KR20100016882A - Protective films and preparation methods thereof - Google Patents

Abstract

PURPOSE: A protective film and a manufacturing method thereof are provided to prevent foreign materials from being attached on an outer wall of a building. CONSTITUTION: A protective film comprises an adhesion prevention layer(1), a base material sheet(2), and an adhesive layer(3). The adhesion prevention layer comprises particle elements(1a) and binder element(1b). The base material sheet is formed on the bottom surface of the adhesion prevention layer. The adhesive layer is formed on the bottom surface of the base material sheet.

Description

Protective films and preparation methods

The present invention relates to a protective film and a method for manufacturing the same, and more specifically, an anti-adhesion layer having a binder component and a particle component contained in the binder component in a protruding state; And it relates to a protective film comprising a base sheet formed on the lower portion of the anti-sticking layer.

In general, illegal advertisements are attached to walls of various buildings and structures, such as power poles, concrete surfaces of building exterior walls, outdoor units of air conditioners, and distribution boxes. These advertisements are attached to the back of the leaflet in the form of glue using an adhesive such as glue, or the adhesive in the form of a sticker on the back of the adhesive directly attached to the surface of the facility, these advertisements are not easy to remove. In addition, the removal of such illegal advertisements caused excessive manpower and costs, and caused a problem of shortening the lifespan and ultimately damaging the city's aesthetics by deforming or damaging the facilities themselves by repeated removal.

Therefore, in order to prevent the attachment of illegal advertisements, efforts have been made in various aspects to provide a structure capable of preventing attachment to facilities to which illegal advertisements are attached, in addition to administrative measures.

Republic of Korea Patent Publication No. 2006-0085610 makes a relatively thick irregular shape on the surface of the synthetic rubber plate of a certain thickness, and cover the electric pole around the wheel with a certain width, and then fixed the upper and lower portions of the uneven plate with a steel band The illegal advertisement blocking sheet is disclosed. However, in this case, it is not easy to use because it has an anti-sticking effect but the appearance of Jeonju is not only very clunky but also very difficult to construct. In addition, there is a problem that is difficult to attach to the protruding portion, such as a distribution box or a smooth surface.

The present invention is to solve the above problems can block the attachment of various types of foreign matter to various external structures and building exterior walls, can be applied regardless of the type and shape of the adhered surface, and a protective film having excellent transparency and It aims at providing the manufacturing method.

The present invention provides an anti-adhesion layer having a binder component and a particle component contained in the binder component in a protruded state as a means for solving the above problems; And it provides a protective film comprising a base sheet formed on the lower portion of the adhesion prevention layer.

The present invention also provides a method for producing a protective film comprising the step of forming an anti-sticking layer by applying a mixture containing a binder component and a particle component to a base sheet as another means for solving the above problems.

The protective film of the present invention has excellent workability that can be applied regardless of the type and shape of the surface, such as a power pole, concrete surface of the building exterior wall, air conditioner outdoor unit, or distribution box panel. In addition, when the protective film of the present invention is applied to the adhered surface, it blocks the attachment of various types of advertisements, promotional materials and other foreign matters, and can be easily removed even after the attachment. Can be. In addition, since the protective film of the present invention has excellent transparency, even if the protective film is applied to the adhered surface, the contents of the adhered surface can be clearly seen, even after being directly applied to the surface of the outdoor advertisement to be protected. I can recognize it.

The present invention provides an adhesion preventing layer having a binder component and a particle component contained in the binder component in a protruding state; And it relates to a protective film comprising a base sheet formed on the lower portion of the anti-sticking layer. The protective film of the present invention can be prepared separately from the advertisement material, and has excellent workability, which can be applied regardless of the type and form of the adherend because of its excellent flexibility and transparency.

Hereinafter, the protective film according to the present invention will be described in more detail.

Adhesion prevention layer

In the protective film of the present invention, the anti-adhesion layer includes a binder component and a particle component contained in the binder component in a protruding state to the outside. The term "adhesion prevention layer" used in the present invention means various forms including a sticker, a label, and an adhesive tape on the protective film when the protective film of the present invention is attached to various exterior structures, building exterior walls, doors, windows and the like. It refers to a layer that can block the adhesion of advertisements, promotional materials and other foreign matter, and even if attached to it can be easily removed.

Particle components included in the adhesion prevention layer are contained in the binder component in a state of protruding outward. Particles protruding to the outside improves the adhesion prevention and release function of various foreign matters. A part of the particle component contained in the binder component protrudes outward, and the average height of the protrusion of the particle component may be 0.5 µm to 250 µm, preferably 1 µm to 67 µm, more preferably 1 µm to 33 µm. have. If the average height is less than 0.5 μm, foreign matter adhesion prevention and release functions of the adhesion preventing layer may be deteriorated. If the average height exceeds 250 μm, the particle component may be detached from the binder component.

The particle component is not particularly limited as long as it is a component having excellent weather resistance against ultraviolet rays, and specifically, polymer beads, ceramic beads, glass beads, or metal beads may be used alone or in combination. More specifically, the particle component may include teflon, polystyrene, rubber, polymethyl (meth) acrylate, urethane, polypropylene, polyethylene, nylon, vinyl chloride resin, urea, melamine, polycarbonate, aluminum hydroxide, titanium dioxide, potassium carbonate, It may include one or more selected from the group consisting of silica, silicon, glass, synthetic quartz, aluminum oxide, zirconium and indium tin oxide (ITO).

In addition, the shape of the particle component is preferably a spherical, plate-like, irregular shape or polyhedron, and can be used, such as hollow beads, hollow beads, beads with pores on the surface or beads without pores on the surface.

The particle component preferably has an average particle diameter of 1 to 1,000 µm, more preferably 1 to 200 µm, and most preferably 1 to 100 µm. When the average particle diameter is less than 1 μm, the particle component does not protrude to the outside and sinks inside the anti-sticking layer, thereby preventing the adhesion and release effect of various foreign substances, and when exceeding 1000 μm, it is mixed with the binder component to the base sheet. It is difficult to apply thinly and the particle component can contact the coater and damage the coater.

The content of the particle component is preferably 0.1 to 25 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the binder component.

Since the transparency of the anti-sticking layer is changed according to the transparency and the amount of the particle component used in the present invention, the transparency of the protective film may be controlled by controlling the transparency and the amount of the particle component depending on the purpose of use of the protective film.

The binder component included in the anti-adhesion layer includes a release composition and a curable composition.

The release composition included in the binder component includes a) a silicone-modified (meth) acrylic acid ester copolymer; b) a film forming agent; c) silicone additives; And d) a diluent. Hereinafter, the component of a mold release composition is demonstrated more concretely.

a) silicone denaturation ( Meta Acrylic Acid Ester Copolymer

The a) silicone-modified (meth) acrylic acid ester-based copolymer contained in the release property composition is represented by (i) (meth) acrylic acid ester monomer, ii) (meth) acrylic acid hydroxyalkyl ester monomer, and iii) It is preferable that it is a copolymer of the compound to become.

[Formula 1]

Where

R1, R2, and Y are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms,

n is an integer of 60 to 600.

The method for producing the a) silicone-modified (meth) acrylic acid ester copolymer is not particularly limited, and examples thereof include i) (meth) acrylic acid ester monomers; Ii) (meth) acrylic acid hydroxyalkyl ester monomers; Iii) a compound represented by the above formula; And a polymerization initiator, and can be produced by conventional methods such as radical polymerization.

a) Specific examples of the i) (meth) acrylic acid ester monomer which is a component of the silicone-modified (meth) acrylic acid ester copolymer include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, isopropyl (meth) acrylic acid, n-butyl 1 carbon number of alkyl such as (meth) acrylic acid, isobutyl (meth) acrylic acid, t-butyl (meth) acrylic acid, 2-ethylhexyl (meth) acrylic acid, lauryl (meth) acrylic acid, or stearyl (meth) acrylic acid (Meth) acrylic acid alkyl esters of from 8 to 8; (Meth) acrylic acid aryl esters having 6 to 20 carbon atoms of aryl such as (meth) acrylic acid phenyl; (Meth) acrylic acid cyclic alkyl esters having 3 to 12 carbon atoms of a cyclic alkyl group such as (meth) acrylic acid cyclohexyl; (Meth) acrylic acid polyalkylene glycol esters such as polyethylene glycol mono (meth) acrylate and the like; And (meth) acrylic acid alkoxyalkyl esters, and these may be used alone or in combination of two or more thereof. Preferably, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and hexyl (meth) acrylate can be used.

a) Specific examples of ii) (meth) acrylic acid hydroxyalkyl ester monomers which are other components of the silicone-modified (meth) acrylic acid ester copolymer include (meth) acrylic acid 2-hydroxypropyl, or (meth) acrylic acid 2-hydroxy Hydroxyethyl and the like, and these may be used alone or in combination of two or more thereof.

The content of the (meth) acrylic acid hydroxyalkyl ester monomer is preferably 2 to 15 parts by weight, more preferably 3 to 8 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester monomer. If less than 2 parts by weight of the surface properties are poor, if more than 15 parts by weight of the isocyanate compound, which is a curing agent is too much cross-linking due to excessive increase in the crosslinking density can be very hard to prevent the adhesion layer made by using it.

a) Another component of the silicone-modified methacrylic acid ester copolymer iii) The compound represented by the following formula (1) preferably has a weight average molecular weight of 5000 to 50000.

[Formula 1]

Where

R1, R2, and Y are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms,

n is an integer of 60 to 600.

The content of the compound represented by the above formula is preferably 5 to 55 parts by weight, more preferably 10 to 30 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester monomer. If the content is less than 5 parts by weight, the effect of preventing the adhesion of various foreign matters is insignificant, and if the content exceeds 55 parts by weight, the drying speed of the anti-sticking layer is slow and the workability is poor.

b) coating film Former

The film forming agent included in the release composition serves to protect the protective film from external contamination. The coating film forming agent which can be used by this invention is not specifically limited, A normal coating film forming agent can be used. Specific examples include antifoaming agents (e.g., silicone type BYK-065), leveling scratch resistance aids (e.g., Tego RAD 2700 of silicone acrylate type), dioctyl phthalate (DOP), or di Dibutyl phthalate (DOP) and the like are preferable.

The content of the film forming agent is preferably 2 to 5 parts by weight, more preferably 3 to 4 parts by weight based on 100 parts by weight of the silicone-modified (meth) acrylic acid ester copolymer. When the content is less than 2 parts by weight, workability is poor, and when it exceeds 5 parts by weight, a phenomenon occurs in burping.

c) silicone additives

Silicone additives contained in the release composition reinforce the silicone-modified acrylic resin to maximize the low pollution effect and the prevention of adhesion of various foreign substances. As the silicone additive in the present invention, a conventional silicone additive may be used, for example, silicone for release paper (for example, silicone KS847H for release paper from Shin-Etu), silicone for low pollution (for example, low for Shin-Etu) Contaminated silicon) or a release agent silicone (for example, Tego's release agent silicone), and the like, and it is more preferable to use a release paper silicone and a low pollution silicone in parallel.

The content of the silicone additive is preferably 10 to 40 parts by weight, more preferably 16 to 30 parts by weight based on 100 parts by weight of the silicone-modified (meth) acrylic acid ester copolymer. If the content is less than 10 parts by weight, the low pollution effect is lowered, and if it exceeds 40 parts by weight, the phenomenon occurs after the drying of the anti-sticking layer and the durability is poor.

d) diluent

The diluent included in the release composition plays a role of adjusting the viscosity to an appropriate viscosity for applying the anti-adhesion layer. Diluents usable in the present invention are not particularly limited as long as they are generally diluents used for paint dilution. Specifically, organic solvents such as methyl ethyl ketone (MEK), toluene, ethyl acetate, butyl acetate (BA), or acetone are preferable. The content of the diluent is preferably 30 to 100 parts by weight, more preferably 40 to 70 parts by weight based on 100 parts by weight of the silicone-modified (meth) acrylic acid ester copolymer. When the content is less than 30 parts by weight, the viscosity is high, the workability is poor, and when it exceeds 100 parts by weight, the film thickness is lowered, which is not preferable because of poor physical properties.

Curable composition contained in a binder contains an isocyanate type compound.

The isocyanate compound contained in the curable composition reacts with the (meth) acrylic acid hydroxy alkyl ester monomer to form a crosslink with a urethane bond. Specific examples of isocyanate compounds include aromatic isocyanate compounds such as hexamethylene diisocyanate (HMDI), aliphatic isocyanate compounds such as isophorone diisocyanate (IPDI), or toluene diisocyanate (TDI). These etc. are mentioned, These can be used individually or in mixture of 2 or more types.

The content of the isocyanate compound is preferably 10 to 30 parts by weight, more preferably 16 to 24 parts by weight based on 100 parts by weight of the silicone-modified (meth) acrylic acid ester copolymer. When the content is less than 10 parts by weight, the drying is delayed and the physical properties are poor, and when it exceeds 30 parts by weight, the protective film becomes hard.

The curable composition contains a solvent together with an isocyanate compound. It is preferable to prepare a binder component by dissolving the isocyanate compound in a solvent to prepare a curable composition and then mixing with the release composition. The solvent that can be used in the present invention is not particularly limited, but methyl ethyl ketone (MEK), butyl acetate (BA), toluene, or xylene can be used. The content of the solvent is preferably 50 to 150 parts by weight based on 100 parts by weight of the isocyanate compound. When the content is less than 50 parts by weight, the viscosity of the curable composition is high, the workability is poor, and when it exceeds 150 parts by weight, the isocyanate content is low, which is not preferable.

The protective film of the present invention includes a base sheet formed under the adhesion preventing layer. The base sheet which can be used in the present invention is not particularly limited as long as it is a material having excellent flexibility and transparency and excellent weather resistance against ultraviolet rays in the outdoors, and it is preferable that the base sheet is a transparent plastic sheet.

Although not limited thereto, the base sheet may be polyethylene, polypropylene, polyethylene terephthalate, acrylic, urethane, polyvinyl chloride, nylon, cellophane, polyvinylidene fluoride, polyvinyl fluoride, polymethyl (meth) acrylate, poly Carbonate, acrylonitrile butylene styrene, ethylene propylene rubber (EPDM), acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), polystyrene, polyethylene naphthalene or polyethylene methyl (meth) acrylic acid It is preferable that it is a transparency film manufactured by. The above heterogeneous mixing means that the base film is composed of two or more copolymers of the above-described resins, or two or more films made of the above-described resins are laminated.

In the present invention, the thickness of the base sheet may vary depending on the use, service life and material, but is preferably 5 to 200 μm, more preferably 10 to 100 μm.

The base sheet has a corona treatment layer, a plasma treatment layer, an acrylic primer treatment layer, a urethane primer treatment layer, or an acrylic-urethane primer treatment on the surface of the substrate sheet in contact with the adhesion prevention layer in order to improve adhesion with the adhesion prevention layer formed on the base sheet. It is preferable to include a layer.

The protective film of the present invention may further include an adhesive layer formed on the lower portion of the base sheet. By including an adhesive layer, it can be attached to various external structures, building exterior walls, etc., without using a separate adhesive means.

The pressure-sensitive adhesive layer is not particularly limited as long as the pressure-sensitive adhesive layer is excellent in transparency and weather resistance to ultraviolet rays in the outdoors, but preferably includes an oily or aqueous pressure-sensitive adhesive of acrylic, rubber, silicone, or epoxy components. Preferably, an adhesive can be suitably selected according to the kind of to-be-adhered surface. Specifically, when the surface to be coated is a metal-coated surface such as an outdoor air conditioner, a distribution box, or a street lamp, oily adhesives may be used regardless of the components.In case of using it on a concrete surface such as a power pole, the initial tack and adhesive force may be reduced. Excellent rubber-based adhesives are preferred. It is also desirable to increase the thickness of the adhesive when used on concrete surfaces rather than on general outdoor advertisements or metal painted surfaces.

1 is a cross-sectional view of a protective film 10 including a pressure-sensitive adhesive layer according to an embodiment of the present invention, the anti-sticking layer 1 includes a particle component 1a and a binder component 1b, The base sheet 2 is formed under the adhesion prevention layer 1, and the adhesive layer 3 is formed under the base sheet 2. The protective film in which the pressure-sensitive adhesive layer is formed can be easily applied when applied to various external structures and building exterior walls, and can prevent adhesion of various foreign matters on the adhered surface.

Attached Figure 2 shows an example in which the protective film according to an embodiment of the present invention is applied to the building outer wall. When there is an outdoor advertisement 4 printed or attached to the building exterior wall 20, when the protective film 10 according to the present invention is attached onto the outdoor advertisement 4, the protective film 10 is excellent. Due to the transparency, not only can the outdoor advertisement be recognized from the outside, but also various kinds of foreign matters can be prevented from being attached, thereby protecting the outdoor advertisement.

The present invention also relates to a method for producing a protective film comprising applying a mixture containing a binder component and a particle component to a base sheet to form an anti-sticking layer.

A binder component is manufactured by mixing a mold release composition and a curable composition, and mix | bonds particle | grains with the said binder component, and apply | coats to a base material sheet, and forms an adhesion prevention layer. The release composition is prepared by mixing a silicone-modified (meth) acrylic acid ester copolymer, a film forming agent, a silicone additive, and a diluent, and the curable composition is prepared by mixing an isocyanate compound with a solvent.

Specific details of the silicone-modified (meth) acrylic acid ester copolymer, coating film forming agent, silicone additive, diluent, isocyanate compound, solvent and particles are as described above.

The base sheet is polyethylene, polypropylene, polyethylene terephthalate, acrylic, urethane, polyvinyl chloride, nylon, cellophane, polyvinylidene fluoride, polyvinyl fluoride, polymethyl (meth) acrylate, polycarbonate, acrylonitrile butyl It may be prepared from a copolymer comprising at least one monomer selected from the group consisting of styrene styrene, ethylene propylene rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, polystyrene, polyethylene naphthalene, and polyethylenemethyl (meth) acrylic acid.

The method of applying the mixture including the binder component and the particle component to the base sheet is not particularly limited, and for example, a comma coater, a gravure coater, a microgravure coater, a Mayorbar Coater, Spray Coater, Curtain Coater, Knife Coater, Reverse Roll Coater, Rotary Screen Coater, Lip Coater, or CAP Coater It is available.

In addition, it is preferable to perform corona treatment, plasma treatment, acrylic primer treatment, urethane primer, or acrylic-urethane primer treatment on the surface of the substrate sheet before the mixture containing the binder component and the particle component is applied to the substrate sheet. By performing the surface treatment on the surface in contact with the adhesion prevention layer, the adhesion between the base sheet and the adhesion prevention layer is further improved.

The pressure-sensitive adhesive layer may be further formed on the lower portion of the base sheet on which the anti-sticking layer is formed to manufacture a protective film including the pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer may be formed using an oily or aqueous pressure-sensitive adhesive of acrylic, rubber, silicone, or epoxy components, and the method of forming the pressure-sensitive adhesive layer on the lower portion of the base sheet is not particularly limited.

1 is a cross-sectional view of a protective film according to an embodiment of the present invention.

2 is a cross-sectional view showing a state in which the protective film according to an embodiment of the present invention is constructed on the outer wall of the building.

<Explanation of symbols for main parts of the drawings>

1a: particle component 1b: binder component

1: Antifouling layer 2: Base sheet

3: adhesive layer 10: protective film

4: outdoor advertisement 20: building shaft curtain wall

Claims (15)

An adhesion preventing layer having a binder component and a particle component contained in the binder component in a protruding state; And Protective film comprising a base sheet formed on the lower portion of the adhesion prevention layer. The method of claim 1, Particle component is a protective film, characterized in that the average height of the protrusion is 0.5 ㎛ to 250 ㎛. The method of claim 1, Particle component is a protective film, characterized in that at least one selected from the group consisting of polymer beads, ceramic beads, glass beads and metal beads. The method of claim 1, Particle components are Teflon, polystyrene, rubber, polymethyl (meth) acrylate, urethane, polypropylene, polyethylene, nylon, vinyl chloride resin, urea, melamine, polycarbonate, aluminum hydroxide, titanium dioxide, potassium carbonate, silica, silicone, Protective film, characterized in that it comprises at least one selected from the group consisting of glass, synthetic quartz, aluminum oxide, zirconium and indium tin oxide. The method of claim 1, Particle component is a protective film, characterized in that the average particle diameter of 1 ㎛ to 1,000 ㎛. The method of claim 1, The particle component is a protective film, characterized in that contained in an amount of 0.1 to 25 parts by weight with respect to 100 parts by weight of the binder component. The method of claim 1, The binder component comprises a releasable composition and a curable composition. The method of claim 7, wherein The release composition is a protective film comprising a silicone-modified (meth) acrylic acid ester copolymer, a film forming agent, a silicone additive, and a diluent. The method of claim 8, The silicone-modified (meth) acrylic acid ester copolymer includes a (meth) acrylic acid ester monomer, a (meth) acrylic acid hydroxyalkyl ester monomer, and a compound represented by the following formula (1): [Formula 1]

Wherein R 1, R 2, and Y are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and n is an integer of 60 to 600. The method of claim 7, wherein The curable composition is a protective film comprising an isocyanate compound. The method of claim 1, The base sheet is a protective film, characterized in that the transparent plastic sheet. The method of claim 1, The base sheet is polyethylene, polypropylene, polyethylene terephthalate, acrylic, urethane, polyvinyl chloride, nylon, cellophane, polyvinylidene fluoride, polyvinyl fluoride, polymethyl (meth) acrylate, polycarbonate, acrylonitrile butyl A protective film comprising at least one selected from the group consisting of styrene styrene, ethylene propylene rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, polystyrene, polyethylene naphthalene and polyethylenemethyl (meth) acrylic acid. The method of claim 1, The base sheet is a protective film comprising a corona treatment layer, a plasma treatment layer, an acrylic primer treatment layer, a urethane primer treatment layer or an acrylic-urethane primer treatment layer on the surface in contact with the adhesion prevention layer. The method of claim 1, The protective film, characterized in that it further comprises an adhesive layer formed on the lower portion of the base sheet. A method of producing a protective film comprising applying a mixture comprising a binder component and a particle component to a base sheet to form an anti-sticking layer.

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