KR100856148B1 - Basic solution washable antistatic composition and polymer products manufactured by using the same - Google Patents

Abstract

In the production of electrical and electronic parts or products using polymer films, polymer films or polymer products made by processing them are basic to wipe off dust adsorbed by static electricity or organic substances on the surface while handling polymer products in the process. It is often washed in an aqueous solution. At this time, in the case of a polymer product having an antistatic layer, in particular, an antistatic layer having a conductive polymer as an active ingredient, washing with a basic solution such as sodium hydroxide or potassium hydroxide aqueous solution may cause all the antistatic layers to come off and the antistatic property disappears. There is this. In order to prevent this, the present invention is to provide an antistatic composition having a chemical resistance that does not peel off the antistatic layer formed on the surface even after washing in a basic aqueous solution, and a polymer film and a related polymer product prepared using the same. Using the technique of the present invention, it is possible to prepare a polymer product in which antistatic properties are maintained without peeling off the antistatic layer formed on the surface even when placed in a basic aqueous solution and washed. By using the technology of the present invention it is possible to provide a stable polymer film having chemical resistance to a polymer film product, such as a spacer for a flexible printed circuit board or an antistatic triacetate cellulose film or a product using the same.

Description

Basic solution washable antistatic composition and polymer products manufactured by using the same}

The present invention relates to an antistatic composition that can be washed with a basic washing solution such as sodium hydroxide or potassium hydroxide aqueous solution, and more particularly, to prepare an antistatic polymer product that can be used in a process of washing with a basic aqueous solution, that is, resistant to basic solvents. The present invention relates to an antistatic composition and a polymer antistatic polymer product prepared using the same.

The polymer film used for the electric and electronic parts or the polymer product manufactured therefrom is used by forming an antistatic layer on the surface in order to prevent problems such as adsorption of dust around the circuit by the generation of static electricity during the manufacturing process or circuit breakage. There are a variety of techniques for forming an antistatic layer on the surface, it may be used to form an antistatic layer using a surfactant-type antistatic agent or a conductive polymer as an active ingredient.

These antistatic layers are effective to prevent the generation of static electricity on the surface of the product, such as polymer film, can prevent problems such as dust adsorption or circuit cutting.

However, these methods have a big problem in the process. That is, the surface of the product is contaminated with various organic substances such as silicone oil during the handling of polymer products such as films. Therefore, in order to clean the surface of the polymer product, it is put in a basic solution such as sodium hydroxide or potassium hydroxide aqueous solution and used. At this time, 2-10% aqueous solution of sodium hydroxide or potassium hydroxide solution is used normally.

At this time, the polymer film using the surfactant as an antistatic agent is easily washed and removed in the process of washing with a basic aqueous solution as described above, so that the antistatic performance is lost after the cleaning process is finished, and also the conductive polymer as an active ingredient In the case of the polymer film in which the antistatic layer is formed, the conductive polymer is dedoped by the basic solvent, and thus the electrical conductivity is lowered after the washing process. Therefore, a film, an injection molded product or a polymer processed product manufactured by using the same process having to be washed in a basic aqueous solution has a big disadvantage in that a permanent antistatic treatment cannot be performed using a surfactant or a conductive polymer.

For example, in the case of a flexible printed circuit board spacer tape, in the case of a flexible printed circuit board, an antistatic layer containing a conductive polymer as an active ingredient is formed on a surface of a polyester film, and then a mountain of constant height is formed on both edges. It is rolled up with a flexible printed circuit board and transported to a reel. In this way, the spacer used for shipping may have an antistatic effect very effectively by forming an antistatic layer containing a conductive polymer as an active ingredient. However, in the case of an antistatic spacer for a process, after forming an antistatic layer containing a conductive polymer as an active ingredient and using the spacer for a process, the surface of the conductive polymer may be placed in a 2-10% aqueous solution of sodium hydroxide or potassium hydroxide while being washed. All of the antistatic layer is peeled off and the antistatic property disappears. In addition, in the case of the triacetate cellulose film, which is a main component of the polarizing film, the problem of adsorption of dust by the generation of static electricity during the process is severe. Therefore, an antistatic layer must be formed on the surface of the film to prevent it. The antistatic layer is not effective. In addition, a polyimide film used as a flexible printed circuit board is used by laminating a polyimide film and a copper film, and a large amount of electrostatic cells are generated on the surface of the polyimide film during various rolls during the manufacturing process. In order to prevent this, the surface of the polyimide film may be antistatically treated, but for the reasons described above, the surface of the polyimide film cannot be antistatically treated.

Therefore, there is a need for the invention of a new technology that can maintain the antistatic property without damaging the antistatic layer formed on the surface even when put in a basic aqueous solution.

It is an object of the present invention to provide an antistatic composition that can be used in a process of washing in a basic aqueous solution and an antistatic polymer product prepared by applying the same to a polymer surface to form an antistatic layer on the surface.

The present invention relates to an antistatic composition for preparing an antistatic polymer product that can be used in a process of washing with an aqueous basic solution, that is, to resist basic solvents, and a polymer antistatic polymer product prepared using the same.

In order to achieve the object of the present invention, a thermosetting resin capable of forming a three-dimensional network by using an antistatic agent that is not damaged by basic solvents such as sodium hydroxide or potassium hydroxide aqueous solution and curing at a temperature condition of 20-250 degrees Celsius as a binder component. And antistatic components that are not damaged by basic solvents as an active ingredient, mixed with an appropriate solvent to prepare an antistatic composition and coated on the surface of the polymer to produce an antistatic polymer product and reprocess it to produce polymer products for various electronic parts. The method of making was used.

The antistatic composition of the present invention is prepared by mixing 0.1-20 parts by weight of a metal oxide or carbon nanotube, 0.5-20 parts by weight of an epoxy or phenolic thermosetting resin, 0.02-5 parts by weight of a curing agent, and 55-99.38 parts by weight of a solvent. As an antistatic coating liquid, an antistatic layer having a thickness of 0.05-10 microns is formed by applying, drying and curing the surface of the base film. In the antistatic coating solution, it is possible to use a 0.05-5 parts by weight of a release agent based on 100 parts by weight of the antistatic coating solution in order to improve the release property, and also use an interfacial binder to enhance the dispersing effect of the metal oxide or carbon nanotube. It is possible to use 0.01-5 parts by weight based on 100 parts by weight of the metal oxide or carbon nanotube content.

The polymer film produced by the above-described method can be produced by polymerizing the final antistatic properties by molding with heat or pressure.

In preparing the antistatic coating solution, even when washed in a basic aqueous solution by using a metal oxide or carbon nanotubes as an antistatic component, the electrical conductivity does not change and the antistatic properties are maintained as it is. The metal oxide may be metal oxide particles such as tin oxide, indium oxide, zinc oxide, titanium oxide, and the like, and may be used as metal oxide particles doped with arsenic, indium, antimony, or other Group 5 elements to show conductivity. The single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers or graphite may be used. The metal oxides or carbon nanotubes can be used without limitation in shape and size, but preferably may use the particles having a particle size of 0.002-5 microns to have the same antistatic effect or less visible light It is effective because the scattering can be suppressed to improve transparency. In addition, the metal oxide is a material having an electrical conductivity in the range of 10 ^{-5-10 3} S / cm, it is applicable to the metal oxide itself or metal oxide of the form doped with other components such as arsenic, indium, antimony, etc. Flakes or fibrous metal oxides of spherical or aspect ratio (long side length / short side length) of 1 or more may be used. In some cases, the metal oxide is sold in a form in which the metal oxide is dispersed. In this case, since the surface of the metal oxide is modified and then dispersed in the solvent, there is no need to perform a separate operation.

The resin that can be used as the binder in the present invention can be used as long as the resin having a three-dimensional network structure after a curing reaction, for example epoxy or phenolic resin can be used. Specific examples include glycidyl ether type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, glycidyl ester type epoxy resins, and glycidylamine type. Epoxy resins, etc. These epoxy resins can be used individually or in mixture of 2 or more types. The epoxy resin serves to enhance the chemical stability and durability of the antistatic layer by forming a three-dimensional network structure when a hardening reaction is induced by the addition of some of the curing agent. Therefore, even if the washing process in the basic aqueous solution as described above is effective because there is no phenomenon that the antistatic layer falls off. The curing agent added to the epoxy resin is selected from one or more of the curing agents selected from amines, polyamides, acid anhydrides, imidazoles, melamines, mercaptans, isocyanates, etc., depending on the type and curing conditions of the epoxy resins. do. The epoxy resin and the curing agent are mixed with a metal oxide or carbon nanotube in a predetermined amount and applied to the base film, and then, when inducing a curing reaction, an antistatic layer having excellent durability and chemical resistance is formed, thus preventing the antistatic even after washing with a basic solution. The property remains constant.

When the metal oxide or carbon nanotubes are mixed with an epoxy resin and a curing agent by the above method, the surface of the metal oxide or carbon nanotubes is pretreated with an interfacial binder and then mixed with the binder resin. Since the dispersing effect is excellent and the interfacial bonding force with the binder resin is also enhanced, the same effect can be achieved even at a low content. As the interfacial binder, various silane-based interfacial binders such as acrylate-based, epoxy-based, amino-based, and vinyl-based silanes can be used, and titanate-based and aluminum-based interfacial binders can also be used. After the interfacial binder was added to a suitable solvent with a metal oxide or carbon nanotube and stirred for about 24 hours, the solvent was removed at a temperature of 50-150 degrees Celsius to obtain a metal oxide surface-treated with the interfacial binder, which was again appropriate. It is effective to redisperse in a solvent and mix with binder resin. In this case, the content of the interfacial binder is added in 0.01-5 parts by weight of the interfacial binder based on 100 parts by weight of the metal oxide or carbon nanotube content, more preferably 0.02-1 part by weight.

In treating the surface of the metal oxide or carbon nanotubes in the same manner as described above, the surface treatment can be more effectively performed by applying ultrasonic waves or using dispersion equipment such as a sand grinder and a ball mill.

The release property enhancer used in the present invention may be a release property enhancer made of any one or more of fluorine-based, silicon-based and ethylene oxide-based release agents, or a mixture thereof. It is important to maintain the proper content of the present invention because too many of these release enhancers may cause the release promoter molecules to crawl too much to the surface and rather act as impurities during the process.

Examples of the solvent that can mix these components include water, alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol and isobutyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ether solvents such as solvent, diethyl ether, dipropyl ether, dibutyl ether, alcohol ether solvents such as ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, N-methyl Amide solvents such as 2-pyridyridone, 2-pyridyridone, N-methylformamide, N, N-dimethylformamide, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, diethyl sulfone and tetra Any one of sulfone solvents such as methylene sulfone, nitrile solvents such as acetonitrile, amine solvents such as alkylamine, cyclic amine, aromatic amine, and organic solvents such as toluene and xylene Or two or more may be mixed.

The method of applying the antistatic coating solution to the surface may be used almost any coating method, such as spray method, electrodeposition coating method, impregnation method, roll coating method, bar coating method, gravure method, reverse gravure method, After curing with drying for 30-30 minutes at a temperature of 20-250 degrees Celsius it is possible to form an antistatic layer having excellent coating properties.

The thickness of the antistatic layer coating film is appropriate for the thickness of 0.02-10 microns after drying and curing. If the thickness of the antistatic layer is less than 0.02 micron, it is difficult to obtain a uniform antistatic effect and uncomfortable. If the antistatic layer exceeds 10 microns, the antistatic property enhancing effect is insignificant and opaque, which is not preferable.

In coating the base polymer surface with the antistatic coating solution containing the metal oxide as an active ingredient, when the difference in the surface tension between the base polymer and the solution is large, the wettability and adhesion of the solution are poor, and the base polymer surface is corona treated to treat the surface of the base polymer surface. It is effective to increase the wettability and adhesion of the coating solution by having a tack of at least 35 dynes / area.

In addition, when primer-treated compounds such as urethane, acrylic, amide, imide, amic acid, ester, silane, and epoxy compounds or silicate compounds to improve adhesion between the antistatic layer and the base polymer, It is effective because it can improve the adhesion. When these primer components are primed on the surface of the polymer film, it is more effective to use these components by mixing them in a 0.01-30 weight ratio with respect to a solvent that can be used in the present invention.

The base film that can be used in the present invention includes an ester film, an imide film, an etherimide film, a carbonate polymer film, an olefin polymer film such as cyclic olefin or polypropylene, a film made of polyvinyl chloride resin, and styrene. It can be applied to various kinds of polymer films, such as all polymers or laminated polymers, regardless of the type of resins or films made of various acrylic resins, oxide polymer films such as polyphenylene oxide, and high heat resistant polymer films such as polyether sulfone. Do. Particularly, in the case of the polyimide film, when the spacer for the process is manufactured using the technology of the present invention, the spacer can be used without changing the spacer from the cleaning process to the integrated circuit chip curing process. In addition, by forming the antistatic layer on the surface of the triacetate cellulose, which is the base film for polarizing film, which is the most important film among the display products using the liquid crystal polymer, the antistatic layer is formed on the surface to prevent the generation of static electricity during various processes. The surface of the antistatic layer is not damaged even after the washing process using the basic aqueous solution is very effective. In addition to the above application, if the antistatic layer is formed on the polyimide surface of the fabric for flexible printed circuit board using the above-described technique, it can withstand the washing of basic aqueous solution and is effective.

If both edges are to be embossed from the antistatic film produced by the method of the present invention, heat and pressure may be applied to create convex embossing on the edges. This is the same as in the known art.

     The present invention will be described in more detail with reference to the following examples. However, these examples do not limit the scope of the present invention.

Comparative Example 1

4 grams of 3,4-polyethylenedioxythiophene aqueous solution, 9 grams of an acrylic binder having a molecular weight of 10,000, 0.2 grams of ethylene glycol, and 0.2 grams of 1-methyl-2-pyridyridone were used as ethyl alcohol and isopropyl alcohol. 25 grams of mixed solvent was mixed to prepare a conductive coating solution, which was then coated on a 125 micron thick polyester film with a thickness of 1 micron and dried at 100 ° C. for 2 minutes.

Thereafter, a 5% aqueous solution of caustic soda was poured into an ultrasonic cleaner having a frequency of 40 kHz and 300 watts, and then, an antistatic polyester film prepared by the above method was put therein and ultrasonically cleaned for 40 minutes.

The surface resistance of the polyester film before the ultrasonic cleaning was 10 ⁵ ohms / area, but after ultrasonic cleaning in a 5% aqueous solution of caustic soda, the surface resistance was 10 ¹² ohms / area or more, it was confirmed that the insulation after the ultrasonic cleaning.

Comparative Example 2

5 grams of 3,4-polyethylenedioxythiophene aqueous solution and 5 grams of 6-functional urethane acrylate oligomer, 5 grams of trifunctional urethane acrylate monomer, 0.3 gram of methylbenzoylformate, 20 grams of isopropyl alcohol and ethylene glycol monoethyl ether Mix with 20 grams to make an antistatic agent. The antistatic liquid was dried on the surface of the polyester film and then coated to a thickness of 0.7 micron, dried at 100 ° C. for 1 minute, and cured by applying 800 millimeters of Joules using a metal halide lamp to form an antistatic layer on the surface.

The surface resistivity of the polyester film prepared by the above technique was 10 ⁶ ohms / area, and the surface resistance was observed to be 10 ¹² ohms / area after ultrasonic cleaning in a 5% aqueous solution of caustic soda. As a result of observing the surface, all of the antistatic layer on the surface fell off.

Comparative Example 3

Comparative Example 3 is a 125-micron-thick polyimide film on the surface of an antistatic coating solution containing 1 gram of doped tin oxide with a particle size of 1 micron and 1 gram of a urethane binder in 12 grams of a water / alcohol (50:50) mixed solvent. After drying on the surface to form an antistatic layer to a thickness of 1 micron to prepare an antistatic polyimide film.

The surface resistance of the polyimide film produced by the above technique was measured at 10 ⁸ ohms / area. The film was placed in a 5% aqueous solution of caustic soda according to the method of Comparative Example 1, and the surface resistance was observed. After the ultrasonic cleaning time, the surface resistance did not change until 40 minutes. Resistance was observed above 10 ¹² ohms / area and turned into insulating.

In the case of the antistatic layer using the conductive polymer and the metal oxide, which is a conventional antistatic layer forming technology, from Comparative Examples 1-3, the antistatic layer formed on the surface by dissolving the binder component or the conductive polymer component is dissolved in a caustic soda solution of 5%. It can be seen that it is greatly damaged.

<Example 1>

Example 1 is a surface treatment of tin oxide particles of 3 microns size doped with antimony with an acrylate-based silane interfacial agent, and after treating 5 grams of tin oxide with 0.1 grams of silane having a methacrylate functional group, methylcellulose The antistatic coating liquid mixed with 30 grams of solvent, 2.5 grams of epoxy resin, and 0.75 grams of a curing agent was dried on the surface of a 125 micron-thick polyimide film to form an antistatic layer having a thickness of 1.0 micron to prepare an antistatic polyimide film. .

The surface resistance of the polyimide film produced by the above technique was measured to be 10 ⁸ ohms / area. The film was cut to a suitable size and sonicated in a 5% aqueous solution of caustic soda for 90 minutes and measured at 10 ⁸ ohms / area without change in resistance.

<Example 2>

Example 2 is a carbon nanotube instead of tin oxide as an antistatic agent, and is the same as Example 1 except that 0.7 grams of the surface treated with an epoxy silane binder after acid treatment of the carbon nanotubes were used. .

The surface resistance of the polyimide film produced by the above technique was measured to 10 ⁹ ohms / area. The film was cut to a suitable size and sonicated in a 5% aqueous solution of caustic soda for 90 minutes and measured at 10 ⁹ ohms / area without change in resistance.

<Example 3>

Example 3 is the same as that of Example 1 except for using the glycidoxy propyl trimethoxysilane as the epoxy-based silane interfacial binder.

The surface resistance of the polyimide film produced by the above technique was measured to be 10 ⁸ ohms / area. The film was cut to a suitable size and sonicated in a 5% aqueous solution of caustic soda for 90 minutes and measured at 10 ⁸ ohms / area without change in resistance. In addition, as a result of sonication in a 10% aqueous potassium hydroxide solution for 90 minutes, the resistance was measured at 10 ⁹ ohms / area, and it was confirmed that the basic aqueous solution of high concentration was endured without significant resistance change.

<Example 4>

Example 4 is the same as Example 1 except for using a 125 micron-thick polyethylene terephthalate film as the base polymer film.

The surface resistance of the film was measured to 10 ⁸ ohms / area. The film was cut to an appropriate size and sonicated in a 5% aqueous solution of caustic soda for 90 minutes, and measured to 10 ⁸ ohms / area without change in resistance.

<Example 5>

Example 5 was first coated with a primer on the surface of the polyimide film with a solution of 0.5 grams of epoxy silane interfacial binder (glycidoxypropyltrimethoxysilane) and 67 grams of isopropyl alcohol, and then Except for applying the antistatic liquid is the same as in Example 3.

The surface resistance of the polyimide film produced by the above technique was measured to be 10 ⁸ ohms / area. The film was cut to an appropriate size and sonicated in a 5% aqueous solution of caustic soda for 90 minutes, and the resistance was measured to 10 ⁸ ohms / area without change in resistance. In addition, as a result of sonication in a 10% aqueous potassium hydroxide solution for 90 minutes, the resistance was measured to 10 ⁸ ohms / area to confirm that the resistance was maintained as it is.

<Example 6>

Example 6, except that the antistatic polyester film prepared by the method of Example 4 was cut to a width of 35.1 millimeters and then embossed with a convex shape of 1.2 millimeters in height on both edges to produce a spacer tape. Is the same as

The surface resistance of the middle portion of the embossed spacer produced by the above technique was 10 ⁸ ohms / area and the resistance of the embossed portion rose slightly to 10 ⁹ ohms, but the antistatic property was maintained. The embossed spacer was cut into a suitable size, placed in a 5% aqueous solution of caustic soda, and sonicated for 90 minutes. The surface resistance of the center portion and the embossed portion remained unchanged.

When the antistatic layer containing the metal oxide, the curable resin binder, and the curing agent of the present invention as an active ingredient is formed on the surface of the base polymer, the antistatic layer on the surface may not be damaged even when placed in a basic aqueous solution, and thus may be used as the polymer film for the washing process. The antistatic polymer film surface-treated in the same manner maintains antistatic properties even after washing and identification using a basic aqueous solution during the manufacturing process, and in particular, a polymer product in the form of embossing or other processing using heat and pressure There is no change in the surface resistance even after the washing process using a basic aqueous solution has the effect of maintaining the antistatic properties.

Claims (12)

0.1-20 parts by weight of a metal oxide or carbon nanotube, 0.5-20 parts by weight of a curable resin, 0.02-5 parts by weight of a curing agent, and 55-99.38 parts by weight of a solvent. Antistatic composition that can be reused without changing resistance The antistatic composition according to claim 1, wherein the metal oxide is a metal oxide including indium oxide, tin oxide, titanium oxide, and zinc oxide having an average particle diameter of 0.002-5 microns. The antistatic composition according to claim 1, wherein the carbon nanotubes are carbon nanotubes including single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, or graphite. [Claim 2] The antistatic composition according to claim 1, wherein the curable resin is a resin composed of an epoxy resin or a phenol resin alone or in a mixture thereof. The method of claim 1, wherein in dispersing the metal oxide or carbon nanotubes together with the curable binder, a silane-based interfacial agent containing an acrylate, epoxy, vinyl, or amino-based methacrylate in advance Antistatic composition characterized in that the surface treatment to improve the dispersibility and interfacial bonding force. 6. The permanent antistatic composition according to claim 5, wherein the content of the interfacial binder is 0.01 to 5 parts by weight based on 100 parts by weight of the metal oxide or carbon nanotube. The permanent antistatic composition according to claim 1, wherein 0.05-5 parts by weight of a release property-adding additive is added to 100 parts by weight of the antistatic solution. 8. The permanent antistatic composition according to claim 7, wherein the release property imparting additive is a silicone-based, fluorine-based, or acrylic-based additive. An antistatic polymer product according to any one of claims 1 to 8 is applied to the surface of the base polymer to form an antistatic layer, which can be reused without changing the surface resistance after washing in a basic washing solution. 10. The antistatic polymer product according to claim 9, wherein the surface polymer has a surface tension of at least 35 dyne / area by corona treatment to enhance adhesion between the base polymer and the antistatic layer. 10. The method according to claim 9, wherein the urethane, acrylic, amide, imide, amic acid, ester, silane, epoxy, or silicate compounds are added in an amount of 0.01-30% by weight to improve adhesion between the base polymer and the antistatic layer. Antistatic polymer product characterized in that the primer treatment by mixing. The base polymer according to claim 9, wherein the base polymer is an ester film, an imide film, an etherimide film, a carbonate polymer film, an olefin polymer film including cyclic olefin or polypropylene, a film made of polyvinyl chloride resin, or a styrene type. Forms in which any one or these components are mixed among a film made of a resin or a cellulose polymer, a film made of various acrylic resins, an oxide polymer film containing polyphenylene oxide, and a high heat resistant polymer film containing polyether sulfone Antistatic polymer product, characterized in that the polymer film, or a laminated film of the form in which each polymer is laminated.