KR20190092924A - A Protection Film and A Manufacturing Method Thereof - Google Patents

Abstract

The present invention relates to a protective film and a method of manufacturing the protective film, which is manufactured by crosslinking the reactive butyl rubber to a mixture of butyl rubber and reactive butyl rubber modified from the butyl rubber. Specifically, the manufacturing method comprises a first step of ionizing butyl rubber with an initiator to manufacture butyl rubber radical; a second step of making reactive butyl rubber with the butyl rubber radical as a reactive modifier; and a third step of mixing the butyl rubber and the reactive butyl rubber and crosslinking the reactive butyl rubber.

Description

Protective Film and A Manufacturing Method Thereof

The present invention relates to a protective film and a method for manufacturing the same, and more particularly, to a protective film and a method for manufacturing the same, which are stable at high temperatures and low temperatures and which do not leave stains upon removal.

In general, the structure of a mobile phone is composed of a touch unit consisting of a liquid crystal display (LCD panel) and a keypad, and almost all portable information terminals other than the mobile phone, for example, a mobile phone, a personal digital assistant (PDA), and a portable multimedia player (PMP). ), Notebooks, electronic dictionaries, digital cameras, game equipment, etc., as seen on a mobile phone can be seen that has a liquid crystal screen and keypad or key input unit.

Such a portable terminal protects the device by attaching a protective film on the LCD screen, the key input unit (keypad) or the body surface, and the conventional protective film is composed of a backing paper having an adhesive on the bottom of the transparent synthetic resin film and protecting the adhesive. .

Accordingly, the conventional protective film is to separate the backing paper from the adhesive immediately before use and attach it to the information terminal surface to protect the adhesive surface, and to protect the expensive portable information terminal against the impact on the LCD screen, the keypad part or the body. It will protect you.

However, the prior art had the following problems.

When the protective film is removed from the terminal surface when using a protective film having a high adhesive strength, there was a problem that the stain remains by the residual adhesive.

Patent Publication No. 1997-052434

In order to solve the above problems, an object of the present invention is to provide a protective film and a method of manufacturing the same after the adhesive strength is high and the adhesive does not remain after removing the film.

In order to achieve the above object, the production method of the protective film of the present invention is characterized in that is produced by crosslinking the reactive butyl rubber in a mixture of butyl rubber and the reactive butyl rubber modified butyl rubber.

In addition, another embodiment of the method of manufacturing the protective film of the present invention, the first step of producing a butyl rubber radical by ionizing butyl rubber (Butyl rubber) with an initiator, and the butyl rubber radical reactive as a reactive modifier And a third step of making butyl rubber, and a third step of mixing the butyl rubber and the reactive butyl rubber and crosslinking the reactive butyl rubber.

The reactive modifier has a double bond, the reactor is -OH, -COOH, -NH2. It is characterized by including any one or more of -NH-, -SH.

In the third step, with respect to 100 parts by weight of the butyl rubber, the reactive butyl rubber is characterized in that the crosslinking by mixing in a proportion of 20 parts by weight to 100 parts by weight.

Protective film which is another embodiment of the present invention is characterized in that it is produced by the above-described manufacturing method.

In the protective film and a method of manufacturing the same according to the present invention has the following effects.

Although the adhesive strength is similar for the protective film used for the display of the existing terminal, there is no adhesive remaining after removing the protective film, there is an advantage that the stain is not always kept clean.

1 is a view showing a chemical reaction formula of the protective film manufacturing process according to the present invention.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings, preferred embodiments of the protective film and a method for producing the same.

The method for producing a protective film according to the present invention may be prepared by crosslinking butyl rubber and reactive butyl rubber modified with butyl rubber.

In more detail, the above-described manufacturing method, the first step of producing a butyl rubber radical by ionizing butyl rubber (Butyl rubber) as an initiator, and reactive butyl rubber (Reactive) as a reactive modifier and butyl rubber), and a third step of crosslinking the butyl rubber and the reactive butyl rubber.

First, a butyl rubber is provided in the method of manufacturing the protective film of the present invention. The butyl rubber may be prepared by the air bond of polyisobutane and isoprene.

In a first step, as shown in Figure 1, the butyl rubber is made of butyl rubber radical. The butyl rubber is made of butyl rubber radical using an initiator in the butyl rubber. At this time, the butyl rubber may be reacted by dissolving the butyl rubber in a solvent to facilitate the reaction with the initiator. As the solvent, various solvents may be applied. For example, cyclohexane may be used.

In addition, various initiators may be used as the initiator. For example, in the present invention, azobisisobytyronitrile (AIBN) may be used.

In the second step, reactive butyl rubber is prepared by using the butyl rubber radical modifier. The modifier is a reactive modifier, and a functional group is bonded among modifiers in which a double bond is present in a molecular formula, and the functional group is -OH (hydroxy group), -COOH (carboxyl group), -NH 2 (primary amine group), -NH- (secondary amine group). ), -SH (thiol) may be bonded to any one or more.

More specifically, the reactive modifier may be used acrylic acid (maleic anhydride), 2-hydroxyethyl acrylate (2-Hydroxyethyl Acrylate).

In the third step, the butyl rubber and the reactive butyl rubber are mixed to crosslink the reactive butyl rubber. In the crosslinking of the reactive butyl rubber, a crosslinking agent is used. Various crosslinking agents may be applied to the crosslinking agent, and in the present invention, isocyanurate of hexamethylene diisocyanate which is trifunctional isocyanate may be used.

In addition, a crosslinking catalyst may be further used in crosslinking, for example, dibutyltin laurate may be used.

Hereinafter, the manufacturing method of the protective film according to the present invention will be described in detail with reference to the experimental example.

1. Reactive Butyl Rubber Synthesis

Example 1

500 g of cyclohexane (cyclohexane) was added to a 1 L flask, and 60 g of butyl rubber (Exxon butyl 268) was slowly added thereto to dissolve the butyl rubber. After confirming that the butyl rubber was completely dissolved in the solvent, 6 g of acrylic acid (acrylic acid) and 0.65 g of radical initiator (AIBN, Wako) were added, and nitrogen gas was added to create an inert atmosphere. . Thereafter, a radical polymerization reaction was performed under reaction conditions of 65 ° C./5 hours, 70 ° C./5 hours, and 75 ° C./3 hours to prepare a reactive butyl rubber solution. The prepared solution was then slowly dropped into acetone to precipitate the reactive butyl rubber and to remove the unreacted reactive modifier and the remaining radical initiator. Thereafter, the precipitated reactive butyl rubber was vacuum dried at 60 ° C. for 24 hours to prepare a reactive butyl rubber (BR_AA) finally grafted with a reactive modifier.

Example 2

500 g of cyclohexane (cyclohexane) was added to a 1 L flask, and 60 g of butyl rubber (Exxon butyl 268) was slowly added thereto to dissolve the butyl rubber. After confirming that the butyl rubber was completely dissolved in the solvent, 6 g of maleic anhydride (reactive modifier) and 0.65 g of radical initiator (AIBN, Wako) were added, and nitrogen gas was added to create an inert atmosphere. Slowly raised. Thereafter, a radical polymerization reaction was performed under reaction conditions of 65 ° C./5 hours, 70 ° C./5 hours, and 75 ° C./3 hours to prepare a reactive butyl rubber solution. Thereafter, the prepared solution was slowly dropped into acetone to precipitate the reactive butyl rubber and to remove the unreacted reactive modifier and the remaining radical initiator. Thereafter, the precipitated reactive butyl rubber was vacuum dried at 60 ° C. for 24 hours to prepare a reactive butyl rubber (BR_AA) finally grafted with a reactive modifier.

Example 3

500 g of cyclohexane (cyclohexane) was added to a 1 L flask, and 60 g of butyl rubber (Exxon butyl 268) was slowly added thereto to dissolve the butyl rubber. After confirming that the butyl rubber was completely dissolved in the solvent, 6 g of 2-hydroxyethyl acrylate (2-Hydroxyethyl Acrylate) and 0.65 g of radical initiator (AIBN, Wako) were added and nitrogen gas was added to create an inert atmosphere. The temperature was slowly raised to 65 afterwards. Thereafter, a radical polymerization reaction was performed under reaction conditions of 65 ° C./5 hours, 70 ° C./5 hours, and 75 ° C./3 hours to prepare a reactive butyl rubber solution. Thereafter, the prepared solution was slowly dropped into acetone to precipitate the reactive butyl rubber and to remove the unreacted reactive modifier and the remaining radical initiator. Thereafter, the precipitated reactive butyl rubber was vacuum dried at 60 ° C. for 24 hours to prepare a reactive butyl rubber (BR_AA) finally grafted with a reactive modifier.

2. Manufacture of protective film

Example 4

6 g of BR-AA prepared in Example 1 and 6 g of butyl rubber (Exxon butyl 268) were added to 88 g of cyclohexane, and then completely dissolved at room temperature to prepare an adhesive. 0.18 g (3 parts by weight of BR_AA) of isocyanurate of hexamethylene diisocyanate, a trifunctional isocyanate as a crosslinking agent, and 0.0012 g of dibutyItin dilaurate as a crosslinking catalyst (BR_AA 0.02 parts by mass) was added, followed by mixing and stirring to prepare a rubber-based pressure-sensitive adhesive solution. Thereafter, the prepared pressure-sensitive adhesive was applied onto a corona surface-treated polyethylene film, and dried at 90 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. After the heat treatment for 10 hours at 60 ℃ to finally prepare a pressure-sensitive adhesive sheet of the surface protection film.

Example 5

6 g of BR-MA prepared in Example 2 and 6 g of butyl rubber (Exxon butyl 268) were added to 88 g of cyclohexane, and then completely dissolved at room temperature to prepare an adhesive. 0.18 g (3 parts by weight of BR_AA) of isocyanurate of hexamethylene diisocyanate, a trifunctional isocyanate as a crosslinking agent, and 0.0012 g of dibutyItin dilaurate as a crosslinking catalyst (BR_AA 0.02 parts by mass) was added, followed by mixing and stirring to prepare a rubber-based pressure-sensitive adhesive solution. Thereafter, the prepared pressure-sensitive adhesive was applied onto a corona surface-treated polyethylene film, and dried at 90 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. After the heat treatment for 10 hours at 60 ℃ to finally prepare a pressure-sensitive adhesive sheet of the surface protection film.

Example 6

6 g of BR-EHA prepared in Example 3 and 6 g of butyl rubber (Exxon butyl 268) were added to 88 g of cyclohexane, and then completely dissolved at room temperature to prepare an adhesive. 0.18 g (3 parts by weight of BR_AA) of isocyanurate of hexamethylene diisocyanate, a trifunctional isocyanate as a crosslinking agent, and 0.0012 g of dibutyItin dilaurate as a crosslinking catalyst (BR_AA 0.02 parts by mass) was added, followed by mixing and stirring to prepare a rubber-based pressure-sensitive adhesive solution. Thereafter, the prepared pressure-sensitive adhesive was applied onto a corona surface-treated polyethylene film, and dried at 90 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. After the heat treatment for 10 hours at 60 ℃ to finally prepare a pressure-sensitive adhesive sheet of the surface protection film.

Example 7

6 g of BR-AA prepared in Example 1 and 6 g of butyl rubber (Exxon butyl 268) were added to 88 g of cyclohexane, and then completely dissolved at room temperature to prepare an adhesive. 0.3 g (5 parts by weight of BR_AA) YH-300, a trifunctional epoxy, which is a crosslinking agent, was added thereto, followed by mixing and stirring to prepare a rubber-based pressure-sensitive adhesive solution. Thereafter, the prepared pressure-sensitive adhesive was applied onto a corona surface-treated polyethylene film, and dried at 90 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. After the heat treatment for 10 hours at 60 ℃ to finally prepare a pressure-sensitive adhesive sheet of the surface protection film.

Example 8

6 g of BR-AA prepared in Example 1 and 6 g of butyl rubber (Exxon butyl 268) were added to 88 g of cyclohexane, and then completely dissolved at room temperature to prepare an adhesive. 0.3 g (5 parts by weight of BR_AA) of CAT-AK (metal-chelateme, ternary), which is a metal chelate crosslinking agent, was added thereto, followed by mixing and stirring to prepare a rubber-based pressure-sensitive adhesive solution. Thereafter, the prepared pressure-sensitive adhesive was applied onto a corona surface-treated polyethylene film, and dried at 90 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. After the heat treatment for 10 hours at 60 ℃ to finally prepare a pressure-sensitive adhesive sheet of the surface protection film.

Example 9

6 g of BR-AA prepared in Example 1 and 6 g of polyisobutylene (Oppanol B100, BASF) were added to 88 g of cyclohexane, and then completely dissolved at room temperature to prepare an adhesive. Here is 0.18 g of isocyanurate of hexamethylene diisocyanate (Desmodur N3300) which is a crosslinking agent (3 parts by mass with respect to BR_AA), and 0.0012 g of dibutyItin dilaurate as a crosslinking catalyst (0.02 mass with respect to BR_AA). Part) was added, and the mixture was stirred to prepare a rubber pressure-sensitive adhesive solution. Thereafter, the prepared pressure-sensitive adhesive was applied onto a corona surface-treated polyethylene film, and dried at 90 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. After the heat treatment for 10 hours at 60 ℃ to finally prepare a pressure-sensitive adhesive sheet of the surface protection film.

Example 10

6 g of BR-AA prepared in Example 1 and 6 g of polyisobutylene (Oppanol B50, BASF) were added to 88 g of cyclohexane, and then completely dissolved at room temperature to prepare an adhesive. Here is 0.18 g of isocyanurate of hexamethylene diisocyanate (Desmodur N3300) which is a crosslinking agent (3 parts by mass with respect to BR_AA), and 0.0012 g of dibutyItin dilaurate as a crosslinking catalyst (0.02 mass with respect to BR_AA). Part) was added, and the mixture was stirred to prepare a rubber pressure-sensitive adhesive solution. Thereafter, the prepared pressure-sensitive adhesive was applied onto a corona surface-treated polyethylene film, and dried at 90 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. After the heat treatment for 10 hours at 60 ℃ to finally prepare a pressure-sensitive adhesive sheet of the surface protection film.

Example 11

Into 88 g of cyclohexane, 2.4 g of BR-AA prepared in Example 1 and 9.6 g of butyl rubber (Exxon butyl 268) were added and completely dissolved at room temperature to prepare an adhesive. 0.18 g (3 parts by weight of BR_AA) of isocyanurate of hexamethylene diisocyanate, a trifunctional isocyanate as a crosslinking agent, and 0.0012 g of dibutyItin dilaurate as a crosslinking catalyst (BR_AA 0.02 parts by mass) was added, followed by mixing and stirring to prepare a rubber-based pressure-sensitive adhesive solution. Thereafter, the prepared pressure-sensitive adhesive was applied onto a corona surface-treated polyethylene film, and dried at 90 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. After the heat treatment for 10 hours at 60 ℃ to finally prepare a pressure-sensitive adhesive sheet of the surface protection film.

Example 12

Into 88 g of cyclohexane, 9.6 g of BR-AA prepared in Example 1 and 2.4 g of butyl rubber (Exxon butyl 268) were added and completely dissolved at room temperature to prepare an adhesive. 0.18 g (3 parts by weight of BR_AA) of isocyanurate of hexamethylene diisocyanate, a trifunctional isocyanate as a crosslinking agent, and 0.0012 g of dibutyItin dilaurate as a crosslinking catalyst (BR_AA 0.02 parts by mass) was added, followed by mixing and stirring to prepare a rubber-based pressure-sensitive adhesive solution. Thereafter, the prepared pressure-sensitive adhesive was applied onto a corona surface-treated polyethylene film, and dried at 90 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. After the heat treatment for 10 hours at 60 ℃ to finally prepare a pressure-sensitive adhesive sheet of the surface protection film.

Example 13

12 g of BR-AA prepared in Example 1 was added to 88 g of cyclohexane, and then completely dissolved at room temperature to prepare an adhesive. 0.18 g (3 parts by weight of BR_AA) of isocyanurate of hexamethylene diisocyanate, a trifunctional isocyanate as a crosslinking agent, and 0.0012 g of dibutyItin dilaurate as a crosslinking catalyst (BR_AA 0.02 parts by mass) was added, followed by mixing and stirring to prepare a rubber-based pressure-sensitive adhesive solution. Thereafter, the prepared pressure-sensitive adhesive was applied on a corona surface-treated polyethylene film, and dried at 90 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. After heat treatment at 60 ℃ for 10 hours to finally prepare a pressure-sensitive adhesive sheet of the surface protection film.

Comparative Example 1

12 g of butyl rubber (Exxon butyl 268) was added to 88 g of cyclohexane, and completely dissolved at room temperature to prepare a rubber-based pressure-sensitive adhesive solution. Thereafter, the prepared pressure-sensitive adhesive was applied onto a corona surface-treated polyethylene film, and dried at 90 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. After the heat treatment for 10 hours at 60 ℃ to finally prepare a pressure-sensitive adhesive sheet of the surface protection film.

Comparative Example 2

12 g of polyisobutylene (Oppanol B50, BASF) was added to 88 g of cyclohexane, and then completely dissolved at room temperature to prepare an adhesive solution. Thereafter, the prepared pressure-sensitive adhesive was applied onto a corona surface-treated polyethylene film, and dried at 90 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. After the heat treatment for 10 hours at 60 ℃ to finally prepare a pressure-sensitive adhesive sheet of the surface protection film.

division Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Adhesive Strength (N / 25mm) 1.63 1.59 1.58 1.68 1.71 1.56 High temperature stability
(N / 25mm) 2.42 2.34 2.36 2.38 2.42 2.33 Low temperature stability
(N / 25mm) 1.78 1.92 2.03 2.02 2.11 2.27 Heat resistance Residual adhesive radish radish radish radish radish radish stain radish radish radish radish radish radish Weather resistance Residual adhesive radish radish radish radish radish radish stain radish radish radish radish radish radish

division Example 10 Example 11 Example 12 Example 13 Comparative Example 1 Comparative Example 2 Adhesive Strength (N / 25mm) 1.86 2.04 1.52 1.37 1.88 2.42 High temperature stability
(N / 25mm) 2.46 2.54 1.96 1.76 3.42 4.03 Low temperature stability
(N / 25mm) 1.99 2.06 1.77 1.71 2.48 3.27 Heat resistance Residual adhesive radish radish radish radish radish U stain radish radish radish radish U U Weather resistance Residual adhesive radish radish radish radish radish U stain radish radish radish radish U U

 [Assessment Methods]

Adhesion strength test: After cutting the specimen into 25mm width, the adhesive strength was measured 20 minutes after the specimen was attached to the SUS 304 BA plate.

High Temperature Stability Test: After cutting the specimen to 25mm width, the specimen was attached to the SUS 304 BA plate, and then stored at 70 ° C. for 72 hours to measure the adhesive strength at room temperature.

Low temperature stability test: After cutting the specimen into 25mm width, the specimen was attached to the SUS 304 BA plate, and then stored at 0 ° C. for 3 hours, and then measured the adhesive strength at room temperature.

Heat resistance test: After cutting the specimen into 25mm width, the specimen was attached to the SUS 304 BA plate, and then stored at 70 ° C. for 72 hours.

Weathering test: After cutting the specimen into 25mm width, the specimen was attached to the SUS 304 BA plate and left for 1 month in the open air.

As described in Table 1 and Table 2, Examples 4 to 13 have the adhesive strength is the product properties applicable to the product in the range of 1.5 to 2.5 required as a product, Example 13 has the lowest value of 1.37, Example 11 has the highest value of 2.04.

In addition, it can be confirmed that after the heat and weather test, the residual adhesive did not remain in Examples 4 to 13.

As such, the technical configuration of the present invention described above can be understood by those skilled in the art that the present invention can be implemented in other specific forms without changing the technical spirit or essential features of the present invention.

Therefore, the above-described embodiments are to be understood in all respects as illustrative and not restrictive, and the scope of the present invention is indicated by the following claims rather than the above description, and the meanings and ranges of the claims and their equivalent concepts. All changes or modifications derived from the invention should be construed as being included in the scope of the present invention.

Claims (5)

Method for producing a protective film, characterized in that the cross-linking of the reactive butyl rubber to a mixture of butyl rubber and the reactive butyl rubber modified by the butyl rubber. A first step of ionizing butyl rubber with an initiator to produce butyl rubber radical;
A second step of forming the reactive butyl rubber using the butyl rubber radical as a reactive modifier; And
And a third step of mixing the butyl rubber and the reactive butyl rubber and crosslinking the reactive butyl rubber. The method of claim 1,
The reactive modifier,
Having a double bond, the reactor is -OH, -COOH, -NH2. -NH-, -SH protective film production method comprising at least any one of -SH. The method of claim 1,
In the third step,
With respect to 100 parts by weight of the butyl rubber, the reactive butyl rubber is a protective film production method, characterized in that the cross-linking by mixing in a proportion of 20 parts by weight to 100 parts by weight. Claim 1 is a protective film, characterized in that produced by the manufacturing method.

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