KR101269196B1 - A self-adhesive protection film having improved properties and an article attached with the same - Google Patents

Abstract

The present invention relates to a self-adhesive protective film with improved performance and an article attached thereto, and more particularly, using a polyolefin-based resin as a carrier layer raw material and an elastomeric resin as a raw material for the adhesive layer. The present invention relates to a self-adhesive protective film having a multilayer structure having excellent adhesiveness, cutting property, no residue, and mechanical properties, and an article to which the self-adhesive protective film is attached.

Description

A self-adhesive protection film having improved properties and an article attached with the same}

The present invention relates to a self-adhesive protective film with improved performance and an article attached thereto, and more particularly, using a polyolefin-based resin as a carrier layer raw material and an elastomer resin as a raw material for the adhesive layer. The present invention relates to a self-adhesive protective film having a multilayer structure having excellent adhesiveness, cutting property, no residue, and mechanical properties, and an article to which the self-adhesive protective film is attached.

The protective film is known as a protective film, a masking film or a cover film. Unlike a general protective film, a self-adhesive protective film does not need to apply a separate adhesive, and thus the film itself has adhesive properties so that the protective film can be adhered to the substrate. do.

This protective film is a film that protects various parts and materials used in IT products and construction materials, and is applied to IT products such as mobile phones, LCDs, LEDs, home appliances and electronics, as well as building materials and interior materials, and transfers various parts materials. And to prevent contamination from outside during long term storage.

Recently, as IT parts and materials are complicated and miniaturized, demands for the development of defect-free high-performance protective film without a transfer problem that is a cause of failure are increasing from demand companies.

Conventional solvent-type protective film manufacturing processes include the base film loading (releasing) process, the coating process of the prepared coating solution on the film, the drying process for removing the remaining solvent in the coating solution, aging process, and cutting by application product. Process and the like. The pressure-sensitive adhesive used in the solvent-type adhesive protective film is an acrylic type, and a solvent is used when coating. The solvent used is toluene, xylene, butyl acetate, etc., which may cause dizziness and headache for workers due to the toxicity of the solvents. Can be. In addition, since it emits volatile organic compounds (VOCs) that are harmful to the atmosphere during the drying process, it is necessary to develop fundamental alternative technologies, namely process development.

Recently, a solvent-free self-adhesive protective film that does not use a solvent has been proposed as a technology to replace the manufacturing process of such a solvent-type protective film. The non-solvent type self-adhesive protective film has the advantage of overcoming such low recyclability, while the solvent type protective film has a low recycling property due to the adhesive applied to the surface.

Due to the advantages of the self-adhesive protective film as described above, the need for development and interest is very high, but domestic product level is still insufficient for SME manufacturers.

In general, in order to give a self-adhesive property, when the protective film is processed by a blow method or a casting method, multi-layer processing is performed by co-extrusion of ethylene vinyl acetate, ethylene acrylic acid, VLDPE, etc. Will be

However, the conventional coextruded multilayer film to which the adhesive layer of vinyl acetate is applied has a disadvantage in that it is inferior to the conventional solvent-type adhesive protective film in adhesive strength and heat resistance. In addition, a defect occurs in the extrusion process of the film, there is a disadvantage that the rate of defective products is high, which is limited to apply to an optical sheet requiring a high quality.

Self-adhesive protective film should have high adhesive force, minimize change over time in order to enhance heat resistance, be easy to cut after adhesion with substrate, free from residue on substrate after peeling off film, and impart transparency. , Mechanical strength control such as tensile strength and elongation of multilayer film should be available.

Therefore, the inventors of the present invention, while studying in view of the above, using a polyolefin resin as a carrier layer raw material and an elastomer resin as an adhesive layer raw material to prepare a self-adhesive protective film of a multi-layer structure consisting of a carrier layer and an adhesive layer The present invention was completed by confirming that the self-adhesive protective film has excellent adhesiveness, cutting property, no residue, mechanical properties, and the like by examining its adhesiveness, cutting property, residue-free property, mechanical properties, and the like.

An object of the present invention is to provide a self-adhesive protective film of a multi-layer structure exhibiting excellent adhesion, cutting properties, residue-free, mechanical properties.

Another object of the present invention is to provide an article to which the self-adhesive protective film of the multilayer structure is attached.

In order to solve the above problems,

A carrier layer formed of a polyolefin resin; And an adhesive layer formed of a mixture of 40 to 80 wt% polyolefin resin and an elastomer resin having 20 to 60 wt% epoxy group, hydroxyl group or amine group,

The elastomer resin having an epoxy group, a hydroxyl group or an amine group of the adhesive layer provides a self-adhesive protective film having a melt index of 1 to 4 g / 10 minutes and a density of 0.85 to 0.95 g / cm ³ .

The term 'self-adhesiveness' used in the present invention does not use any other pressure-sensitive adhesive, and does not apply additional pressure or heat, and also does not use mechanical means such as pushpins, screws, staples, nails, wires, etc. It means the property of the film which can adhere | attach.

The term 'protective film' used in the present invention means a film that is attached to the protected surface of the adherend to protect the adherend from scratching or peeling.

In the present invention, the carrier layer is formed of polyolefin resin.

In the present invention, it is preferable that the polyolefin resin of the carrier layer comprises polyethylene having a melt index of 0.5 to 8 g / 10 minutes and a density of 0.90 to 1.10 g / cm ³ .

In the present invention, the polyolefin resin of the carrier layer is characterized in that it comprises 40 to 80% by weight of the first polyethylene and 20 to 60% by weight of the second polyethylene.

In the present invention, the polyolefin resin may be prepared by a polymerization method using a Ziegler-based catalyst, a chromium-based catalyst, a metallocene-based catalyst, and the like, and the copolymer may be in the form of a random copolymer or a block copolymer, and a molecule The structure may be any of atactic, isotactic or syndiotactic, and the polymerization method may be any of a low pressure method, a medium pressure method or a high pressure method. It is possible to mix | blend additives, such as a heat stabilizer, a ultraviolet absorber, an antistatic agent, a fluorescent agent, with such polyolefin resin by a well-known method.

In the present invention, the thickness of the carrier layer is preferably 20 to 30 ㎛.

If the thickness of the carrier layer is thinner than the lower limit, the mechanical strength of the film is weak, and if the thickness is thicker than the upper limit, the flexibility of the film is poor.

In the present invention, the adhesive layer is formed of a mixture of 40 to 80% by weight of a polyolefin resin and 20 to 60% by weight of an elastomer resin having an epoxy group, a hydroxyl group or an amine group. If the blending ratio of the elastomer resin is larger than the above range, the film is difficult to form and if less than the above range, the reliability may be lowered.

Elastomer resin refers to a synthetic polymer material that is similar in properties to rubber, which has a property of returning to its original shape when deformed, that is, it is resilient, tough and wear-resistant, and resistant to chemicals. Elastomer resin has the advantage of high adhesive strength, but it is difficult to be separated again after adhesion, it is difficult to exhibit self-adhesiveness and cohesive, so it is not easy to manufacture a film form has been limited to apply to the protective film.

In the present invention, in order to utilize the high adhesive strength of the elastomer resin and at the same time give easy separation and easy film formation, a mixture obtained by mixing a polyolefin resin in an appropriate blending ratio in the elastomer resin is provided as an adhesive layer.

In the present invention, the pressure-sensitive adhesive layer is more preferably a pressure-sensitive adhesive layer formed of a mixture of 40 to 60% by weight of polyolefin resin and 40 to 60% by weight of elastomer resin in terms of ease of film formation and reliability.

In the present invention, the elastomer resin may be selected from the group consisting of ethylene-based, styrene-based, propylene-based, acrylonitrile-based, butadiene-based, acrylic-based, isoprene-based, polyurethane-based and silicone-based elastomer resin, but is not limited thereto. .

In the present invention, the elastomer resin preferably has a weight average molecular weight in the range of 500 to 2,000,000. If the weight average molecular weight of the elastomer resin is outside the above range there is a disadvantage that the film processing is difficult.

In the embodiment of the present invention, SG-P3TEA (manufactured by Nagase, Japan) was used as the elastomer resin containing 15 wt% epoxy resin.

In the present invention, the polyolefin resin used in the adhesive layer is as described in the carrier layer.

In the present invention, the thickness of the adhesive layer is preferably 10 to 20 ㎛.

If the thickness of the adhesive layer is thinner than the lower limit, there is a disadvantage that the reliability is low, and if the thickness is thicker than the upper limit, there is a disadvantage that the manufacturing cost increases.

In the present invention, the thickness ratio of the carrier layer and the adhesive layer is preferably 20 to 30: 10 to 20. This is to excellently control the durability and mechanical strength of the protective film.

In the present invention, the self-adhesive protective film of the multilayer structure may be attached to the surface of the plastic, metal or glass, but is not limited thereto.

The self-adhesive protective film according to the present invention can be obtained by conventional inflation methods and / or casting methods.

The present inventors manufacture a self-adhesive protective film of a multi-layer structure as described above and by examining the adhesiveness, cutability, residue-free, mechanical properties to the self-adhesive protective film has excellent adhesiveness, cutability, residue-free, mechanical properties It was confirmed.

The present invention also provides an article to which the self-adhesive protective film of the multilayer structure described above is attached.

In the present invention, the article is an optical sheet, a mobile phone, a computer monitor, a television, a dry film photoresist (DFR), a plastic board building panel display device, a membrane touch panel, a carrier film or an entry sheet of a flexible printed circuit board, construction It may be, but is not limited to, materials, precision glass, automotive interiors, children's toys, kitchen containers or air-conditioning appliances.

The present invention uses a polyolefin resin as a carrier layer raw material and an elastomer resin as an adhesive layer raw material to prepare a self-adhesive protective film having a multi-layered structure composed of a carrier layer and a pressure-sensitive adhesive layer, such as adhesiveness, cutting property, no residue, mechanical properties, and the like. This excellent self-adhesive protective film can be provided and applied to home appliances, electronic products, building materials and the like can greatly contribute to the productivity improvement of various parts and materials industries.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples.

Example  1-5 and Comparative example  1-3: Preparation of self-adhesive protective film

Using the following resins to prepare a self-adhesive protective film in the mixing ratio of Table 1 and the thickness ratio of each layer.

Specifically, first, the resin of each layer in the pellet state obtained through dry blending or melt blending of the pellet state resin is weighed and introduced into each hopper, followed by two conventional single or twin screw extruders (Jenn Chong Plastics Machinery Works Co. Ltd.). , JC-LH series through melt extrusion at the carrier conditions of 250 ℃ in the carrier layer, 150 ℃ in the case of the adhesive layer and the film laminated through the die by the air cooling or water cooling method to finally have a thickness of 30 to 50 A self-adhesive surface protective film having a multilayer structure of µm was obtained. At this time, the self-adhesive protective film was prepared in a clean room of the class 1,000 ~ 10,000.

Material Information

Resin A: Low density polyethylene with a melt index of 1.2 g / 10 min and a density of 0.93 g / cm 3

Resin B: High density polyethylene with a melt index of 0.9 g / 10 min and a density of 0.96 g / cm 3

Resin C: Medium density polyethylene with melt index of 5.2 g / 10 min and density 0.94 g / cm 3

Resin D: Epoxy 15 wt% -containing elastomer resin SG-P3TEA (manufacturer Nagase, country of origin Japan)

Resin E: Ethylene-vinylacetate copolymer containing 12 wt% of vinyl acetate having a melt index of 1.1 g / 10 min and a density of 0.94 g / cm 3

Resin F: Ethylene-vinylacetate copolymer containing 18% by weight of vinyl acetate having a melt index of 2.1 g / 10 min and a density of 0.95 g / cm 3

division Resin composition Layer thickness ratio (㎛) Carrier layer Adhesive layer Carrier layer Adhesive layer Example 1 Resin A /
Resin B
(80/20) Resin C /
Resin D
(40/60) 25 15 Example 2 Resin A /
Resin B
(60/40) Resin C /
Resin D
(40/60) 25 15 Example 3 Resin A /
Resin B
(40/60) Resin C /
Resin D
(40/60) 25 15 Example 4 Resin A /
Resin B
(80/20) Resin C /
Resin D
(60/40) 25 15 Example 5 Resin A /
Resin B
(80/20) Resin C /
Resin D
(80/20) 25 15 Comparative Example 1 Resin A /
Resin B
(80/20) Resin E 35 15 Comparative Example 2 Resin A /
Resin B
(80/20) Resin D 35 15 Comparative Example 3 Resin A /
Resin B
(80/20) Resin F 35 15

Experimental Example  1: Physical property investigation of the self-adhesive protective film of the present invention

Physical properties of the self-adhesive protective film of the present invention was measured as follows.

Adhesion strength is measured by using a 3kg roller at room temperature on a protective film and pulling it at 300mm / min speed using a universal testing machine after 30 minutes to measure the adhesive strength (g / 25mm) as a peel force between the film and the substrate. It was.

The change rate of the adhesive strength with time was left for 2 days in an oven at 50 ° C., and then the change rate was observed by a 180 ° peel test at a width of 25 mm and a peel rate of 300 mm / min.

The cutting property was evaluated by measuring the cutting property of the protective film by comprehensively judging the ease of cutting, whether the edges were drooped and whether or not powder was generated while sticking the film specimen to the substrate and cutting it to a certain size (○ Good, △ Normal, X Poor).

No residue was evaluated in two steps by visually evaluating the material remaining on the substrate after peeling off the film (○ present, no X).

Transparency was measured on the basis of ASTM D 1003: 200 using haze meter.

Mechanical properties were determined by measuring the tensile strength and elongation by KS M 3001: 2001 standard using Instron.

The measurement results are shown in Table 2 below.

division Adhesive strength
(g / 25mm) depreciation
% Change Cutability No residue Haze
(%) The tensile strength
(MPa) Elongation rate
(%) Example 1 51 15 △ × 20 25 1300 Example 2 50 14 ○ × 19 23 1250 Example 3 51 14 ○ × 21 23 1290 Example 4 28 16 ○ × 15 19 1100 Example 5 12 14 ○ × 10 17 950 Comparative Example 1 24 120 △ ○ 20 12 750 Comparative Example 2 36 125 △ ○ 21 11 800 Comparative Example 3 42 140 △ ○ 20 10 813

As can be seen from Table 2, the self-adhesive protective film of the embodiment is stronger than the protective film of the comparative example, the adhesive strength is stronger, the rate of change is significantly smaller, the cutability is excellent, there is no residue, and the tensile strength and elongation is more Excellent. Therefore, the self-adhesive protective film of the present invention was confirmed to be more excellent in terms of adhesiveness, cutting properties, residue-free properties and mechanical properties through the above results.

Claims (10)

A carrier layer formed of a polyolefin resin; And an adhesive layer formed of a mixture of 40 to 80 wt% polyolefin resin and an elastomer resin having 20 to 60 wt% epoxy group, hydroxyl group or amine group,
Elastomeric resin having an epoxy group, a hydroxyl group or an amine group of the adhesive layer is a self-adhesive protective film having a melt index of 1 to 4 g / 10 minutes, density 0.85 to 0.95 g / cm ³ .
The self-adhesive protective film of claim 1, wherein the polyolefin resin of the carrier layer comprises polyethylene having a melt index of 0.5 to 8 g / 10 minutes and a density of 0.90 to 1.10 g / cm ³ .
The self-adhesive protective film of claim 2, wherein the polyolefin-based resin of the carrier layer comprises 40 to 80 wt% of low density polyethylene and 20 to 60 wt% of high density polyethylene.
According to claim 1, wherein the pressure-sensitive adhesive layer is a self-adhesive layer formed of a mixture of 40 to 60% by weight of a polyolefin resin and an elastomer resin having 40 to 60% by weight of an epoxy group, a hydroxyl group or an amine group Adhesive protective film.
The elastomer resin according to claim 1, wherein the elastomer resin having an epoxy group, a hydroxyl group or an amine group is composed of ethylene, styrene, propylene, acrylonitrile, butadiene, acrylic, isoprene, polyurethane and silicone elastomers. Self-adhesive protective film, characterized in that selected from.
The self-adhesive protective film of claim 5, wherein the elastomer resin has a weight average molecular weight of 500 to 2,000,000.
According to claim 1, wherein the thickness ratio of the carrier layer and the adhesive layer is a self-adhesive protective film, characterized in that 20 to 30: 10 to 20.
The self-adhesive protective film of claim 1, wherein the self-adhesive protective film is attached to a surface of plastic, metal or glass.
An article with a self-adhesive protective film according to any one of claims 1 to 8.
10. The carrier film or entry sheet of claim 9, wherein the article is an optical sheet, a cell phone, a computer monitor, a television, a dry film photoresist (DFR), a plastic board building panel display device, a membrane touch panel, a flexible printed circuit board. , Building materials, precision glass, automotive interior, children's toys, kitchen containers or heating and heating equipment.