KR101646198B1 - Polyethylene Naphthalate Film - Google Patents

Abstract

More particularly, the present invention relates to a polyethylene naphthalate film which is excellent in transparency while having low manufacturing cost, excellent scratch resistance, excellent dimensional stability by heat (low coefficient of linear thermal expansion) A polyethylene naphthalate film which can be used for applications requiring high surface hardness such as substrates for manufacturing processes, substrates for flexible displays including electronic paper (e-paper) or OLED, substrates for solar cells, and substrates for hard coatings used in touch panels . To this end, the polyethylene naphthalate film according to the present invention is characterized in that the nano diamond powder is incorporated into the polyethylene naphthalate resin in an amount of 0.2 to 10 wt% based on the solid content with respect to the total amount of the polyethylene naphthalate resin, preferably the total light transmittance is 85% , A pencil hardness of 1B to 1H and a coefficient of linear thermal expansion of less than 20 ppm / ° C.

Nano Diamond Powder, Soft Display, Hard Coating, Polyethylene Naphthalate, Pencil Hardness

Description

Polyethylene Naphthalate Film < RTI ID = 0.0 >

More particularly, the present invention relates to a polyethylene naphthalate film which is excellent in transparency while having low manufacturing cost, excellent scratch resistance, excellent dimensional stability by heat (low coefficient of linear thermal expansion) A polyethylene naphthalate film which can be used for applications requiring high surface hardness such as substrates for manufacturing processes, substrates for flexible displays including electronic paper (e-paper) or OLED, substrates for solar cells, and substrates for hard coatings used in touch panels .

Generally, soft display is lightweight, thinner and larger than conventional CRT displays, and commercialization is accelerating now. Furthermore, since the flexible display has flexibility inherent in the physical properties thereof, it is possible to perform a roll-to-roll process, which is very advantageous in terms of cost reduction and is expected to be widely used in various applications in the future Is the material.

However, the substrate is used in the user to withstand the high temperature during the transistor formation process, and the dimensional stability before and after the formation of the device is required. However, in the case of the polymer organic substrate, there is a use temperature range, When exposed to high temperature for a long time, the dimensional change is severe.

In order to improve this, there is a case of designing a multilayer thin film such as constituting a primer coating layer (Japanese Patent Application Laid-Open No. 2003-094564). In the case of making glass fiber or glass flake (Japanese Patent Application Laid-Open Nos. JP2004-161444, JP2004-164601 , JP2004-180583). However, in the case of the former, the number of steps increases, which increases the manufacturing cost, and in the latter case, it is difficult to produce extrusion.

Further, the hardness of the polyester fabric is 2B or less (polyethylene terephthalate (PET) has a scratch resistance of about 3B), and the hardness of the coating layer and the base film during the hard coating for the touch panel causes the film to cry , It may cause cracks. However, by increasing the hardness of the base film itself, the difference in hardness between the base film and the coating layer can be reduced, the adhesion can be enhanced, and a separate primer layer coating is not required.

In addition, the diamond size is excellent in transmittance in a visible light region (400 to 800 nm) in nano unit (1 to 100 nm), and is suitable as a display material.

The present invention relates to a method for manufacturing a semiconductor device, which can be applied to a manufacturing process of a semiconductor, such as an electronic paper (e-paper), a flexible display including an OLED, a solar cell, And to provide a film for substrate used for a battery. In addition, the nano diamond powder is mixed into the base film for the touch panel, thereby increasing the hardness and enhancing the scratch resistance.

Disclosure of the Invention The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a resin composition which is low in manufacturing cost, excellent in scratch resistance, excellent in dimensional stability by heat (low coefficient of linear thermal expansion) (Having a high total light transmittance) of a polyethylene naphthalate film.

As a result, it is possible to use polyethylene terephthalate (PET) which can be used for applications requiring high surface hardness such as substrates for semiconductor manufacturing processes, substrates for flexible displays including electronic paper (e-paper) or OLEDs, substrates for solar cells, To provide a naphthalate film.

These and other objects and advantages of the present invention will become more apparent from the following description of a preferred embodiment thereof.

The above object is achieved by a polyethylene naphthalate film characterized in that a nano diamond powder is incorporated into a polyethylene naphthalate resin in an amount of 0.2 to 10 wt% based on the solid content of the entire polyethylene naphthalate resin.

Here, it is assumed that the polyethylene naphthalate film has a high hardness of pencil hardness of 1B to 1H, a coefficient of linear thermal expansion of less than 20 ppm / DEG C, and a total light transmittance of 85% or more.

Preferably, the nanodiamond powder has a size of 1 to 100 nm.

Preferably, the nanodiamond powder further comprises an additive such as a dispersion improving agent for dispersing the nanodiamond powder when the resin is mixed with the resin.

Preferably, the polyethylene naphthalate resin is characterized in that at least one of isophthalic acid, phthalic acid, terephthalic acid and derivatives thereof is copolymerized or blended with naphthalene dicarboxylic acid or a derivative thereof in an amount of 10 to 50 wt%.

Preferably, the polyethylene naphthalate film has a high surface hardness such as a substrate for a semiconductor manufacturing process, a substrate for a flexible display including an electronic paper (e-paper) or an OLED, a substrate for a solar cell, And is used for a purpose that is required.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain an excellent transparency (high total light transmittance) with low manufacturing cost, excellent scratch resistance, excellent dimensional stability by heat (low coefficient of linear thermal expansion)

And can be used in applications requiring high surface hardness such as substrates for semiconductor manufacturing processes, substrates for soft displays including electronic paper (e-paper) or OLED, substrates for solar cells, and substrates for hard coatings used in touch panels Effect.

Hereinafter, the present invention will be described in detail with reference to examples of the present invention. It will be apparent to those skilled in the art that these embodiments are provided by way of illustration only for the purpose of more particularly illustrating the present invention and that the scope of the present invention is not limited by these embodiments .

The polyethylene naphthalate film according to the present invention is a film obtained by mixing 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid or 2,7-naphthalenedicarboxylic acid, preferably 2,6-naphthalenedicarboxylic acid A polyethylene naphthalate resin obtained by esterification or ester exchange reaction in which an acid or its lower alkyl (having 6 or less carbon atoms) diester is condensed with ethylene glycol, followed by polymerization reaction, is obtained, and the resulting polyethylene naphthalate resin is subjected to annual or simultaneous biaxial stretching A film is obtained. Here, in the case of forming the resin, a solid phase polymerization step may be carried out in order to increase the IV (intrinsic viscosity) in some cases. In order to reduce the cost of polyethylene naphthalate, it is preferable to copolymerize or blend at least one or more kinds of isophthalic acid, phthalic acid, terephthalic acid and their respective derivatives, that is, lower alkyl diester derivatives. During the condensation reaction, a polymerization-only germanium catalyst is used as the catalyst to be used to provide a polymeric material with reduced levels of contaminants such as catalyst residues, unwanted inorganic deposits, and by-products of other polymer manufacturing processes. The film produced therefrom has an effect of improving the transparency and the surface peace degree, and is improved in transparency and suitable for use as a substrate for a display.

In the polyethylene naphthalate film according to the present invention, the nanodiamond powder is polymerized in the polymerization step in an amount of 0.2-10 wt% based on the total solid content of the naphthalene dicarboxylic acid or its derivative. In some cases, it is also good to make a master batch chip and to mix chips in the film extrusion process.

The size of the nano diamond powder of the polyethylene naphthalate film according to the present invention is preferably 1 to 100 nm. When the size of the nanodiamond is longer than the wavelength of the visible light (micrometer unit), the transmittance of the total light is lowered, which is not suitable as a display material and the size of the diamond must be nanometer units (especially 1 to 100 nm) shorter than the wavelength of visible light It is suitable as display material because of high total light transmittance.

When the nanodiamond powder is dispersed and added, an additive such as a dispersion improving agent may be added to improve dispersion.

Also, the polyethylene naphthalate film according to the present invention has a coefficient of linear thermal expansion (KS M3060) of less than 20 ppm / ° C at a temperature rise from -30 ° C to 30 ° C.

Further, when it is measured according to the degree of scratch occurrence (the scratch occurrence hardness is selected by rubbing No. 5 and scratch 3 times) when the substrate is scratched by a pencil hardness method (JIS K5400) at a load of 1000 g and a speed of 150 mm / min at a 45 angle, It was confirmed that the polyethylene naphthalate film according to the present invention was improved in the range of 1B to 1H with a high degree of scratching, while easily scratching with 3B.

Further, the total light transmittance (%) was measured with Hazemeter (model: NDH-300A) made by Nippon Denshoku Co., and it was confirmed that the total light transmittance of the polyethylene naphthalate film according to the present invention was 85% or more.

Hereinafter, the constitution of the present invention and the effect thereof will be described in more detail through examples, comparative examples and analysis of physical properties of polymers. However, this embodiment is intended to explain the present invention more specifically, and the scope of the present invention is not limited to these embodiments.

[Example 1]

Transesterification of dimethyl-2,6-naphthalene dicarboxylate with ethylene glycol 0.05 wt% of manganese acetate tetrahydrate based on the solids content of the catalyst, 0.05 wt% of GeO ₂ based on the solid content as a polymerization catalyst was added, The diamond powder was added in an amount of 2 wt% based on the solid content, and then the transesterification reaction was completed. The phosphorus thermal heat stabilizer before polymerization was added in an amount of 0.05 wt% based on the solid content, followed by polymerization reaction to obtain a polymer chip. Next, the polymer chips were extruded using a twin screw extruder, extruded, and the resulting sheet was biaxially stretched to obtain a film having a thickness of 100 탆.

[Example 2]

Except that 70 mol% of dimethyl-2,6-naphthalene dicarboxylate (DM-2,6-NDCA) and 30 mol% of dimethyl terephthalate (DMT) were polymerized with ethylene glycol, ≪ / RTI >

[Example 3]

Except that 70 mol% of dimethyl 2,6-naphthalene dicarboxylate (DM-2,6-NDCA) and 30 mol% of dimethyl isophthalate (DMI) were polymerized with ethylene glycol, ≪ / RTI >

[Example 4]

A film was obtained in the same manner as in Example 1 except that a polymerization reaction was conducted by adding 7 wt% of a nano diamond powder having a size of 4 nm to dimethyl-2,6-naphthalene dicarboxylate and ethylene glycol.

[Comparative Example 1]

Dimethyl-2,6-naphthalenedicarboxylate and ethylene glycol were charged in an amount of 2 wt% based on a solid basis, and polymerization was carried out in the same manner as in Example 1, to obtain a film.

[Comparative Example 2]

Transesterification of dimethyl-2,6-naphthalenedicarboxylate with ethylene glycol 0.05 wt% of manganese acetate tetrahydrate based on the solids content of the catalyst, and 0.05 wt% of GeO ₂ based on solid content as a polymerization catalyst were added to complete the transesterification reaction And 0.05% by weight of a phosphorus thermal stabilizer before polymerization was added thereto in a solid content of 0.05 wt%, and the polymerization reaction was completed to obtain a polymer chip. Next, the polymer chips were extruded using a twin screw extruder, extruded, and the resulting sheet was biaxially stretched to obtain a film having a thickness of 100 탆.

[Comparative Example 3]

Except that 70 mol% of dimethyl-2,6-naphthalene dicarboxylate (DM-2,6-NDCA) and 30 mol% of dimethyl terephthalate (DMT) were polymerized with ethylene glycol, ≪ / RTI >

[Comparative Example 4]

Except that 70 mol% of dimethyl-2,6-naphthalene dicarboxylate (DM-2,6-NDCA) and 30 mol% of dimethyl isophthalate (DMI) were polymerized with ethylene glycol, ≪ / RTI >

[Comparative Example 5]

A film was obtained in the same manner as in Comparative Example 1, except that a polymer chip was obtained by adding 25 wt% of a nano diamond powder having a size of 4 nm to dimethyl-2,6-naphthalene dicarboxylate and ethylene glycol.

[Experimental Example]

1. The coefficient of linear thermal expansion is measured according to KS M3060.

2. Pencil hardness method is according to JIS K5400.

3. The glass transition temperature is measured with a Perkin-Elmer DSC7 at a rate of 10 ° C / min up to 280 ° C and measured at a second temperature rise.

The results of the above experimental examples are shown in Table 1 below.

[Table 1]

Example
One Example
2 Example
3 Example
4 Comparative Example
One Comparative Example
2 Comparative Example
3 Comparative Example
4 Comparative Example
5 Polymer PEN DM-2,6 NDCA 70 mol%, DMT 30 mol% DM-2,6 NDCA 70 mol%, DMI 30 mol% PEN PEN PEN DM-2,6 NDCA 70 mol%, DMT 30 mol% DM-2,6 NDCA 70 mol%, DMI 30 mol% PEN Nano
Diamond Size (nm) 4 4 4 4 2000 4 Nano
Diamonds content (wt%) 2 2 2 7 2 - - - 25 Coefficient of linear thermal expansion
(ppm / DEG C) 17 18 17 14 18 25 28 27 13 Glass transition temperature
(° C) 125 111 106 129 106 121 106 103 131 Pencil hardness HB 1B 1B HB HB 2B 3B 3B - Total light transmittance (%) 89.9 90.1 88.6 85.5 80.2 88.8 87.6 88.2 - Film formation O O O O O O O O X

As can be seen from the above Table 1, as the content of the nano diamond powder increases, the coefficient of linear thermal expansion decreases (that is, the dimensional stability against heat increases), the pencil hardness and the glass transition temperature increase, There arises a problem that the film is not torn and formed in the biaxial stretching process. Also, when the size of the diamond powder is large (2000 nm) among those containing the same content, the total light transmittance which is important for the display material is 80.2% to 85% or less. When the diamond powder is a nano- The transmittance was 89.9%.

Therefore, the polyethylene naphthalate film according to the present invention can be used for a semiconductor manufacturing process, a flexible display including an electronic paper (e-paper) or an OLED, a substrate material used for a solar cell, and a substrate film for a hard coating used for a touch panel It can be suitably used for applications requiring hardness.

Claims (6)

In the polyethylene naphthalate film, The nano diamond powder was incorporated into the polyethylene naphthalate resin in an amount of 7 wt% based on the solid content of the entire polyethylene naphthalate resin, The size of the nanodiamond powder is 1 to 100 nm, A pencil hardness of 1B to 1H, a linear thermal expansion coefficient of less than 20 ppm / DEG C, and a total light transmittance of 85% or more. delete delete The method according to claim 1, And a dispersion improving agent for dispersing the nanodiamond powder when the resin is mixed with the resin. The method according to claim 1 or 4, Wherein the polyethylene naphthalate resin is obtained by copolymerizing or blending at least one of isophthalic acid, phthalic acid, terephthalic acid and derivatives thereof with 10 to 50 wt% together with naphthalene dicarboxylic acid or a derivative thereof. 6. The method of claim 5, The polyethylene naphthalate film is used for a substrate for a semiconductor manufacturing process, a substrate for a flexible display including an electronic paper (e-paper) or an OLED, a substrate for a solar cell, and a substrate for hard coating used in a touch panel. Phthalate film.