical characteristic change rate (left for 180 days) Hi (early) 0.33 0.34 0.33 0.3 0.45 0.5 0.45 Hf
(After neglect) 0.37 0.39 0.38 0.35 0.49 0.53 0.49 △H 0.04 0.05 0.05 0.05 0.04 0.03 0.04 colorimeter b* -7.25 -6.28 -4.2 -6.25 -6.26 -6.31 -6.28 Surface resistance (Ω/sq) 5.85E+07 4.14E+09 1.72E+12 3.24E+09 4.55E+09 3.89E+09 3.68E+09 water resistance 6.56E+07 4.55E+09 3.25E+12 3.56E+09 5.25E+09 4.02E+09 3.87E+09 transferability OK OK OK OK OK OK OK Side wall evaluation ○ ○ ○ ○ ○ △ △

Comparative Example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Water dispersible antistatic composition (4) (5) (One) - (10) Optical properties Haze (%) 0.33 0.34 1.56 1.48 1.41 Total light transmittance (%) 90.4 90.7 90.52 89.69 90.6 Optical properties change rate (left for 180 days) Hi (early) 0.33 0.34 1.56 1.48 1.41 Hf
(After neglect) 1.14 1.09 1.61 1.49 1.45 △H 0.81 0.75 0.05 0.01 0.04 colorimeter b* 1.03 1.44 -1.24 2.5 -1.29 Surface resistance (Ω/sq) 3.56E+09 1.25E+09 3.89E+07 Over 2.56E+07 water resistance OVER OVER 4.35E+07 - 2.86E+07 transferability OK NG OK - OK Side wall evaluation △ △ × × ×

As shown in Table 1, it can be seen that the polyester film according to the present invention is excellent in both optical properties and antistatic properties, and it can be seen that it exhibits antistatic performance even after direct contact with moisture. In addition, the color of the film confirmed by the colorimeter was blue, making it suitable for use as an optical film.

Additionally, in Examples 1 to 5, it was confirmed that high-resolution fine patterns could be formed when applied to DFR.

As shown in Comparative Examples 1 and 2 in Table 2, when a surfactant-type antistatic agent and an acrylic water dispersion were used, initial surface resistance was developed, but it was confirmed that the antistatic performance was lost after direct contact with moisture. In addition, it was confirmed that the optical properties were deteriorated due to the large haze change, and the color of the film confirmed by the colorimeter was yellow, making it unsuitable for use as an optical film.

In Comparative Examples 3 to 5, it was confirmed that the initial haze was high and the optical properties were poor. In addition, it was confirmed that the side wall characteristics were not good when applied to DFR.

As described above, the present invention has been described with specific details, limited embodiments, and drawings, but these are provided only to facilitate a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention Anyone skilled in the art can make various modifications and variations from this description.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and the scope of the patent claims described below as well as all modifications that are equivalent or equivalent to the scope of this patent claim shall fall within the scope of the spirit of the present invention. .

Claims (11)

It includes a polyester base layer made of particle-free polyester resin and an antistatic coating layer laminated on one or both sides of the polyester base layer,
The polyester base layer does not contain inorganic particles and is a biaxially oriented polyethylene terephthalate film,
The antistatic coating layer includes 5 to 50% by weight of a conductive polymer solution with a solid content of 1 to 3% by weight, 1 to 20% by weight of a polyurethane-based water-dispersible binder solution with a solid content of 30 to 40% by weight, and 3 to 50% by weight of an organic solvent. %, a polyester film formed by applying and stretching a water-dispersible antistatic composition containing 0.01 to 5% by weight of colloidal silica with a solid content of 10 to 40% by weight and the remaining amount of water. According to clause 1,
The polyester film is a polyester film whose b* is less than 0 as measured by a colorimeter. According to clause 1,
The polyester film has a total light transmittance of 90% or more, an initial haze of less than 0.5%, and a haze change amount ΔH according to Equation 1 below of 0.1% or less.
[Equation 1]
△H = Hf - Hi
(In Equation 1 above, Hf is the haze of the polyester film measured after being left at 25°C and RH 50% for 180 days, Hi is the haze of the initial polyester film before leaving, and the unit is %.) According to clause 1,
The polyester film has an initial surface resistance SRf of 10 ¹³ Ω/sq or less, and the surface resistance SRi measured after being immersed in water for 45 minutes, dried at 60°C for 10 minutes, and left at 25°C and RH 60% for 30 minutes is A polyester film ^{with a surface resistance change amount △SR of 10 1 Ω} /sq or less according to Equation 2 below.
[Equation 2]
△SR = SRf - SRi
(In Equation 2 above, SRf is the surface resistance of the polyester film measured after being immersed in water for 45 minutes, dried at 60°C for 10 minutes, and left at 25°C and RH 60% for 30 minutes, and SRi is the initial polyester film. is the surface resistance, and the unit is Ω/sq.) According to clause 1,
The conductive polymer is a polyester film that is a conductive polymer solution doped with a dopant of one or more conductive polymers selected from the group consisting of polyaniline-based, polypyrrole-based, polythiophene-based and their derivatives. According to clause 1,
The colloidal silica is a polyester film with an average particle diameter of 50 to 500 nm. According to clause 1,
The water-dispersible antistatic composition is a polyester film further comprising at least one selected from wetting agents, emulsifiers, and crosslinking agents. delete According to clause 1,
The thickness of the polyester base layer is 10 to 250 ㎛,
A polyester film wherein the antistatic coating layer has a thickness of 10 to 150 nm. delete A high-resolution dry film resist comprising the polyester film of any one of claims 1 to 7 and 9.