KR20190078225A - Antistatic film and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an antistatic film and a method of manufacturing the same. More specifically, the present invention relates to an antistatic film and a method of manufacturing the same, wherein the antistatic film includes a polymer base film; and a polymer composite coated on the polymer base film. The polymer composite includes a non-thermoplastic resin, a conductive filler and an amino-silane; the conductive filler is dispersed in the non-thermoplastic resin; and the amino-silane is combined with the non-thermoplastic resin.

Description

[0001] The present invention relates to an antistatic film and a manufacturing method thereof,

More particularly, the present invention relates to an antistatic film having excellent chemical resistance and electric conductivity and having no change in surface resistance even at a low temperature and a high temperature, and a method for producing the antistatic film.

Semiconductors are inspected several times in the manufacturing process to check whether the function is normal or abnormal. This is done by using a tester equipped with various measuring equipments in the computer. Electrical testing of semiconductor devices using such a tester includes electrical die sorting (EDS) in a wafer state, final test in a semiconductor package type final test, Reliability testing of the semiconductor chip and the semiconductor package in the assembled state.

The final test may be a room temperature electrical final test, a cold temperature electrical final test at a temperature lower than room temperature, or a hot temperature electrical final test at a temperature higher than room temperature test). Although there are many types of reliability tests for the reliability test, there is a burn-in test as a typical reliability test using a socket. The burn-in test is a test for applying a harsh condition such as a high temperature and a high voltage to a semiconductor device in order to screen an initial defect of the semiconductor device, thereby removing the semiconductor device having a possibility of initial failure before shipping the product.

As described above, in order to inspect a semiconductor device, it is made of a kit capable of accommodating a semiconductor device. Such a kit is typically laser-processed at the time of manufacture, and is subjected to a washing process after laser processing.

However, such inspection cost kits can cause static electricity problems, and if static electricity is generated in semiconductors, they can be transmitted to the internal circuits, thereby damaging the reliability of semiconductors. As a result of charging of static electricity, There is a problem.

Accordingly, to solve this problem, it is possible to apply an insulating characteristic polyimide layer to the inspection cost kit and to include the conductive material in it, so that the static electricity generated can be discharged immediately. 1 is a schematic view showing a form in which a polyimide layer is applied to the above inspection cost kit. 1, a polyimide layer 20 is coated on a mold cartridge 10 and a semiconductor chip 30 is provided on the polyimide layer 20 to inspect semiconductor chips in a high- Is performed.

However, since the organic solvent is used in the cleaning process of the kit for semiconductor inspection equipment, it is required to have chemical resistance to the organic solvent, and an antistatic film capable of maintaining a constant electric conductivity because there is no change in sheet resistance even at the temperature Has not yet been developed.

Accordingly, it is an object of the present invention to provide an antistatic film excellent in chemical resistance and electrical conductivity and free from surface resistance change even at a low temperature and a high temperature.

Another object of the present invention is to provide a method for producing an antistatic film which is excellent in chemical resistance and electric conductivity and has no surface resistance change even at a low temperature and a high temperature.

In order to solve the above problems, the present invention relates to a polymer base film; And a polymer composite coated on the polymer substrate film, wherein the polymer composite comprises a non-thermoplastic resin, a conductive filler and an amino-silane, the conductive filler is dispersed in the non-thermoplastic resin, and the amino - silane is bonded to the non-thermoplastic resin.

The present invention also relates to a method for producing a non-thermoplastic resin solution, comprising the steps of: preparing a non-thermoplastic resin solution; Adding a conductive filler and a dispersant to the non-thermoplastic resin solution, dispersing the conductive filler in the non-thermoplastic resin solution, and adding amino-silane to prepare a mixed solution; And coating the mixed solution on a polymer base film, followed by heat treatment.

According to the present invention, by adding a non-thermoplastic resin to an antistatic film, the chemical resistance to an organic solvent can be improved.

The antistatic film according to the present invention is excellent in heat resistance and can maintain the surface resistance value constant even at a high temperature during semiconductor inspection.

In addition to the use of metal nanoparticles in addition to the conductive filler, the amount of expensive carbon nanotubes can be minimized, the electric conductivity can be further improved, and the process cost can be greatly reduced.

1 is a schematic view showing a form in which a polyimide layer is applied to the above inspection cost kit.
2 is a schematic view showing an antistatic film according to the present invention.
3 is a flowchart showing a method for producing an antistatic film according to the present invention.

The above and other objects, features, and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings, which are not intended to limit the scope of the present invention. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail. Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the drawings, the same reference numerals are used to denote the same or similar elements.

The present invention relates to a polymer-based film; And

A polymer composite coated on said polymer substrate film,

The polymer composite includes a non-thermoplastic resin, a conductive filler and an amino-silane, wherein the conductive filler is dispersed in the non-thermoplastic resin, and the amino-silane is bonded to the non-thermoplastic resin And an antistatic film.

2 is a schematic view showing an antistatic film according to the present invention. Hereinafter, the present invention will be described in detail with reference to FIG.

An antistatic film in accordance with the present invention comprises a polymeric substrate film (110) and a polymeric composite (120).

The polymer base film 110 may be a polyimide resin or a polyamideimide resin. The polyimide resin or polyamideimide resin is excellent in thermal stability, has an advantage of excellent mechanical and electrical properties, and has a high glass transition temperature, so that there are many restrictions on the processing and there is a characteristic that it is relatively easy to charge.

Further, in the antistatic film 100 according to the present invention, the polymer composite 120 includes a non-thermoplastic resin, a conductive filler, and an amino-silane.

The non-thermoplastic resin used in the antistatic film according to the invention generally means a resin which does not exhibit softening or adhesion even when heated. In the present invention, it means a resin that maintains its shape without wrinkling or stretching by heating at 450 ° C for 2 minutes in the state of a film, or a resin having substantially no glass transition temperature. The glass transition temperature can be obtained from the value of the inflection point of the storage elastic modulus measured by a dynamic viscoelasticity measuring device (DMA). Further, when the glass transition temperature is not substantially, it means that pyrolysis is started before the glass transition state is reached.

As the non-thermoplastic resin in the antistatic film 100 according to the present invention, at least one selected from the group consisting of polyimide, polyamide, polyamine, aramid, and mixtures thereof may be used.

The non-thermoplastic resin has a glass transition temperature of 340 ° C or more, a modulus of 1 to 3 GPa, a tensile strength of 100 to 300 MPa, and a thermal decomposition temperature of 500 to 650 ° C.

The antistatic film 100 according to the present invention can improve the chemical resistance of the organic solvent by using the non-thermoplastic resin as described above, maintain the surface resistance value constant even at a high temperature during the semiconductor inspection, Is excellent.

In the antistatic film (100) according to the present invention, when the non-thermoplastic resin is a polyimide resin, it can be produced using diamines and dianhydrides. Examples of the diamine include 4,4'-Oxydianiline (ODA), para-Phenylene Diamine (pPDA), meta-Phenylene Diamine (mPDA), p-methylenediamine methylene diamine (mMDA), 4,4'-oxyphenylenediamine (OPDA), and the like can be used as the dianhydride. Examples of the dianhydride include 1, 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 2,4,5-benzenetetracarboxylic dianhydride 4,4'-Biphenyltetracarboxylic Dianhydride (BPDA), 4,4-Oxydiphthalic dianhydride (ODPA) and the like can be used .

The diamine and the dianhydride may be used in a molar ratio of 1: 0.99 to 0.99: 1.

In the antistatic film 100 according to the present invention, the surface resistance value of the non-thermoplastic resin has a value higher than that required for the antistatic film. Therefore, it is preferable to mix the conductive filler with the non-thermoplastic resin, and after dispersing the conductive filler in the solvent, a dispersant may be further added for dispersion stability. Specific examples of the dispersing agent include sodium dodecyl sulfate (SDS), Triton X (Sigma), Tween 20 (Polyoxyethyelene Sorbitan Monooleate) and CTAB (Cetyl Trimethyl Ammonium Bromide).

As the conductive filler, carbon nanotubes can be preferably used. Methods for synthesizing carbon nanotubes include an electric discharge method, a laser ablation method, a plasma chemical vapor deposition method, a thermochemical vapor deposition method, and an electrolytic method. The carbon nanotubes usable in the present invention are limited to those obtained by a specific synthetic method It is not.

Carbon nanotubes are divided into single wall carbon nanotubes, double wall carbon nanotubes and multi wall carbon nanotubes depending on the number of walls. There are no limitations on the types of carbon nanotubes usable in the present invention, but single-wall carbon nanotubes and multi-wall carbon nanotubes have antistatic properties Is a kind of conductive carbon material which can exhibit semiconducting properties and is excellent in conductivity compared to other materials, exhibits excellent electrical characteristics for a small amount of input, and has a very small impurity content, and is therefore suitable for use in the present invention.

Multi-wall carbon nanotubes are preferable for manufacturing low-cost products.

The size of the carbon nanotubes is preferably 1 to 25 nm in diameter, more preferably 10 to 20 nm. The length of the carbon nanotubes is preferably 0.11 to 15 mu m, more preferably 0.1 to 10 mu m in terms of electrical conductivity. Accordingly, the aspect ratio of the carbon nanotubes may be 300 or more.

The content of the carbon nanotubes is preferably 0.1 to 2.0 parts by weight based on the total weight of the non-thermoplastic resin. When the content of the carbon nanotubes is less than 0.1 part by weight, the antistatic film has a low electrical conductivity and the antistatic effect is not exhibited. When the content is more than 2.0 parts by weight, the carbon nanotubes are dispersed evenly in the non- There is a problem that the manufacturing cost is greatly increased because the unit price of the carbon nanotubes is high.

In the antistatic film 100 according to the present invention, the amino-silane has a molecular structure in which an amine group and a silane group are present at both ends of the molecule. Specifically, 3-aminopropyltrimethoxysilane, 3- (3-aminopropyltriethoxysilane), and mixtures thereof.

The amino-silane is preferably included in an amount of 0.5 to 1.5 parts by weight based on the total weight of the non-thermoplastic resin. When the amino-silane is contained in an amount of less than 0.5 part by weight, the dispersion of nanoparticles is not smoothly performed when the metal nanoparticles are added, and when the aminosilane is coagulated by the reaction of the metal nanoparticles with the free acid, There arises a problem that a coating layer is not formed. When the amount exceeds 1.5 parts by weight, even if amino-silane is further added in terms of process efficiency, there is no change in the physical properties of the antistatic film, It is insignificant.

In addition, in the antistatic film 100 according to the present invention, the polymer composite 120 may further include metal nanoparticles.

The metal nanoparticles may be at least one selected from the group consisting of copper (Cu), silver (Ag), gold (Au), iron (Fe), and titanium (Ti) To 1 mu m. When the size of the metal nanoparticles is less than 50 nm, there is a problem that the decrease of the contact resistance between the carbon nanotubes due to the addition of the metal nanoparticles is limited and the surface resistance value is not improved. On the other hand, There is a problem that the metal nano-particles are not uniformly dispersed.

The metal nanoparticles are preferably included in an amount of 0.02 to 0.07 part by weight based on the total weight of the non-thermoplastic resin. When the amount of the metal nanoparticles is less than 0.02 parts by weight, the surface resistance value is not improved. When the amount of the metal nanoparticles is more than 0.07 parts by weight, the metal nanoparticles are not uniformly dispersed.

The antistatic film 100 according to the present invention includes a conductive filler and metal particles as described above and has a surface resistance in the range of 1 x 10 ⁴ to 1 x 10 ¹³ ? / Square.

As described above, the antistatic film 100 according to the present invention is described in the case where the polymer composite 120 is provided on one side of the polymer base film 110. However, the antistatic film 100 may be applied to the semiconductor field, It is possible to prevent the defective product, the IC breakage, the malfunction of the robot and the computer from occurring due to dust adhesion or electrostatic discharge, so that the polymer base film Or may be provided on both sides of the base 110.

The present invention also relates to a method for producing a non-thermoplastic resin solution, comprising the steps of: preparing a non-thermoplastic resin solution;

Adding a conductive filler and a dispersant to the non-thermoplastic resin solution, dispersing the conductive filler in the non-thermoplastic resin solution, and adding amino-silane to prepare a mixed solution; And

And coating the mixed solution on the polymer base film and then heat treating the film.

3 is a flowchart showing a method for producing an antistatic film according to the present invention. Hereinafter, the present invention will be described in more detail with reference to FIG.

The method for producing an antistatic film according to the present invention includes a step (S100) of producing a non-thermoplastic resin solution.

In the method for producing an antistatic film according to the present invention, the non-thermoplastic resin solution may be prepared by mixing a diamine and a dianhydride under a nitrogen atmosphere, especially when the solution is a polyimide.

The non-thermoplastic resin may be at least one selected from the group consisting of polyimide, polyamide, polyamine, aramid, and mixtures thereof as described above.

Next, in the method for producing an antistatic film according to the present invention, a conductive filler and a dispersant are added to the non-thermoplastic resin solution, the conductive filler is dispersed in the non-thermoplastic resin solution, and amino- (S200).

The conductive filler may be selected from the group consisting of a single wall carbon nanotube, a double wall carbon nanotube, and a multi wall carbon nanotube. (SDS), Triton X (Sigma), Tween 20 (Polyoxyethyelene Sorbitan Monooleate) and CTAB (Cetyl Trimethyl Ammonium Bromide) can be used as the dispersing agent.

The conductive filler is preferably included in an amount of 0.1 to 2.0 parts by weight based on the total weight of the non-thermoplastic resin. The reason for limitation is as described above.

Also, the amino-silane may be selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and mixtures thereof, and the amino- The silane is preferably included in an amount of 0.5 to 1.5 wt% of the total weight of the non-thermoplastic resin solution. The reason for limitation is as described above.

In this case, the amine group of the amino-silane bonds with the non-thermoplastic resin to prevent the conductive filler from being uniformly dispersed in the non-thermoplastic resin. In particular, when the metal filler is further included, Bonding of the thermoplastic resin can be prevented.

In addition, the method for producing an antistatic film according to the present invention includes a step (S300) of coating the above mixed solution on a polymer base film and then performing a heat treatment.

The polymer base film may be a polyimide resin, a polyamideimide resin, or the like as described above. After the polymer base film is coated on the polymer base film, heat treatment may be performed in multiple stages at a temperature range of 80 to 350 ° C. Specifically, it can be carried out at 80 캜 for 10 minutes and then at 200 캜 for 10 minutes and subsequently at 350 캜 for 10 minutes.

When the heat treatment temperature is lower than 80 캜, the polymer materials are not cured and problems occur in forming the coating layer. When the heat treatment temperature is more than 350 캜, the polymer materials are oxidized to deteriorate the physical properties of the antistatic film.

The method for producing an antistatic film according to the present invention may further include metal nanoparticles in the mixed solution.

The antistatic film according to the present invention can further reduce the amount of the conductive filler, particularly the carbon nanotubes, and further improve the electrical conductivity of the antistatic film by further including the metal nanoparticles.

The metal nanoparticles may be at least one selected from the group consisting of copper (Cu), silver (Ag), gold (Au), iron (Fe), and titanium (Ti) 50 nm to 1 탆. The metal nanoparticles are preferably included in an amount of 0.02 to 0.07 part by weight based on the total weight of the non-thermoplastic resin.

Example 1: Preparation of Antistatic Film 1

1. Production of polyimide resin

435 g of N, N-dimethylacetamide as a solvent was added to a 4-neck flask (double jacket type) under a nitrogen atmosphere, and 31 g of 4,4-oxydianiline was added thereto. After dissolving, 33 g of pyromellitic dianhydride was added to prepare polyamic acid, which is a polyimide resin.

2. Preparation of polymer composites

The carbon nanotubes, which are conductive fillers, were added to the polyamic acid prepared in the above process in an amount of 2.0 parts by weight based on the total weight of the polyamic acid, and the same amount of the dispersing agent as the amount of the carbon nanotubes was added, followed by dispersing the carbon nanotubes. Amino-silane was added to the polyamic acid solution in which the carbon nanotubes thus prepared were dispersed, in an amount of 1 part by weight based on the total weight of the polyamic acid, followed by stirring for 1 hour. This reaction yielded a polymer composite in which the carboxyl group of the polyamic acid and the amine group of the amino-silane were bonded to each other to disperse the carbon nanotubes.

3. Antistatic layer manufacturing

The polymer composite solution prepared above was coated on both sides of a polyimide film to have a thickness of 2.5 탆 and then heat-treated at 80 캜 for 10 minutes, 200 캜 for 10 minutes, and 350 캜 for 10 minutes to obtain a polyimide film coated with a polymer composite .

Example 2: Preparation of antistatic film 2

A polyimide film coated with a polymer composite was prepared in the same manner as in Example 1, except that 0.05 part by weight of Cu nanoparticles was added to the polyimide film-coated polymer composite in terms of the total weight of the polyamic acid.

Example 3: Preparation of antistatic film 3

A polyimide film coated with a polymer composite was prepared in the same manner as in Example 1 except that the polymer composite coated on the polyimide film was added with 1.7 parts by weight of carbon nanotubes based on the total weight of the polyamic acid.

Example 4: Preparation of antistatic film 4

Polymer composite coated with a polymer composite was prepared in the same manner as in Example 3, except that 0.05 part by weight of metal nanoparticles was added to the polymer composite solution in terms of the total weight of the polyamic acid.

Example 5: Preparation of antistatic film 5

A polyimide film coated with a polymer composite was prepared in the same manner as in Example 1, except that the carbon nanotubes were added to the polyimide film-coated polymer composite in an amount of 0.8 parts by weight based on the total weight of the polyamic acid.

Example 6: Preparation of Antistatic Film 6

A polyimide film coated with a polymer composite was prepared in the same manner as in Example 1 except that the polymer composite coated on the polyimide film was charged with 0.5 part by weight of carbon nanotubes based on the total weight of the polyamic acid

Comparative Example 1

0.5 parts by weight of a carbon nanotube as a conductive filler was added to polyamic acid, 0.05 parts by weight of Cu nanoparticles were added to a solution in which carbon nanotubes were dispersed after the same amount of a dispersant as the amount of the carbon nanotubes was added, The same method was used.

Experimental Example 1: Analysis of electrical conductivity and chemical resistance of antistatic film

The electrical conductivity of the antistatic film according to the present invention was analyzed. The results are shown in Table 1, and the chemical resistance was also tested.

Sample Surface resistance (Ω / square) Example 1 7.16 x 10 ⁴ Example 2 2.32 x 10 ⁴ Example 3 8.45 × 10 ⁵ Example 4 3.16 × 10 ⁵ Example 5 1.46 x 10 ⁹ Example 6 2.98 × 10 ¹² Comparative Example 1 No film formation

As shown in Table 1, the surface resistance value of Example 2 (2.0 parts by weight of carbon nanotubes + 0.05 parts by weight of Cu nanoparticles) was the lowest, and Example 1 (2.0 parts by weight of carbon nanotubes) Showed the lowest surface resistance value. In the case of Example 3 (1.7 parts by weight of carbon nanotubes), the content of carbon nanotubes was lower than that of Example 1 and the surface resistance value was increased. Example 5 (0.8 parts by weight of carbon nanotubes), Example 5 0.5 weight part of the tube), the surface resistance value becomes higher as the content of the carbon nanotubes is lowered.

In Comparative Example 1, no amino-silane was contained and the non-thermoplastic resin was solidified and no film was formed.

The surface resistance of the antistatic film according to the present invention measured after washing with acetone was 3.98 × 10 ⁵ Ω / square. Even if the surface of the antistatic film was treated with an organic solvent, It is not so large that the chemical resistance is excellent.

Experimental Example 2: Heat resistance analysis of antistatic film

The heat resistance of the antistatic film according to the present invention was analyzed, and the results are shown in Table 2 below.

The heat resistance test of the antistatic film was carried out in an oven at 170 DEG C, and the antistatic film was retained for 100 hours to analyze the change of the surface resistance.

Sample Surface resistance (Ω / square) 0 hours 24 hours 48 hours 72 hours 100 hours Example 4 3.16 × 10 ⁵ 3.98 × 10 ⁵ 2.51 × 10 ⁵ 2.51 × 10 ⁵ 3.98 × 10 ⁵

As shown in Table 2, the antistatic film according to the present invention has a rate of change of surface resistance (initial surface resistance - surface resistance at residence time / initial surface resistance) of -20% to less than 100% + 26%, indicating that the change of the surface resistance is not large, and therefore, the heat resistance is excellent.

While the present invention has been particularly shown and described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It is therefore to be understood that such changes and modifications are intended to be included within the scope of the present invention unless they depart from the scope of the present invention.

100: Antistatic film
110: polymer base film
120: polymer composite

Claims (21)

Polymer based film; And
A polymer composite coated on said polymer substrate film,
The polymer composite includes a non-thermoplastic resin, a conductive filler, and an amino-silane, wherein the conductive filler is dispersed in the non-thermoplastic resin, and the amino-silane is bonded to the non-thermoplastic resin Antistatic film.
The method according to claim 1,
Wherein the polymer base film is a polyimide resin or a polyamideimide resin.
The method according to claim 1,
Wherein the non-thermoplastic resin is at least one selected from the group consisting of polyimide, polyamide, polyamine, aramid, and mixtures thereof.
The method according to claim 1,
Wherein the conductive filler is selected from the group consisting of single wall carbon nanotubes, double wall carbon nanotubes, and multi wall carbon nanotubes. Prevention film.
The method according to claim 1,
Wherein the conductive filler is contained in an amount of 0.1 to 2.0 parts by weight based on the total weight of the non-thermoplastic resin.
The method according to claim 1,
Wherein the amino-silane is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and mixtures thereof.
The method according to claim 1,
Wherein the amino-silane is contained in an amount of 0.5 to 1.5 parts by weight based on the total weight of the non-thermoplastic resin.
The method according to claim 1,
Wherein the polymer composite further comprises metal nanoparticles.
9. The method of claim 8,
Wherein the metal nanoparticles are at least one selected from the group consisting of copper (Cu), silver (Ag), gold (Au), iron (Fe), and titanium (Ti).
9. The method of claim 8,
Wherein the metal nanoparticles are included in an amount of 0.02 to 0.07 part by weight based on the total weight of the non-thermoplastic resin.
9. The method of claim 8,
Wherein the antistatic film has a surface resistance value of 1 x 10 ⁴ to 1 x 10 ¹³ Ω / square.
Preparing a non-thermoplastic resin solution;
Adding a conductive filler and a dispersant to the non-thermoplastic resin solution, dispersing the conductive filler in the non-thermoplastic resin solution, and adding amino-silane to prepare a mixed solution; And
And coating the mixed solution on the polymer base film, followed by heat treatment.
13. The method of claim 12,
Wherein the non-thermoplastic resin is at least one selected from the group consisting of polyimide, polyamide, polyamine, aramid, and mixtures thereof.
13. The method of claim 12,
Wherein the conductive filler is selected from the group consisting of single wall carbon nanotubes, double wall carbon nanotubes, and multi wall carbon nanotubes. (2).
13. The method of claim 12,
Wherein the conductive filler comprises 0.1 to 2.0 parts by weight of the total weight of the non-thermoplastic resin.
13. The method of claim 12,
Wherein the amino-silane is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and mixtures thereof. Gt;
13. The method of claim 12,
Wherein the amino-silane is contained in an amount of 0.5 to 1.5 parts by weight based on the total weight of the non-thermoplastic resin.
13. The method of claim 12,
Wherein the heat treatment is performed in multiple stages at a temperature ranging from 80 to 350 占 폚.
13. The method of claim 12,
Wherein the metal nanoparticles are further included in the mixed solution.
20. The method of claim 19,
Wherein the metal nanoparticles are at least one selected from the group consisting of copper (Cu), silver (Ag), gold (Au), iron (Fe), and titanium (Ti).
20. The method of claim 19,
Wherein the metal nanoparticles are contained in an amount of 0.02 to 0.07 part by weight based on the total weight of the non-thermoplastic resin.

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