KR20090075360A - Adhesive film with good antistatic characteristics and durability - Google Patents

Abstract

An adhesive film is provided to ensure excellent endurance and antistatic property at the same time and to prevent the contamination of adherend. An adhesive film(101) with excellent endurance and antistatic property comprises an anti-static layer(3) and an adhesive sheet(10) which successively includes an adhesive layer(2) and a release film(1) to both sides of the anti-static layer. Or the adhesive film comprises the anti-static layer, the release film formed at one side of the anti-static layer, and the adhesive sheet which successively includes an adhesive layer and the release film at the other side of the anti-static layer.

Description

Adhesive film with excellent antistatic performance and durability {ADHESIVE FILM WITH GOOD ANTISTATIC CHARACTERISTICS AND DURABILITY}

The present invention relates to an adhesive film having excellent antistatic performance and durability, and more particularly, an adhesive film having excellent antistatic performance and excellent antistatic performance and excellent antistatic performance and durability capable of preventing contamination of the adherend. It is about.

In general, adhesive films and sheets are mainly used for adhesion of electronic components, protective films, optical films for displays, and the like, and their use is gradually increasing. In addition, the pressure-sensitive adhesive film and the sheet is a structure in which the pressure-sensitive adhesive is coated on the film form of the hydrophobic polymer is likely to generate static electricity.

Such static electricity causes many problems in the production of electronic products. That is, contaminants such as dust enter the electronic products due to static electricity, which causes permanent or temporary damage to the electronic products. In addition, in the case of the liquid crystal display, static electricity is generated when the optical film is laminated, thereby affecting the liquid crystal alignment and causing defects.

Therefore, in order to prevent such static electricity, an antistatic function is required. Conventional methods for imparting an antistatic function have been imparted by coating an antistatic material on the outer surface of the film or by mixing on an adhesive. However, when the antistatic layer is coated on the outer surface of the film, there is a problem that the coating surface may be vulnerable to moisture when peeled off during the reliability test. In addition, if the antistatic function is imparted on the adhesive, the antistatic agent may move to the surface of the adhesive in the case of the ionic system, and may be peeled off over time. There is a problem that can reduce the transparency by using a large amount to achieve a chain structure of the material.

In the prior art of the adhesive film and sheet imparting the antistatic function, in the case of Korean Patent Publication No. 2007-0054250, the antistatic performance was realized by coating the film surface, and in the case of Korean Patent Publication No. 2006-0049137, Hybrid charging performance is realized.

However, the coating method of the conventional technique is not competitive in terms of cost or process by coating directly on an expensive optical film, and the method of mixing and using an acrylic adhesive has a high heat-resistant condition due to a lack of properties and stability of the adhesive layer. As time passes, peeling may occur between the interfaces. In addition, in the case of a general protective film, it can be used because it is removed after a certain time has elapsed, but in the case of an adhesive for a polarizing plate used for a liquid crystal display, since it is permanently bonded, the antistatic migration to the surface is large in reliability. This is a problem.

The present invention has been made to solve the above problems, the object of the present invention has excellent durability and at the same time excellent antistatic performance and excellent antistatic performance and durability that can prevent contamination of the adherent adhesive film excellent Is to provide.

The object is achieved by an antistatic performance and durability excellent pressure-sensitive adhesive film having a pressure-sensitive adhesive sheet and a release layer formed on both sides of the antistatic layer and the antistatic layer sequentially.

In addition, the object of the present invention is to provide an antistatic performance and a durable adhesive film having an antistatic layer, a release film formed on one surface of the antistatic layer, and an adhesive sheet having a pressure sensitive adhesive layer and a release film sequentially formed on the other surface of the antistatic layer. Is achieved by

Here, the pressure-sensitive adhesive layer is characterized in that formed with an acrylic pressure-sensitive adhesive composition.

In addition, the antistatic layer is characterized in that it comprises an antistatic functional material, such as nanofiber conductive material, conductive nano organic particles, conductive nano inorganic particles or ionic compounds.

Preferably, the surface resistance of the pressure-sensitive adhesive layer is characterized in that less than 10 ¹² / □.

According to the pressure-sensitive adhesive film excellent in antistatic performance and durability according to the present invention, it has the effect of having excellent durability and at the same time excellent antistatic performance and to prevent contamination of the adherend.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings of the present invention. These examples are only presented by way of example only to more specifically describe the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples. .

In the adhesive film having excellent antistatic performance and durability according to the first embodiment of the present invention, the adhesive layer 2 and the release film 1 are sequentially formed on both sides of the antistatic layer 3 and the antistatic layer 3. It is characterized by comprising an adhesive sheet (10).

In addition, the antistatic performance and durability of the adhesive film according to the second embodiment of the present invention, the antistatic layer 13, the release film 1 formed on one surface of the antistatic layer 13, and the antistatic layer 13 On the other side of the) is characterized in that the pressure-sensitive adhesive layer (2) and the release film (1) is provided with a pressure-sensitive adhesive sheet 10 sequentially configured.

The pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film excellent in antistatic performance and durability according to the present invention is 0.1 to 10 parts by weight of vinyl monomers crosslinkable with 90 to 99.9 parts by weight of an acrylate having an alkyl group of 4 to 12 carbon atoms or acrylic It is preferable that it is an acrylic adhesive composition for optical films obtained by copolymerizing 0.1-10 weight part of monomers.

The acrylic polymer used in the present invention preferably has a weight average molecular weight of 100,000 or more and 3 million or less, preferably 300,000 or more and 2 million or less, more preferably 500,000 or more and 1.5 million or less, and a weight average molecular weight of 100,000 or more. If it is small, the adhesive remains due to the decrease in cohesion, and if it is more than 3 million, the viscosity increases, which is because workability worsens. Here, the said weight average molecular weight means what was measured by gel permeation chromatography (GPC). In the present invention, the acrylic oligomer having a weight average molecular weight of 3000 to 50000 may be mixed and used.

In addition, the antistatic layer of the adhesive film excellent in antistatic performance and durability according to the present invention can exhibit the charging performance using a material such as conductive polymer, ionic, tin oxide, carbon nanotube, carbon nanotube and conductive polymer It is excellent in charging characteristics to use.

As an antistatic agent having an antistatic performance, in the case of a cationic antistatic agent having a cationic functional group, anionic electrification having an anionic functional group such as quaternary ammonium salt, pyridinium salt, first, second or third amino group, etc. In the case of the inhibitor, sulfonate and sulfate ester salts, phosphonates, phosphate ester salts, and the like, alkylbetaines and derivatives thereof, imidazoline and its derivatives, alanine and its derivatives, positive antistatic agents, amino alcohols and the like Ionic antistatic agents, such as nonionic antistatic agents, such as its derivative (s), glycerin and its derivative (s), polyethyleneglycol, and its derivative (s), are used. In addition, it is also possible to polymerize a monomer having an ion conductive group, and such an ion conductive polymer may be alkyl trimethyl ammonium salt, acylyl amido propyl trimethyl ammonium metho sulfate, alkyl benzyl methyl ammonium salt, acyl chloride, polydimethylamino Quaternary ammonium groups, such as styrene copolymer which has quaternary ammonium groups, such as (meth) acrylate copolymer which has quaternary ammonium groups, such as ethyl methacrylate, and polyvinyl benzyl trimethylammonium chloride, and polydiallyl dimethylammonium chloride Anionic types such as cationic types such as diallylamine copolymers having an alkyl group, alkyl sulfonates, alkylbenzene sulfonates, alkyl sulfate ester salts, alkyl ethoxy sulfate ester salts, alkyl phosphate ester salts, and sulfonic acid group-containing styrene copolymers Zwitterions such as alkyl betaine, alkyl imidazolium betaine and carbo betaine graft copolymers Brother. Fatty acid alkylolamides, di (2-hydroxyethyl) alkylamines, polyoxyethylenealkylamines, fatty acid glycerin esters, polyoxyethylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxysorbitan fatty acid esters, poly Nonionic antistatic agents such as oxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyethylene glycol, polyoxyethylene diamine, copolymers made of polyester and polyamide, methoxy polyethylene glycol, (meth) acrylate, Conductive polymers such as polyaniline, polypyrrole, polythiophene, tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, A conductive material such as iron, cobalt, copper iodide, and an alloy or mixture thereof can be used to exhibit charging performance.

These compounds listed above may be used alone or in combination of two or more thereof. In addition, these conductive materials continue to evolve and can be used in various mixtures, and thus do not limit such materials themselves. General purpose resins such as polyester, acrylic, polyvinyl, urethane, epoxy, and the like used in the antistatic resin and the conductive resin may be used, and as the crosslinking agent, a curable resin such as an epoxy compound or an asoate may be used. As the organic solvent, methyl ethyl ketone, acetone, ethyl acetate, isopropanol, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, methanol, ethanol, xylene and the like can be used. It can also be used as a mixed solvent of these. Coating methods include spray coating, air knife coating, curtain coating, nip coating, gravure coating and the like. The thickness of the antistatic resin layer, the conductive polymer or the conductive resin is usually 0.01 to 5 μm, preferably about 0.01 to 1 μm, and the thickness of the conductive material layer is usually 20 to 10000 mm 3, preferably 50 to 5000 mm 3.

The adhesive sheet used for this invention is equipped with the adhesive layer containing the above-mentioned adhesive composition, and the form of an adhesive sheet is not specifically limited. In the case of the adhesive sheet as described above, it is referred to in various forms such as sheets, tapes, protective films, and the like.

In addition, the thickness of the pressure-sensitive adhesive sheet is not particularly limited, but is generally a transparent plastic film, such as 10 to 2000㎛, the pressure-sensitive adhesive layer can be added to one or both sides of the substrate, the thickness of the pressure-sensitive adhesive layer is usually 1 to 1 to. 500 micrometers, Preferably it is 5-100 micrometers. The adhesive sheet may or may not have a base material, and in the case of the adhesive sheet without the base material, the pressure-sensitive adhesive composition may be applied onto a release film and dried to laminate the release film. For example, it is suitable for fixing an optical filter and an optical film. As an optical film, the film of a polarizing plate, a PDP filter, a touch panel, etc. are mentioned. These optical films, cellulose films such as triacetate cellulose, polycarbonate films, polyester films such as polyethylene terephthalate, polyethersulfone films, polyethylene, polypropylene, cycloolefins, and polyolefins having a norbornene structure, Optical products such as polyolefin-based acrylic resin plates, polycarbonate plates, glass plates, etc., such as ethylene propylene copolymer, are bonded through the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention to provide optical products such as LCDs, PDPs, and touch panels. It can manufacture preferably.

Example 1

1 is a cross-sectional view of a pressure-sensitive adhesive film excellent in antistatic performance and durability having an antistatic performance produced by the first embodiment of the present invention. As shown in Figure 1, the antistatic performance and durability excellent pressure-sensitive adhesive film 101 according to the present invention has a pressure-sensitive adhesive sheet (10) consisting of a pressure-sensitive adhesive layer (2) and a release film (1) on both sides therebetween The prevention layer 3 is comprised. According to the following manufacturing method to prepare an adhesive film excellent in antistatic performance and durability of Example 1.

A: Preparation of Acrylic Copolymer

First, 150 g of ethyl acetate solvent is injected into a 1,000-kW reactor equipped with a cooling device to prepare an acrylic pressure-sensitive adhesive, under which nitrogen gas is refluxed, easy to adjust temperature, and to control an exothermic reaction, and 33 g of butyl acrylate and methyl A mixture of monomers including 6 g of acrylate, 7 g of acrylic acid and 0.3 g of hydroxybutyl acrylate was added and stirred for 30 minutes to remove oxygen. Thereafter, after maintaining the temperature in the reactor at 60 ° C. under nitrogen atmosphere, 0.017 g of azobisdimethylvaleronitrile (ADMVN) was added thereto, followed by polymerization for 4 hours to 8 hours to obtain an acrylic copolymer polymer. In order to confirm the reproducibility of the experiment, the same experiment was performed five times, and the number average molecular weight and dispersion degree of the prepared acrylic polymer were measured using GPC, and the number average molecular weight was 2 million to 2.5 million, and the molecular weight distribution was 3.0. To 3.5.

B: Preparation of Acrylic Adhesive Composition

65 parts by weight of ethyl acetate (EAc), which is a solvent, is diluted with respect to 100 parts by weight of the acrylic copolymer prepared in A, and 2 g of tolylene diisocyanate adduct of trimethylolpropane, an isocyanate curing agent, and a silane as a crosslinking agent as a polar compound. An acrylic adhesive was prepared by uniformly mixing 1 g of a vinyl trimethoxysilane as a coupling agent. Sequentially added and uniformly stirred to prepare an acrylic pressure-sensitive adhesive composition.

C: Formation of the First Adhesive Layer

The acrylic pressure-sensitive adhesive composition prepared in B was coated on a biaxially stretched polyester release film having a thickness of 38 μm using a bar coater, and dried at 110 ° C. for 2 minutes to obtain a uniform pressure-sensitive adhesive layer having a thickness of 10 μm.

D: Formation of Antistatic Layer on First Adhesive Layer

10 g of a conductive polymer poly (3,4-ethylenedioxythiophene) dispersion (Bayer, BaytronP) dissolved in ethanol and 20 g of a urethane-based binder (Alberg Dingk, U710, Germany) were dissolved in 70 g of ethyl alcohol. Mixing to prepare an antistatic solution. An antistatic layer was formed to a thickness of 0.1 μm by using a spray method on the antistatic liquid prepared on the first adhesive layer.

E: Forming a second pressure-sensitive adhesive layer to produce an adhesive film excellent in antistatic performance and durability

After forming a uniform pressure-sensitive adhesive layer having a thickness of 10 ㎛ in the same manner as in C, after laminating the second adhesive layer on the antistatic layer formed on the first adhesive layer prepared in D, it is aged at room temperature for 7 days to charge A pressure-sensitive adhesive film with excellent anti-permeability and durability was prepared.

Example 2

In the formation of the antistatic layer, a pressure-sensitive adhesive film having excellent antistatic performance and durability was prepared in the same manner as in Example 1 except that 2 g of carbon nanotubes (HollowCNT 50, manufactured by Nano Carbon Co., Ltd.) were mixed and used.

Example 3

An adhesive film having excellent antistatic performance and durability was prepared in the same manner as in Example 1 except that 15 g of an ionic (PEL-20A, Japanese carlit) was mixed with 85 g of ethanol in the formation of an antistatic layer.

Example 4

2 is a cross-sectional view of the antistatic performance and excellent adhesion film having an antistatic performance and the antistatic performance prepared by the second embodiment of the adhesive film excellent in antistatic performance and durability according to the present invention. As shown in Figure 2, the antistatic performance and durability of the pressure-sensitive adhesive film 104 of the present invention is a pressure-sensitive adhesive sheet 10 and a release film made of a pressure-sensitive adhesive layer (2) and a release film (1) according to the first embodiment The antistatic layer 3 is comprised between (1).

The pressure-sensitive adhesive was prepared in the same manner as in A and B of Example 1, and a pressure-sensitive adhesive layer was formed to a thickness of 20 μm in the same manner as in C. 0.2 g of single-walled carbon nanotubes (KH SWNT-Semiconducting, KH Chemical Co., Ltd.) was dispersed in 10 g of ethanol on the pressure-sensitive adhesive layer, and then coated at about 100 nm in the same manner as in D to form an antistatic layer and to laminate a polyester-based release film. To prepare an adhesive film excellent in antistatic performance and durability.

Example 5

The pressure-sensitive adhesive was prepared in the same manner as in A and B of Example 1, and a pressure-sensitive adhesive layer was formed to a thickness of 20 μm in the same manner as in C. An antistatic solution was prepared by mixing 10 g of ITO (AIS-E030, manufactured by Mijitech Co., Ltd.) and 20 g of a urethane binder (U710, German ALBERDINGK Co., Ltd.) on 70 g of ethyl alcohol. The antistatic solution was coated at about 100 nm in the same manner as in D to form an antistatic layer, and a polyester-based release film was laminated to prepare an adhesive film having excellent antistatic performance and durability.

Comparative Example 1

3 is a cross-sectional view of an adhesive film having excellent antistatic performance and durability according to a comparative example. As shown in FIG. 3, the adhesive film 106 having excellent antistatic performance and durability according to a comparative example is composed of an adhesive layer 15 in which an antistatic agent is mixed between the release films 1 on both sides.

3 g of an ionic antistatic agent (PEL-20A, Japanese carlit) was mixed with an adhesive prepared in the same manner as in Example 1, and an adhesive layer was formed in the same manner as in Example 1 B and C, except that the adhesive layer was a single The layer was coated with a thickness of 20 μm and the polyester-based release film was laminated to prepare an adhesive film having excellent antistatic performance and durability.

Comparative Example 2

As a solid on the surface of the corona-treated polarizer (AMN-3244EV, manufactured by Ace Digitech Co., Ltd. or AMN-3244SVAG25), 0.5 wt% of conductive polymer resin (Bayer, BaytronP; poly3,4-ethylenedioxythiophene and 0.8 wt% of polystyrenesulfonic acid) 100 parts by weight of an aqueous dispersion containing water), 400 parts by weight of an acrylic binder resin (Nippon Carbide, Y8003B), 100 parts by weight of melamine crosslinking agent (Cytec, CYMEL385) and 50 parts by weight of a fluorine-based silane coupling agent to prevent antistatic A coating solution was prepared. At this time, the content of the solid content was to contain 2.0% by weight based on the total antistatic coating liquid. The prepared antistatic coating solution was applied to one surface of the corona discharge treated polarizer using a Mayer bar. The thickness after the drying was applied so as to be 50 nm, and the coating liquid applied in a drying section at 100 to 120 ° C. was dried. The pressure-sensitive adhesive layer was formed on the coated surface of the film in the same manner as in A, B, and C of Example 1, except that the pressure-sensitive adhesive layer was coated with a single layer with a thickness of 20 μm and the polyester-based release film was laminated to prevent antistatic performance. An excellent pressure-sensitive adhesive film was prepared.

Experimental Example

Experimental Example 1: Evaluation of Durability Reliability

Optical absorption of the polarizing plate (AMN-3244EV, manufactured by Ace Digitech Co., Ltd., or AMN-3244SVAG25, width: 90 mm, length: 170 mm) laminated on the glass substrate (110 mm × 190 mm × 0.7 mm) onto the glass substrate (110 mm × 190 mm × 0.7 mm). The shaft was attached with the cross. At this time, the pressure applied was about 5kg / cm ² and the clean room operation was performed so that no bubbles or foreign substances were generated. The specimens were left for 1000 hours at 60 ° C and 95% relative humidity to observe the heat and moisture resistance. The heat resistance was observed at 85 ℃ for 1000 hours after the bubble or peeling. Immediately after evaluating the state of the specimen was carried out at room temperature for 24 hours. Evaluation criteria for reliability are as follows and the results are shown in Table 1.

○: no bubbles or peeling

△: bubble or peeling phenomenon

×: bubble or peeling phenomenon

Experimental Example 2: Measurement of Surface Resistance

After removing the release film from the polarizing plate laminated with the adhesive film prepared above, the surface resistance of the adhesive surface was measured. Surface resistance was measured after applying a voltage of 100V for 1 minute at 23 ℃, 50% relative humidity environment using a resistivity meter (TREK INC., 152-CE-EX). The results are shown in Table 1.

TABLE 1

Surface resistance Heat resistance Heat resistant Example 1 10 ⁷ ○ ○ Example 2 10 ⁵ ○ ○ Example 3 10 ¹¹ △ △ Example 4 10 ⁵ ○ ○ Example 5 10 ⁶ ○ ○ Comparative Example 1 10 ¹¹ × × Comparative Example 2 10 ¹¹ △ △

As can be seen in Table 1, the antistatic performance and durability of the pressure-sensitive adhesive film according to the present invention can be confirmed that the excellent antistatic performance, but also excellent heat and moisture resistance and heat resistance. In addition, the antistatic performance and durability of the pressure-sensitive adhesive film according to the present invention has an advantage in that the antistatic material is located in the middle of the pressure-sensitive adhesive layer does not migrate to the pressure-sensitive adhesive surface and has excellent durability. In Example 3, the ionic antistatic agent is used, and the chargeability and durability are lower than those of the other nonionic ionic materials, but the same ionic system as in Example 3 but the layer structure is different. It can be seen that the durability is superior to the case of.

1 is a cross-sectional view of the adhesive film excellent in antistatic performance and durability having an antistatic performance produced by the first embodiment of the present invention.

Figure 2 is a cross-sectional view of the pressure-sensitive adhesive film excellent in antistatic performance and durability having an antistatic performance prepared by the second embodiment of the present invention.

3 is a cross-sectional view of the pressure-sensitive adhesive film excellent in antistatic performance and durability having an antistatic performance prepared by a comparative example.

<Brief description of symbols for the main parts of the drawings>

1: release film 2: adhesive layer

3, 13: antistatic layer 10: adhesive sheet

15: pressure-sensitive adhesive layer mixed with antistatic agent

101, 104, 106: Adhesive film with excellent antistatic performance and durability

Claims (5)

In the adhesive film excellent in antistatic performance and durability, Antistatic layer, An adhesive film having excellent antistatic performance and durability, characterized in that the adhesive sheet and the release film is provided on both sides of the antistatic layer sequentially comprising an adhesive sheet. In the adhesive film excellent in antistatic performance and durability, Antistatic layer, Release film formed on one surface of the antistatic layer, An adhesive film having excellent antistatic performance and durability, characterized in that the other surface of the antistatic layer is provided with a pressure-sensitive adhesive layer sequentially composed of a pressure-sensitive adhesive layer and a release film. The method according to claim 1 or 2, The pressure-sensitive adhesive layer is formed of an acrylic pressure-sensitive adhesive composition, characterized in that the antistatic performance and durability excellent pressure-sensitive adhesive film. The method of claim 4, wherein The antistatic layer is characterized in that it comprises an antistatic functional material, such as conductive material, conductive nano organic particles, conductive nano-organic particles or ionic compounds on the fibrous, excellent antistatic performance and durability adhesive film. The method of claim 4, wherein Surface resistance of the pressure-sensitive adhesive layer is characterized in that 10 ¹² / □ or less, excellent antistatic performance and durability adhesive film.

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