KR100810413B1 - Adhesive composition for surface protective film and surface protective film using the same - Google Patents

Abstract

A pressure sensitive adhesive composition for a surface protective film, and a surface protective film using the composition are provided to improve antistatic property and to prevent the generation of bur in case of cutting a surface protective film. A pressure sensitive adhesive composition comprises 1-5 parts by weight of an ion complex polymer antistatic agent based on 100 parts by weight of an acrylic resin, wherein the ion complex polymer antistatic agent is prepared by reacting at least one cationic metal salt selected from LiPF6, LiBF4, LiSbF6, LiClO4, LiCF3SO3, LiAsF6, LiC(CF3SO3)3, LiN(CF3SO3)2, LiNH2, LiN(C2H5)2, LiNH2, LiN(C2H5)2, LiI, LiBr, LiCl, LiF, NaPF6, NaClO4, NaI, NaSCN, KSCN, KPF6 and KClO4 with a cation conductive organic compound selected from propylene carbonate, ethylene glycol and dimethylformamide and an anion conductive organic compound selected from trilauryl phosphate, trichloromethyl ester and dimethylsulfoxide in turn.

Description

Adhesive composition for surface protection film and surface protection film using the same {Adhesive composition for surface protective film and surface protective film using the same}

1 is a schematic view showing the structure of a surface protection film according to an embodiment of the present invention.

2 is a schematic view showing the structure of a surface protection film according to another embodiment of the present invention.

3 is a schematic view showing the structure of a surface protection film according to another embodiment of the present invention.

* Description of Major Reference Marks *

10: second additional coating layer 20: base film

30: first additional coating layer 40: pressure-sensitive adhesive layer

50: release film

The present invention relates to an adhesive composition for a surface protection film and a surface protection film using the same, and more particularly, to an adhesive composition for a surface protection film for surface protection of an electronic component or an optical component such as a diffusion sheet and a polarizing plate and a surface protection using the same. It is about a film.

In this specification, the inside of a base film means the side in which an adhesive layer and a release film are formed, and the outside of a base film means the opposite side of the said inside.

Surface protective films of electronic parts and optical parts, such as diffusion sheets and polarizing plates, are usually made of plastics, and the plastics have high electrical insulation properties and have a property of accumulating static electricity generated by friction with other materials for a long time. In order to eliminate various problems due to the accumulated static electricity, antistatic measures such as removing, neutralizing or leaking the accumulated electric charges are necessary.

Background Art Conventionally, it is known to add an antistatic agent to the pressure-sensitive adhesive layer itself formed inside the base film as an antistatic technology, and it is known to use an antistatic agent such as an alkali metal salt such as lithium (Li ⁺ ) system as the antistatic agent. .

In particular, Korean Patent Publication No. 2006-0066401 discloses LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , LiAsF ₆ , LiC (CF ₃ SO ₃ ) ₃ , LiN (CF ₃ SO ₃ ) ₂ , LiI , Alkali metal salts or other transition metal salts in which one or more selected from LiBr, LiCl, LiF, NaPF ₆ , NaClO ₄ , NaI, NaSCN, KSCN, KPF ₆ or KClO ₄ are mixed with propylene carbonate, ethylene glycol or dimethyl formamide, etc. Ion-complex polymer antistatic agents ("ELECON" products, NanoCamtec Co., Ltd.) prepared by reacting with cationic conducting organic compounds and anionic conducting organic compounds such as trilauryl phosphite, trischloromethyl ester and dimethyl sulfoxide in turn. It is known to use "the ion complex polymer antistatic agent" in the adhesive composition at a ratio of 0.1 to 10% by weight.

The technique is intended to have improved conductivity even when the pressure-sensitive adhesive layer containing the ion complex polymer antistatic agent is extended to an industrially required thickness level (expanded to about 50 μm). However, the technique is not aware of any problem that static electricity generation is time dependent.

In addition, in the above technique, a conductive polymer coating layer is formed between the pressure-sensitive adhesive layer containing the ionic complex polymer antistatic agent and the base film, and the process is added without any advantages in the antistatic property or the change in the amount of static electricity generated over time. It is disadvantageous in terms of increasing thickness. Furthermore, in the case of forming the conductive polymer coating layer on the base film, the function that the adherend does not stick after peeling the surface protective film (hereinafter referred to as "ESD (Electrostatic discharge)" function) is deteriorated and the change over time appears. There is also a problem.

In addition, in the manufacturing process of the conventional surface protection film as described above, there is a problem that a burr (white matter; hereinafter referred to as "burr") is generated on the cut surface or the periphery in the cutting film or the like which cuts the surface film. What appeared was confirmed by the present inventors.

Since the burr acts as a foreign matter on the optical component, the electronic component, etc., even if a small amount of burr is generated, the defective rate of the product is increased.

Therefore, the need to remove the burr is great, but for this purpose, if a separate process of removing the burr has a problem that greatly reduces the process efficiency, it is necessary to fundamentally prevent burr generation.

However, in the antistatic film of the prior art, including the antistatic film containing the ion complex polymer antistatic agent in the pressure-sensitive adhesive layer, not only did not recognize the problem of burr generation itself, but also burr generation without performing a separate burr removal process There has been no research on how to prevent this inherently.

The present invention is to solve the problems of the prior art as described above, an object of the present invention, in the pressure-sensitive adhesive composition for a surface protective film containing an ion complex polymer antistatic agent in the pressure-sensitive adhesive composition and a surface protective film using the same, It is to provide a pressure-sensitive adhesive composition for a surface protection film and a surface protection film using the same, which not only have sufficient antistatic property, but also a change in the amount of static electricity generated after a time can be secured to a predetermined level or less.

Another object of the present invention is to prevent the generation of burrs at the time of cutting the surface protection film produced, thereby preventing foreign matters from being mixed in the electronic parts or optical parts from the beginning, further adding a separate process for removing the generated burrs It is not necessary to provide a pressure-sensitive adhesive composition for a surface protection film and a surface protection film using the same, which can increase process efficiency.

It is another object of the present invention to have a good adhesion, no sliding phenomenon from the base film, and a function that the adherend does not stick after peeling of the surface protective film (hereinafter referred to as "ESD function"). It is providing the adhesive composition for surface protection films and a surface protection film using the same which are not changed.

In order to achieve the above object, in the present invention, LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , LiAsF ₆ , LiC (CF ₃ SO ₃ ) ₃ , LiN (CF ₃ SO ₃ ) ₂ , Cationic metal salts of at least one selected from LiNH ₂ , LiN (C ₂ H ₅ ) ₂ , LiI, LiBr, LiCl, LiF, NaPF ₆ , NaClO ₄ , NaI, NaSCN, KSCN, KPF _6, or KClO ₄ are propylenecarbo An ion complex polymer antistatic agent prepared by reacting a cationic conducting organic compound selected from nate, ethylene glycol or dimethyl formamide and an anion conducting organic compound selected from trilauryl phosphite, trischloromethyl ester or dimethyl sulfoxide in turn A pressure-sensitive adhesive composition for a surface protection film, comprising 1 to 5 parts by weight of the ion complex polymer antistatic agent per 100 parts by weight of an acrylic resin. The.

In one embodiment of the present invention, the cationic metal salt is preferably one or two selected from LiNH ₂ or LiN (C ₂ H ₅ ) ₂ .

In one embodiment of the present invention, the pressure-sensitive adhesive composition preferably comprises 1 to 5 parts by weight of the ion complex polymer antistatic agent and 1 to 20 parts by weight of the curing agent based on 100 parts by weight of the acrylic resin.

In one embodiment of the present invention, the pressure-sensitive adhesive composition is based on 100 parts by weight of the acrylic resin, 1 to 5 parts by weight of the ion complex polymer antistatic agent, 1 to 20 parts by weight of isocyanate resin and ethyl acetate It is preferable to include from 10 to 30 parts by weight.

In order to achieve the above object, the present invention provides a surface protective film comprising a base film and a coating layer of the pressure-sensitive adhesive composition for a surface protective film formed on the inner side of the base film.

In one embodiment of the present invention, the base film is preferably a PET film.

In one embodiment of the present invention, the base film is preferably made of a polyolefin resin biaxially stretched after applying the antistatic agent before stretching.

In one embodiment of the present invention, the thickness of the coating layer of the adhesive composition is preferably 10 to 50㎛.

In one embodiment of the present invention, it is preferable that the surface protection film is 0.5 kV or less even if the amount of static electricity generation changes over time.

In one embodiment of the present invention, the surface protection film is the first containing 40 to 100 parts by weight of ATO, which is conductive fine particles, based on 100 parts by weight of the urethane or acrylic resin between the base film and the coating layer of the adhesive composition. It is preferable that an additional coating layer is further formed.

In one embodiment of the present invention, it is preferable that the average particle diameter of ATO which is the said conductive fine particles is 0.01-1 micrometer.

In one embodiment of the present invention, the urethane-based or acrylic resin is preferably an ultraviolet curing urethane acrylate resin.

In one embodiment of the present invention, the first additional coating layer is preferably applied to 1 ~ 20㎛.

In one embodiment of the present invention, it is preferable that a second additional coating layer containing a conductive polymer is further formed on the outer surface of the base film, the second additional coating layer preferably further contains an antifouling agent, It is preferable that a said 2nd further coating layer further contains a rubber type resin.

In one embodiment of the present invention, the contact angle of the second additional coating layer is preferably 110 degrees or more.

In one embodiment of the present invention, the haze of the surface protection film on which the first additional coating layer is formed is preferably 1% or less.

In one embodiment of the present invention, the first additional coating layer preferably has a surface resistance of 10 ⁶ ~ 10 ⁹ kPa.

In one embodiment of the present invention, the haze of the surface protection film on which the second additional coating layer is formed is preferably 3% or less.

In one embodiment of the invention, the surface resistance of the second additional coating layer is preferably 10 ⁶ ~ 10 ⁸ kPa.

Hereinafter, an adhesive composition for a surface protection film and a surface protection film using the same according to the present invention will be described in detail.

1 is a schematic view showing the configuration of a surface protection film according to an embodiment of the present invention.

As shown in FIG. 1, in the surface protection film according to one embodiment of the present invention, an adhesive layer 40 is formed on an inner side surface of the base film 20, and a release film is formed on the adhesive layer 40. 50 is formed.

First, in the present invention, when the pressure-sensitive adhesive layer 40 is formed on a base film, 1 to 5 parts by weight of an ion complex polymer antistatic agent is added to 100 parts by weight of a normal pressure-sensitive adhesive component.

The ion complex polymer antistatic agent is known from the Republic of Korea Patent Publication No. 2006-0066401, 2004-0064523, in the present invention, in particular LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , LiAsF ₆ , LiC (CF ₃ SO ₃ ) ₃ , LiN (CF ₃ SO ₃ ) ₂ , LiI, LiBr, LiCl, LiF, NaPF ₆ , NaClO ₄ , NaI, NaSCN, KSCN, KPF ₆ or KClO ₄ Anionic conductive organic compounds, such as trilauryl phosphite, trischloromethyl ester or dimethyl sulfoxide, are added to a reaction product obtained by heating the mixed cationic metal salt with a cationic conductive organic compound such as propylene carbonate, ethylene glycol or dimethyl formamide while stirring. An ion complex polymer antistatic agent prepared by removing the unreacted metal salt from the final reaction product obtained by adding the compound and stirring with heating is used.

Meanwhile, in the present invention, LiNH ₂ or LiN (C ₂ H ₅ ) ₂ is particularly used as the cationic metal salt (these are not disclosed in Korean Patent Publication Nos. 2006-0066401 and 2004-0064523). As compared with the case of using one other cationic metal salt, it is preferable to achieve better chain bonds with the polymer, so that even after a lapse of time, the surface resistance and peeling antistatic property are excellent and surface transition does not occur.

When the ion complex polymer antistatic agent is added in an amount of less than 1 part by weight based on 100 parts by weight of the main ingredient, a change with time may occur, in particular, as the amount of static electricity generated increases over 0.5 kV. When the ion complex polymer antistatic agent exceeds 5 parts by weight with respect to 100 parts by weight of the subject, the change over time occurs less than when added in less than 1 part by weight (see "Testing the amount of static electricity generated when the polarizing plate is peeled off").

In addition, burr generation is caused when the ion complex polymer antistatic agent is added in less than 1 part by weight based on 100 parts by weight of the main ingredient. That is, when the ion complex polymer antistatic agent is contained in an amount of 1 part by weight or more, it is inserted into a portion to be linked during curing to lower the hardness, that is, to sufficiently perform the role of softening at the portion to be linked during curing. Burr is prevented.

When the ion complex polymer antistatic agent is more than 5 parts by weight, the hardness becomes too low during curing, and when the rubbing occurs by hand or by an eraser, the phenomenon occurs. Moreover, there exists a problem that the rolling phenomenon from such a base film becomes larger as time passes.

On the other hand, in the case of containing 1 to 5 parts by weight of the ion complex polymer antistatic agent in a range of 1 to 20 parts by weight based on 100 parts by weight of the main ingredient, particularly in the prevention of burr generation and the rolling phenomenon. desirable.

That is, when the pressure-sensitive adhesive composition is formed, in the case of containing 1 to 5 parts by weight of the ion complex polymer antistatic agent in each composition, it is compared with the case of containing less than 1 part by weight or more than 5 parts by weight of the ion complex polymer antistatic agent. It has the effect that generation | occurrence | production is prevented and the rolling phenomenon from a base film and its aging change are prevented.

However, the function of preventing burr generation by adding more than 1 part by weight of the ion complex polymer antistatic agent may be insignificant if the curing itself is excessively made. In addition, the ion complex resin antistatic agent is added to 5 parts by weight or less to prevent the sliding phenomenon and its change over time may also be negligible if the curing itself occurs too little. Therefore, in the case where the ion complex polymer antistatic agent is added in an amount of 1 to 5 parts by weight, it is necessary to prevent the curing from being excessively occurring or less. For this purpose, it is preferable to add an amount of the curing agent in an amount of 1 to 20 parts by weight.

On the other hand, a solvent is added together with the above-mentioned main agent, the curing agent and the content is added in 10 to 30 parts by weight, which is the range usually added.

A general adhesive may be used as the subject of the adhesive composition, and in the present invention, for example, a high molecular weight 200,000 to 1 million acrylic resin [eg, butyl acrylate, ethylene methacrylate methyl copolymer resin (EMMA), ethyl ethylene acrylate Copolymer resin (EEA), ethylene methyl acrylate copolymer resin (EMA), etc.] can be used.

As the curing agent, for example, an isocyanate type is used, and as the solvent, for example, ethyl acetate (ETHYL ACETATE) is preferably used.

As a method for producing the pressure-sensitive adhesive composition, each of the main ingredient and the solvent is put into the corresponding composition and stirred for 10 minutes, and then the curing agent and the antistatic agent are put into the corresponding composition and mixed for another 10 minutes.

Next, as said base film 20, the polyolefin resin film of PET film is used, for example, 5-200 micrometers in thickness, Preferably the thing of 20-100 micrometers can be used. Moreover, the polyolefin resin film biaxially stretched after apply | coating an antistatic agent before extending | stretching a base film as a modified example can be used.

As a method of coating the adhesive composition on the base film 20, a coating method such as gravure, micro gravure, reverse, and kiss roll is used. The room temperature and humidity at the time of coating are 21-24 degreeC, 55-65% drying temperature is 100-130 degreeC, and drying time is 1.5 to 2 minutes, and coating amount is 10-50 micrometers, Preferably it is 25 micrometers.

2 is a schematic view showing the configuration of a surface protection film according to another embodiment of the present invention.

As shown in FIG. 2, the surface protection film of the present invention includes, for example, ATO (Antimony tin oxide), which is conductive fine particles, based on 100 parts by weight of an ultraviolet curable urethane acrylate resin between the base film 20 and the pressure-sensitive adhesive layer 40; Sb ₂ O ₃ —SnO ₂ ), preferably, the first additional coating layer 30 containing 40 to 100 parts by weight of ATO having an average particle diameter of 0.01 to 1 μm, thereby forming a good ESD function and a good adhesive force. It can be given, and it can also prevent that the said physical property changes with time. On the other hand, the use of conductive fine particles such as ITO in addition to the ATO as a modified embodiment of the present invention is within the same category.

Specifically, the UV curable urethane acrylate resin 100 parts by weight, 20 to 50 parts by weight of isopropyl alcohol, ATO 40 ~ 100 parts by weight having an average particle size of 0.01 ~ 1㎛, as a coating method, gravure, micro gravure, Reverse or kiss rolls are used. Coating thickness shall be 1-20 micrometers (Haze 1% or less). The first additional coating layer 30 thus formed shows a surface resistance of 10 ⁶ to 10 ⁹ Ω.

In the present invention, the first additional coating layer 30 is disposed between the base film 20 and the pressure-sensitive adhesive layer 40 on the inner side of the base film 20 instead of the outer side of the base film 20 to secure the ESD function. It is important to form. That is, although ATO is used for antistatic purposes, when it is provided outside of the base film 20, a good ESD function cannot be achieved. In addition, it is not preferable to form ATO on the outer side surface of the base film 20 also from the side of a haze.

3 is a schematic view showing the configuration of a surface protection film according to another embodiment of the present invention.

As shown in FIG. 3, the surface protection film of the present invention includes a second additional coating layer for antistatic or antistatic and antifouling containing a conductive polymer or a conductive polymer and an antifouling agent on an outer surface of the base film 20. (10) can be formed.

Accordingly, antistatic treatment may be performed on the outside of the base film to prevent contamination of particles and contamination by other contaminants such as fingerprints.

In detail, for example, polythiophene, polyaniline, polypyrrole, or the like is used as a conductive polymer having electrical properties of a metal, mechanical properties, and processability of a polymer. In particular, it is preferable to use polythiophene having the most excellent physical property safety in process conditions such as heat as the conductive polymer. As the antifouling agent, for example, a fluorine-based compound such as a fluoroacrylic binder is used. The second additional coating layer 10 is applied to the base film 20 to be 0.2 to 0.4 g / m ² , for example. At this time, the surface specific resistance is 10 ⁶ to 10 ⁸ Ω. At this time, the surface resistivity is 10 ⁶ ~ 10 ⁸ Ω (Haze 3% or less; Haze can be lowered to 3% or less even when the second additional coating layer 10 is formed).

In the case of the second additional coating layer 10, the contact angle (measurement device: GONIOSTAR Series, Surface tech, Inc.) should be at least about 90 degrees, preferably at least 100 degrees, more preferably at least 110 degrees. Polypropylene has a contact angle of 108 degrees. Paraffin has a contact angle of 110 degrees and Teflon has a contact angle of 112 degrees, and it can be seen that no material is contaminated when the contact angle of Teflon is maintained. In the present invention, the fluorine-based compound is 10 to 25 parts by weight based on 100 parts by weight of the total antistatic and antifouling coating liquid composition, in particular, when the coating liquid of the second additional coating layer 10 is formed, thereby increasing the contact angle of 110 degrees or more. Can be achieved.

Specifically, the antistatic and antifouling coating solution is composed of a conductive polymer (eg, PEDOT / PSS) 1 to 10 wt%, fluoro acrylic binder 10 to 25 wt%, propanol 10 to 20 wt%, water 50 to 80 wt%, coating The method uses gravure, micro gravure, reverse, kiss roll and the like. Drying temperature shall be 100-120 degreeC, and drying time shall be 30 second-2 minutes.

Meanwhile, a cushion function may be added to the second additional coating layer 10 by coating a rubber-based resin using polypropylene as a binder.

Finally, the release film 50 is a silicone release coating after the siloxane antistatic coating having excellent compatibility with silicone, for example, 25㎛ PET film to prevent foreign matter adhesion by the silicon during peeling, furthermore, the silicone The antistatic treatment may be performed on the release film. Accordingly, it is possible to minimize foreign matter mixing due to static electricity that may occur during the skin adhesion process and the lamination process.

Hereinafter, the present invention will be described in more detail by explaining preferred examples and experimental examples of the present invention. However, the present invention is not limited to the following examples, and various forms of embodiments can be implemented within the scope of the appended claims, and the following examples are only ordinary in the art while making the disclosure of the present invention complete. It is intended to facilitate the implementation of the invention to those with knowledge.

Experimental Example 1-Example and Comparative Example

The film lamination structure of each Example and Comparative Example of the present Experimental Example 1 is as follows [the second additional coating layer 10, the base film 20, the release film 50 may be any of those described above. ].

Example 1

Second additional coating layer (10) / base film (20) / first additional coating layer (30) / pressure-sensitive adhesive layer (40-1: 1 part by weight of lithium amide-based ion complex polymer antistatic agent) / release film (50)

Example 2

Second additional coating layer (10) / base film (20) / first additional coating layer (30) / pressure-sensitive adhesive layer (40-2: 2 parts by weight of lithium amide type ion complex polymer antistatic agent) / release film (50)

Example 3

Second additional coating layer (10) / base film (20) / first additional coating layer (30) / pressure-sensitive adhesive layer (40-3: 3 parts by weight of lithium amide-based ion complex polymer antistatic agent) / release film (50)

Example 4

Second additional coating layer 10 / base film 20 / first additional coating layer 30 / pressure-sensitive adhesive layer (40-4: 5 parts by weight of lithium amide-based ion complex polymer antistatic agent) / release film (50)

Comparative Example 1

Second additional coating layer (10) / base film (20) / pressure-sensitive adhesive layer (40 ': lithium amide-based ion complexe polymer antistatic agent not added) / release film (50)

Comparative Example 2

Second additional coating layer (10) / base film (20) / first additional coating layer (30) / pressure-sensitive adhesive layer (40 ': lithium amide-based ion complex rubber antistatic agent not added) / release film (50)

Comparative Example 3

Second additional coating layer (10) / base film (20) / first additional coating layer (30) / pressure-sensitive adhesive layer (40-5: 0.5 parts by weight of lithium amide-based ion complex polymer antistatic agent) / release film (50)

Comparative Example 4

Second additional coating layer 10 / base film 20 / first additional coating layer 30 / pressure-sensitive adhesive layer (40-6: 0.8 parts by weight of lithium amide-based ion complex polymer antistatic agent) / release film (50)

Comparative Example 5

Second additional coating layer 10 / base film 20 / first additional coating layer 30 / pressure-sensitive adhesive layer (40-7: 0.9 parts by weight of lithium amide-based ion complex polymer antistatic agent) / release film (50)

Comparative Example 6

Second additional coating layer (10) / base film (20) / first additional coating layer (30) / pressure-sensitive adhesive layer (40-8: 6 parts by weight of lithium amide-based ion complex polymer antistatic agent) / release film (50)

Comparative Example 7

2nd additional coating layer 10 / base film 20 / 1st additional coating layer 30 / adhesive layer (40 ": 3 weight part of surfactant containing antistatic agent added) / release film 50

The pressure-sensitive adhesive composition (40-1 to 40-8) used in Examples 1 to 4 and Comparative Examples 3 to 6 isocyanate resin (toyo ink, BXX5134) 5 with respect to 100 parts by weight of acrylic resin (toyo ink, BPS5978) 5 Part by weight, 20 parts by weight of ethyl acetate, and a lithium amide-based ion complex polymer antistatic agent (nanocamptec, elecon 1201P) were added and mixed at the respective ratios, and prepared in the pressure-sensitive adhesive layers 40 'of Comparative Examples 1 and 2. The antistatic agent was not added.

The surfactant-containing antistatic agent used in the pressure-sensitive adhesive layer 40 ″ of Comparative Example 7 was 5 parts by weight of isocyanate resin (toyo ink, BXX5134) and 20 parts of ethyl acetate based on 100 parts by weight of acrylic resin (toyo ink, BPS5978). And 3 parts by weight of a tetravalent ammonium surfactant (Junior Chemical) were prepared.

The first additional coating layer 30 in the Examples and Comparative Examples 2 to 7 is 70 parts by weight of ATO, conductive particles having a particle size of 1 μm based on 100 parts by weight of UV-curable urethane acrylate resin and 30 parts by weight of isopropyl alcohol. It is formed by coating the gravure coating on the base film 20 to 4㎛.

[Experimental measurement of static electricity generation during polarizing plate]

The polarizing plate and each of the surface protective films prepared above were laminated with a paper tester (SANGYO). The lamination was performed at 2 kgf pressure and 10 mm / sec in A4 size. After pressing at room temperature (25 ℃), it was left for 30 minutes or 7 days. The maximum amount of static electricity generated was measured while peeling off the surface protective film from the polarizing plate [Measurer: KSD-0103 (KASUGA)].

The experimental results after the 30-minute measurement are shown in Table 1 (unit: kV).

Example 1 Example 2 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 5 Comparative Example 6 Comparative Example 7 Conduct once 0.3 0.2 0.14 16 11 2 0.1 4 Conduct twice 0.5 0.3 0.2 22 8 0.8 0.08 4 3 times 0.5 0.4 0.27 18 7 0.9 0.2 8 4 times 0.3 0.1 0.1 21 8 0.8 0.1 6 5 times 0.3 0.2 0.2 20 5 One 0.1 7

The experimental results after the 7-day measurement are shown in Table 2 (unit: kV).

Example 1 Example 2 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 5 Comparative Example 6 Comparative Example 7 Conduct once 0.4 0.5 0.4 20 18 3 0.4 8 Conduct twice 0.5 0.4 0.5 30 9 1.3 0.2 8 3 times 0.5 0.5 0.35 21 8 2 0.6 10 4 times 0.4 0.4 0.42 22 11 1.4 0.3 11 5 times 0.4 0.5 0.3 25 8 2.2 0.3 9

[Surface Resistance, Adhesive Force, ESD Function, Sliding Phenomenon from Substrate Film, Change with Time, Burr Generation Measurement Experiment]

Surface resistance was measured according to ASTM-D257.

The adhesive force was measured by the KS A1107 measuring method [mixing by adjusting the amount of curing agent (isocyanate resin) desired by the user]. First, after washing the SUS plate stored at 23 ℃ (humidity 65 ℃), dried, and then attached to the cleaned SUS plate 25mm cut sample, and then using a press machine of 2kg load, 5mm / sec One reciprocation was pressed at the speed. Next, the compressed sample was stored at 23 ° C. (humidity 65) for 30 minutes, and after 30 minutes of compression, it was measured using an adhesion tester (peel rate 300 mm / min, peeling angle: 180 degrees).

The ESD function measured whether the polarizing plate did not stick to the hand when the surface protective film was peeled off from the polarizing plate to which the surface protective film was attached. The measurement was performed 20 times and marked "Yes" when all 20 times did not stick, and otherwise indicated "None".

The rolling phenomenon from the base film was evaluated by rubbing the surface protective films produced by using the eraser, and when the surface occurred like an eraser powder, the rolling phenomenon was "Yes", and there was no surface occurrence.

The change over time measured whether the ESD function, the sliding phenomenon from the base film, and the adhesive force were the same even after 7 days, and if there was any change over time, it was all the same as "Yes", and if there was no change over time, it was represented as "none".

Burr generation was measured whether the white powder is generated on the side of the cut when the surface of the surface protective film produced by the knife was cut.

Table 3 shows the measurement results for the examples.

Example 1 Example 2 Example 3 Example 4 Surface resistance 10 ⁷ Ω 10 ⁶ Ω 10 ⁶ Ω 10 ⁶ Ω adhesiveness 7gf 7gf 6gf 7gf EDS function has exist has exist has exist has exist Slide development from base film none none none none Change over time none none none none Burr occurrence none none none none

Table 4 shows the measurement results for the comparative example.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Surface resistance insulate 10 ¹⁴ Ω 10 ¹⁰ Ω 10 ⁸ Ω 10 ⁸ Ω 10 ⁶ Ω 10 ¹⁰ Ω adhesiveness 6gf 7gf 7gf 7gf 7gf 6gf 5gf ESD function none has exist has exist has exist has exist has exist has exist Jungle from substrate film none none none none none has exist has exist Change over time none none none none none Yes (adhesion change) Yes (adhesion change) Burr occurrence has exist has exist has exist has exist has exist none none

As can be seen from the above, in the case of Comparative Example 6, not only the sliding phenomenon of the pressure-sensitive adhesive and the base film occurred, but also the time-dependent change in which the adhesive strength was also decreased. In the case of Comparative Example 7, the adhesive force was not kept constant by transferring the surfactant to the adherend, and defects of the adherend were generated.

On the other hand, according to the surface protection film of the embodiments of the present invention, even after 7 days, the amount of static electricity generated does not increase by 0.5 kV or more, so that good antistatic property lasts for a long time. Further, it was found that by using the ion complex polymer antistatic agent at 1 to 5 parts by weight, burr generation was prevented, and further, there was no change in the phenomena and physical properties from the base film. In addition, it can be seen that when the first additional coating layer containing ATO secures the ESD function.

Meanwhile, in Examples 1 to 4, 0.5 parts by weight and 0.8 parts by weight of an isocyanate resin (toyo ink, BXX5134), which is a curing agent, in the pressure-sensitive adhesive composition, except that the sliding phenomenon from the base film was observed in each case. I get almost the same result with each example.

In addition, when the isocyanate resin (toyo ink, BXX5134), which is a curing agent, was used in an amount of 21 parts by weight and 22 parts by weight in the pressure-sensitive adhesive composition, the same results as in each example were obtained except that a small amount of burr generation began to occur. .

Experimental Example 2-Example and Comparative Example

In order to examine the change of the ESD function according to the position, content and particle diameter of the coating layer containing ATO, etc., in the present Experimental Example 2 as the first additional coating layer 30, 100 parts by weight of UV-curable urethane acrylate resin, isopropyl alcohol Results of the average particle diameter of 0.01 to 1 μm (0.01 μm, 0.1 μm, 0.5 μm, 1 μm) at 30 parts by weight of the following Examples and Comparative Examples 2 to 4 and 5 to 7 parts respectively The same result was obtained, and in the range of 0.01 ~ 1㎛, it was confirmed that there was no difference in the experimental results according to the difference of the average particle diameter). After gravure coating, the pressure-sensitive adhesive layer 40 was formed as in Example 3 of Experimental Example 1, and a release film 50 was formed. In Comparative Example 7, an ATO-containing surface coating layer was formed on the outside of the base film 20 instead of the first additional coating layer 30 (that is, formed at the position of the second additional coating layer 10).

Table 5 shows the ATO content (parts by weight) of the examples.

Example 1 Example 2 Example 3 Example 4 ATO parts by weight 40 60 80 100

Table 6 shows the ATO content (weight parts) of the comparative examples.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 ATO parts by weight No ATO layer 10 20 30 110 120

Except in the case where the ATO-containing surface coating layer is formed on the outer side of the base film 20 in Comparative Example 7, the second additional coating layer 10 was not formed in the Examples and Comparative Examples of Experimental Example 2.

On the other hand, 70 parts by weight of ATO having an average particle size of 1.1 μm (Comparative Example 8), 1.3 μm (Comparative Example 9), 1.5 μm (Comparative Example 10), and 9.5 nm (Comparative Example 11), respectively, in the base film 20. The first additional coating layer 30 was formed with the coating liquid, and the pressure-sensitive adhesive layer 40 was formed.

[Experiment result]

For each Example and Comparative Example, the ESD function, the sliding phenomenon from the base film, the change over time was measured, the measurement method was the same as in Experimental Example 1.

However, in the ESD function, in this Experimental Example 2, the case where all 20 times of the 20 measurements were not indicated was indicated by ○, the case where the 1st to 19th cases were not indicated by △, and the case where all 20 times were attached to the hands × Marked as.

Table 7 shows the experimental results of the examples.

Example 1 Example 2 Example 3 Example 4 ESD function ○ ○ ○ ○ Slide development from base film none none none none Change over time none none none none

Table 8 shows the experimental results of Comparative Examples 1, 7 and 8.

Comparative Example 1 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 ESD function × △ ○ ○ ○ ○ Slide development from base film none none none none none none Change over time none Yes (ESD change) Yes (adhesion change) Yes (adhesion change) Yes (adhesion change) Yes (ESD change)

Table 9 shows the experimental results of Comparative Examples 2-6.

Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 ESD function △ △ △ ○ ○ Slide development from base film none none none has exist has exist Change over time Yes (ESD change) Yes (ESD change) Yes (ESD change) Yes (shrinkage from base film) Yes (shrinkage from base film)

As can be seen from the above, by forming the first additional coating layer containing ATO, in particular, between the base film and the pressure-sensitive adhesive layer, the ESD function can be ensured in contrast to the absence of the ESD function in the absence of the ATO coating layer (Comparative Example 1). Could.

In forming the ATO-containing coating layer, the content of ATO is less than 40 parts by weight with respect to 100 parts by weight of the ultraviolet curable urethane acrylate resin (Comparative Examples 2 to 4) and the outer surface of the ATO-containing coating layer rather than the inside of the base film. (Comparative Example 7), the ESD function was relatively poor.

In forming the ATO-containing coating layer, when the content of ATO is more than 100 parts by weight based on 100 parts by weight of the ultraviolet curable urethane acrylate resin (Comparative Examples 5 and 6), Comparative Examples 2 to 4 and Examples 1 to 4 Unlike in the case of the case, the adhesion from the base film was lowered, causing a slid phenomenon from the crawfish film, and furthermore, it was confirmed that the degree of sliding from the base film also increased after 7 days. This shows that the higher the content of ATO, the more the ESD function, that is, the polarizing plate does not stick to the hand when the polarizing plate is peeled off, but when excessively contained more than a certain amount, it causes the sliding phenomenon from the base film. Jungle phenomena show a tendency to grow over time.

On the other hand, in addition to the content of ATO in order to consider other factors, that is, the particle size of the ATO, as described above, Comparative Examples 8, 9, 10, the average particle size of the ATO was changed to 1.1㎛, 1.3㎛, 1.5㎛, as a result In Comparative Examples 8-10, constant adhesive force was not ensured, and also there existed the time-dependent change of adhesive force. This is because as the size of the ATO increases, the surface becomes uneven, causing a nonuniform adhesion force and a change in the adhesion force over time. In Comparative Example 11, the average particle size of the ATO was 9.5 nm, in which there was no problem of adhesion, but the ESD was slightly lowered over time.

As such, the presence and location of ATO, its content, and also the particle size of ATO at this time affect the ESD function, adhesive force, and its change over time. This fact indicates that the ATO is fixed at a predetermined position (between the base film and the adhesive layer). In quantity, it is preferred that an ATO having a certain particle size should be present in a certain amount at a certain position.

According to the present invention, in the adhesive composition for the surface protection film and the surface protection film using the same, not only have sufficient antistatic property, but also a change in the amount of static electricity generated after a time can be secured to a predetermined level or less. In addition, since the generation of burrs when cutting the manufactured surface protection film is prevented at the source, it is possible to block foreign matters from the electronic parts or optical parts from the beginning, and furthermore, there is no need to add a separate process for removing the burrs generated. It can also increase efficiency. In addition, the ESD function can be achieved and there is no problem of the change of the physical property over time.

Although the present invention has been described in connection with the above-mentioned preferred embodiments, it is possible to make various modifications or variations without departing from the spirit and scope of the invention. Accordingly, the appended claims will cover such modifications and variations as fall within the spirit of the invention.

Claims (23)

LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , LiAsF ₆ , LiC (CF ₃ SO ₃ ) ₃ , LiN (CF ₃ SO ₃ ) ₂ , LiNH ₂ , LiN (C ₂ H ₅ ) ₂ , A cation metal salt obtained by mixing at least one selected from LiI, LiBr, LiCl, LiF, NaPF ₆ , NaClO ₄ , NaI, NaSCN, KSCN, KPF ₆ or KClO ₄ is selected from propylene carbonate, ethylene glycol or dimethyl formamide. A pressure-sensitive adhesive composition for a surface protection film comprising an ion-complex polymer antistatic agent prepared by sequentially reacting an organic conductive compound and an anionic conductive organic compound selected from trilauryl phosphite, trischloromethyl ester or dimethyl sulfoxide. The composition, Per 100 parts by weight of acrylic resin, 1 to 5 parts by weight of the ion complex polymer antistatic agent and 1 to 20 parts by weight of a curing agent, the adhesive composition for a surface protective film. The method of claim 1, The cationic metal salt is one or two selected from LiNH ₂ or LiN (C ₂ H ₅ ) _{2 The} adhesive composition for a surface protective film, characterized in that. delete The method of claim 1, The pressure-sensitive adhesive composition comprises 1 to 5 parts by weight of the ion complex polymer antistatic agent, 1 to 20 parts by weight of isocyanate resin and 10 to 30 parts by weight of ethyl acetate based on 100 parts by weight of the acrylic resin. Adhesive composition for surface protection films to be. Base film; And It is formed on the inner side of the base film, and a coating layer of the adhesive composition for a surface protective film according to any one of claims 1, 2 or 4; surface protection film comprising a. The method of claim 5, wherein Surface protective film using a PET film as the base film. The method of claim 5, wherein The base film is made of a polyolefin resin biaxially stretched after applying the antistatic agent before stretching, surface protection film, characterized in that. The method of claim 5, wherein The thickness of the coating layer of the adhesive composition is a surface protective film, characterized in that 10 to 50㎛. The method of claim 5, wherein The surface protective film is a surface between the base film and the coating layer of the pressure-sensitive adhesive composition further comprises a first additional coating layer containing 40 to 100 parts by weight of ATO, conductive fine particles, based on 100 parts by weight of a urethane or acrylic resin Protective film. The method of claim 9, The average particle diameter of ATO which is the said electroconductive fine particles is 0.01-1 micrometer, The surface protection film characterized by the above-mentioned. The method of claim 9, The urethane-based or acrylic resin is a surface protective film, characterized in that the ultraviolet curing urethane acrylate resin. The method of claim 9, The first additional coating layer is a surface protective film, characterized in that applied in 1 ~ 20㎛. The method of claim 9, The surface protection film of which the haze of the surface protection film in which the said 1st further coating layer was formed is 1% or less. The method of claim 9, The first additional coating layer has a surface resistance of 10 ⁶ ~ 10 ⁹ kPa surface protection film, characterized in that. The method of claim 5, wherein Surface protective film, characterized in that the second additional coating layer containing a conductive polymer further formed on the outer surface of the base film. The method of claim 15, And the second additional coating layer further contains an antifouling agent. The method of claim 16, The second additional coating layer is 1 to 10% by weight of the conductive polymer; 10 to 25% by weight of a fluoroacrylic binder; 10-20% by weight of propanol; And a coating layer of the composition composed of 50 to 80% by weight of water. The method of claim 16, And the second additional coating layer further contains a rubber-based resin. The method of claim 17, The contact angle of the second additional coating layer is a surface protection film, characterized in that more than 110 degrees. The method of claim 15, The surface protection film of which the haze of the surface protection film in which the said 2nd further coating layer was formed is 3% or less. The method of claim 15, The surface resistance film of the said 2nd further coating layer is 10 <^6> -10 <^8> Pa, The surface protection film characterized by the above-mentioned. Base film; And As a surface protection film containing; formed on the inner side of the base film, the coating layer of the pressure-sensitive adhesive composition for a surface protection film, The adhesive composition for the surface protection film is LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , LiAsF ₆ , LiC (CF ₃ SO ₃ ) ₂ , LiN (CF ₃ SO ₃ ) ₂ , LiNH ₂ , LiN (C ₂ H ₅ ) ₂ , Lil, LiBr, LiCl, LiF, NaPF ₆ , NaClO ₄ , Nal, NaSCN, KSCN, KPF ₆ or KCLO ₄ mixed with a cationic metal salt selected from propylene carbonate, ethylene glycol or dimethyl formamide and trilauryl phosphite And 1 to 5 parts by weight of an ionic complex polymer antistatic agent prepared by sequentially reacting with an anion conducting organic compound selected from trischloromethyl ester or dimethyl sulfoxide. Base film; And As a surface protection film containing; formed on the inner side of the base film, the coating layer of the pressure-sensitive adhesive composition for a surface protection film, The adhesive composition for the surface protection film is LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , LiAsF with respect to 100 parts by weight of the acrylic resin so as to prevent the burr from occurring when the surface protection film is cut. ₆ , LiC (CF ₃ SO ₃ ) ₂ , LiN (CF ₃ SO ₃ ) ₂ , LiNH ₂ , LiN (C ₂ H ₅ ) ₂ , Lil, LiBr, LiCl, LiF, NaPF ₆ , NaClO ₄ , Nal, NaSCN, Cationic metal salts mixed with one or more selected from KSCN, KPF ₆ or KCLO ₄ are cationic conducting organic compounds selected from propylene carbonate, ethylene glycol or dimethyl formamide and trilaurylphosphite, trischloromethyl ester or dimethyl sulfoxide. Surface protective film comprising 1 to 5 parts by weight of an ion complex polymer antistatic agent prepared by reaction with an anion conducting organic compound selected from.

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