CN111925766B - Ultraviolet-curable polyurethane adhesive and surface protective film using same - Google Patents
Ultraviolet-curable polyurethane adhesive and surface protective film using same Download PDFInfo
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- CN111925766B CN111925766B CN202010188675.9A CN202010188675A CN111925766B CN 111925766 B CN111925766 B CN 111925766B CN 202010188675 A CN202010188675 A CN 202010188675A CN 111925766 B CN111925766 B CN 111925766B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
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Abstract
The present invention relates to an ultraviolet curing type polyurethane-based adhesive and a surface protective film using the same, and more particularly, to an ultraviolet curing type polyurethane-based adhesive having excellent wettability and peelability and a surface protective film temporarily attached to a surface of an optical and/or transfer member using the ultraviolet curing type polyurethane-based adhesive in order to prevent the member from being damaged during a manufacturing process of an electronic display device or the like.
Description
Technical Field
The present invention relates to an ultraviolet curing type polyurethane-based adhesive and a surface protective film using the same, and more particularly, to an ultraviolet curing type polyurethane-based adhesive having excellent wetting and peeling properties and a surface protective film temporarily attached to a surface of an optical and/or transfer member using the ultraviolet curing type polyurethane-based adhesive in order to prevent the member from being damaged during a manufacturing process of an electronic display device or the like.
Background
In order to prevent defects from occurring on the surface of various display devices including a polarizing film which is one of flat panel display devices (FPDs), a protection window of a mobile phone, and the like, when processing, assembling, inspecting, transporting, and the like are performed, a process is performed in a state where a protection film is attached.
In this case, regardless of the layer structure of the protective film, the layer facing the adherend is an adhesive layer, and the performance of the adhesive layer is a very important factor in determining the adhesion to the adherend, the adhesive transfer phenomenon, and the like.
In this case, there is a problem that a part of the adhesive layer is not uniformly adhered to the surface of the target product but only a part of the adhesive layer is attached to the adherend when the protective film is attached, and on the contrary, there is a problem that contaminants, impurities, or the like remain on the adherend and remain when the adhesive layer is peeled off.
The conventional technology uses a Si polymer in order to maximize wettability for smoothly peeling and bonding an adhesive composition or an adhesive layer, but it is expensive and has a problem of not being widely used, and in the case of using a silicone oil in order to additionally impart wettability, contamination is caused by the residue of the oil on the surface, so that there is a problem of deterioration in touch sensitivity of a touch panel to which the adhesive composition is applied.
Further, an adhesive film composition for semiconductor assembly including rubber, phenolic resin, vulcanizing agent, filler, organic solvent, and the like is described in korean registered patent No. 10-0826420, however, only an adhesive film capable of maintaining reliability of a product by maintaining adhesiveness is mentioned, and there still remains a problem about ensuring wettability and occurrence of residue after peeling the adhesive film.
Documents of the prior art
Patent document
Korean registered patent No. 10-0826420.
Disclosure of Invention
Technical problem to be solved
The present invention was made to solve the above-described conventional problems, and an object thereof is to provide an ultraviolet-curable polyurethane adhesive for a protective film having excellent wettability and peelability.
Further, an object of the present invention is to provide a surface protective film suitable for use in an electronic device such as a flat panel display device by using the ultraviolet curable polyurethane adhesive.
Means for solving the problems
In order to achieve the above object, in an embodiment of the present invention, there is provided a surface protective film relating to a surface protective film including an adhesive layer on a base film, wherein the adhesive layer is made of an ultraviolet-curable urethane-based composition including an ultraviolet-curable urethane acrylate, an acrylic monomer, and a photoinitiator.
Further, in an embodiment of the present invention, there is provided a method for manufacturing a surface protective film, the method including the steps of: preparing an ultraviolet-curable urethane-based composition comprising an ultraviolet-curable urethane acrylate, an acrylic monomer and a photoinitiator; coating the composition on the base film to form an adhesive layer; and ultraviolet curing the adhesive layer.
Effects of the invention
The surface protective film of the present invention ensures a certain level or more of wettability, thereby enabling uniform adhesion and surface protection between the surface to be adhered and the surface protective film without air bubbles, and also reducing the increase in peeling force due to the standing time and heat, thereby significantly reducing the damage of the adherend during peeling. That is, the use of the surface protective film to which the adhesive is applied enables the electronic component to be peeled off without being damaged, and therefore, the process loss can be greatly reduced, which is very useful in this respect.
Drawings
Fig. 1 and 2 are schematic diagrams showing a cross section of a surface protective film manufactured in an embodiment of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily carry out the present invention. The present invention may be realized in various forms and is not limited to the embodiments described herein.
The present invention relates to an ultraviolet-curable polyurethane-based adhesive and a surface protective film using the same, and relates to an ultraviolet-curable polyurethane-based adhesive having excellent wettability and peelability and a surface protective film temporarily attached to a surface of an optical and/or transfer member using the ultraviolet-curable polyurethane-based adhesive in order to prevent the member from being damaged during a manufacturing process of an electronic display device or the like.
Conventionally, since the thermosetting method mainly cures at high temperature, it has been impossible to use a material vulnerable to heat, and there has been a problem that not only is an environmental problem such as air pollution caused by the use of a solvent, but also, since a wide area is required for installing a curing device, energy consumption required for a curing process increases and a process time consumed increases, and thus productivity decreases.
In contrast, the ultraviolet curing method can overcome the disadvantages of the thermal curing method, and has not only high productivity but also little change in the cured film because it has superior storage stability and cures within several seconds at normal temperature as compared with the thermal curing method, and the film manufactured by this method has advantages of superior abrasion resistance, water resistance, solvent resistance, heat resistance, weather resistance, and the like.
In contrast, the present invention provides a surface protective film made of an ultraviolet-curable polyurethane composition.
The surface protective film according to an embodiment of the present invention relates to a surface protective film including an adhesive layer made of an ultraviolet-curable urethane-based composition including an ultraviolet-curable urethane acrylate, an acrylic monomer, and a photoinitiator on a base film.
The ultraviolet curable urethane acrylate contains urethane bonds as repeating units, which are long and have a flexible property. Ultraviolet-curable urethane acrylates have a very wide variety of types, and are classified into aliphatic urethane acrylates and aromatic urethane acrylates according to the type of isocyanate.
As the ultraviolet curing type urethane acrylate, for example, a reactant of a mixture of a polyisocyanate compound and a (meth) acrylate containing a hydroxyl group can be exemplified. The above polyisocyanate compound may be exemplified as a compound having 2 or more isocyanates, for example, aliphatic (aliphatic) or aromatic (aromatic) polyisocyanate, and specifically, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 1, 3-xylylene diisocyanate, 1, 4-phospholene diisocyanate, or the like may be exemplified as an aromatic polyisocyanate, and diphenylmethane-4, 4' -diisocyanate, isophorone diisocyanate (isophorone diisocyanate), 1, 6-hexamethylene diisocyanate, or the like may be exemplified as an aliphatic polyisocyanate. Further, as the above-mentioned (meth) acrylate having a hydroxyl group, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, or 8-hydroxyoctyl (meth) acrylate may be exemplified, but not limited thereto.
Further, as the ultraviolet curable urethane acrylate, for example, a urethane polymer having an isocyanate at a terminal and a reactant including a (meth) acrylate having a hydroxyl group, which are reactants of a mixture including an ester polyol and a polyisocyanate, may be used. Examples of the ester polyol include a polyol and/or a polyether polyol, and an esterification reaction product with an acid component such as a dibasic acid or an anhydride thereof. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, cyclohexanedimethanol, and 3-methyl-1, 5-pentanediol, examples of the polyether polyol include polyalkylene glycol such as polyethylene glycol, polypropylene glycol, and polybutylene glycol, and block or random polymer glycol such as polyethylene propoxy block polymer glycol, and examples of the acid component include dibasic acid such as adipic acid (adipic acid), succinic acid (succinic acid), phthalic acid (phthalic acid), tetrahydrophthalic acid, hexahydrophthalic acid, and terephthalic acid, and anhydrides thereof, but the present invention is not limited thereto. Further, as the polyisocyanate and the (meth) acrylate having a hydroxyl group, the above-mentioned compounds can be used.
Further, as the ultraviolet curing type urethane acrylate, for example, as a reactant including a mixture of a polyether polyol and a polyisocyanate, a reactant including a mixture of a urethane polymer having an isocyanate at a terminal and a (meth) acrylate having a hydroxyl group may also be used.
In addition, the ultraviolet curing type urethane acrylate imparts flexibility by the chemical physical property of the urethane functional group, and the peel strength can be changed according to the number of the acrylic functional groups. In addition, various attributes can be achieved depending on the type of isocyanate. The aliphatic urethane acrylate is optically transparent as a non-yellowing type, and the aromatic urethane acrylate is a yellowing type, which has a characteristic of fast reactivity. In the present invention, the ultraviolet curable urethane acrylate may have a multifunctional functional group, and preferably may have 2 to 5 functional groups.
According to an embodiment of the present invention, the ultraviolet curing type urethane acrylate is preferably an aliphatic urethane acrylate, and more preferably may be a 2 to 5 functional aliphatic urethane acrylate. The functional aliphatic urethane acrylate does not yellow and increases the crosslinking density within a range that does not adversely affect the flexibility, thereby maximizing the wettability and the peelability.
The acrylic monomer is used for the purpose of not only reducing the viscosity of the ultraviolet-curable polyurethane composition but also adjusting the peel force. For example, a monomer having a functional group capable of participating in radical polymerization by ultraviolet irradiation may be used.
According to an embodiment of the present invention, as the monomer, the (meth) acrylate monomer may be exemplified by at least one selected from the group consisting of alkyl (meth) acrylates, alkoxy-group-containing (meth) acrylates, alicyclic group-containing (meth) acrylates, aromatic group-containing (meth) acrylates, heterocyclic ring-containing (meth) acrylates, and multifunctional acrylates.
As the above-mentioned alkyl (meth) acrylate, there may be exemplified alkyl (meth) acrylates having an alkyl group of 1 to 20 carbon elements such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, dodecyl (meth) acrylate, and tetradecyl (meth) acrylate. As the (meth) acrylate having an alkoxy group, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, ethylene glycol phenyl ether (meth) acrylate, polyethylene glycol (degree of polymerization: 2 to 8) phenyl ether (meth) acrylate, ethylene glycol nonylphenyl ether (meth) acrylate, polyethylene glycol (degree of polymerization: 2 to 8) nonylphenyl ether (meth) acrylate, or the like can be exemplified. Examples of the (meth) acrylate having an alicyclic group include an isoborane (meth) acrylate, a dicyclopentenyl (meth) acrylate, and a dicyclopentenyloxy (meth) acrylate. Examples of the (meth) acrylate having an aromatic group include phenylhydroxypropyl (meth) acrylate, benzyl (meth) acrylate, and the like. Examples of the (meth) acrylate having a heterocyclic ring include tetrahydrofurfuryl (meth) acrylate and morpholinyl (meth) acrylate. Examples of the polyfunctional acrylate include 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid (hydroxyvaleric acid) neopentyl glycol di (meth) acrylate, dicyclopentanyl (dicyclopentanyl) di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified di (meth) acrylate, di (meth) acryloyloxyethyl isocyanurate, allyl-modified cyclohexyl di (meth) acrylate, tricyclodecanedimethanol (meth) acrylate, dimethylol dicyclopentanyl di (meth) acrylate, ethylene oxide-modified hexahydrophthalic acid di (meth) acrylate, Tricyclodecane dimethanol (meth) acrylate, neopentyl glycol-modified trimethylpropane di (meth) acrylate, 2-functional acrylate such as adamantane (adamantane) di (meth) acrylate or 9, 9-bis [4- (2-acryloyloxyethoxy) phenyl ] fluorene (fluorone), 3-functional acrylate such as trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate or tri (meth) acryloyloxyethyl isocyanurate, 4-functional acrylate such as diglycerol tetra (meth) acrylate or pentaerythritol tetra (meth) acrylate, 5-functional acrylate such as propionic acid-modified dipentaerythritol penta (meth) acrylate, and the like, And 6-functional acrylates such as dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate, but the present invention is not limited thereto.
The photoinitiator absorbs ultraviolet rays and generates radicals, thereby acting to start the reaction. The absorbed wavelength region differs depending on the kind of the initiator, and most of it does not participate in the reaction. A wavelength of 250 to 360nm is generally absorbed, and in order to absorb a plurality of wavelengths and promote reactivity, 2 or more kinds of initiators may be used in mixture. When the coating thickness of the ultraviolet-curable polyurethane composition is small, the reactivity is better as the content of the initiator is higher, and when the coating thickness of the ultraviolet-curable polyurethane composition is large, the overall curing speed is higher as the content of the initiator is smaller.
According to the embodiment of the present invention, a known photoinitiator such as a benzo system, a hydroxy ketone system, an amino ketone system, a peroxide system, or a phosphine oxide system can be used as the photoinitiator.
According to an embodiment of the present invention, the ultraviolet curing type polyurethane-based composition may be configured to include 30 to 90 parts by weight of an ultraviolet curing type urethane acrylate, 10 to 70 parts by weight of an acrylic monomer, and 0.01 to 10 parts by weight of a photoinitiator.
At this time, when the content of the ultraviolet curable urethane acrylate is less than the range, wettability is insufficient, and when it exceeds the range, it is not easy to adjust viscosity problem and peeling force and is not preferable.
Further, when the content of the acrylic monomer is less than the range, there is little dilution effect to cause a problem of high viscosity, and when exceeding the range, flexibility is lowered and wettability is poor.
Meanwhile, in the case where the content of the photoinitiator is less than the range, there is a disadvantage that the reactivity is slow, and when it exceeds the range, although the reactivity increases, there is a possibility that the adhered surface is contaminated by the unreacted photoinitiator.
According to an embodiment of the present invention, the ultraviolet curable polyurethane-based composition may further include various additive components as needed in addition to the components, and at least one selected from the group consisting of, for example, a plasticizer, a wetting agent, an antioxidant, and an antistatic agent may be exemplified as the additive, but is not limited thereto.
At this time, the additive may be included within a range that does not have a great influence on the properties of the ultraviolet curing type polyurethane-based composition, and specifically, the additive may be included in an amount of 0.01 to 45 parts by weight per 100 parts by weight of the ultraviolet curing type polyurethane-based composition.
The surface protective film according to an embodiment of the present invention may further include a release layer on the adhesive layer. Thereby, even if the adhesive films are overlapped with each other, occurrence of blocking between the adhesive films can be prevented, and especially, the adhesive films can be easily stored in a rolled state.
According to an embodiment of the present invention, the adhesive layer may be manufactured by coating the ultraviolet curable polyurethane-based composition to an appropriate thickness by casting and then irradiating ultraviolet rays to cure it.
At this time, the method of casting the ultraviolet curable polyurethane-based composition is not particularly limited, and may be performed using any one of casting apparatuses selected from the group consisting of a bar coater, a knife coater, a roll coater, a spray coater, a gravure coater, a curtain coater, a comma coater, and a lip coater, for example, in consideration of a desired thickness.
Further, for example, the ultraviolet irradiation may be performed using any one lamp selected from the group consisting of a metal halide lamp, a high-pressure mercury lamp, a black light lamp, an electrodeless lamp, and a xenon lamp (xenon lamp). In the above, the irradiation conditions of the active energy rays, for example, the wavelength, the light amount, or the like are not particularly limited, and may be selected in consideration of the components of the composition, or the like.
According to an embodiment of the present invention, the base film may include at least one resin selected from the group consisting of polyester (polyester) resin, Polycarbonate (PC) resin, Polyimide (PI) resin, Polystyrene (PS) resin, Polyethersulfone (PES) resin, Polyamide (Polyamide) resin, Polyamideimide (Polyamideimide) resin, poly (meth) acrylate resin, silicone resin (silicone) resin, Cyclic Olefin Polymer (COP), and a mixture thereof.
As the polyester resin, at least one selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), and a mixture thereof may be exemplified, but not limited thereto.
The surface protective film manufactured according to an embodiment of the present invention may be characterized in that the thickness of the adhesive layer is 5 to 90 μm.
The surface protective film manufactured according to the embodiment of the present invention may be characterized by a peel force of 10gf/in or less.
The surface protective film manufactured according to the embodiment of the present invention may be characterized by having a haze of 5% or less.
Further, the present invention relates to a method of manufacturing a surface protective film according to an embodiment of the present invention, which may include the steps of: preparing a basement membrane; preparing an ultraviolet-curable polyurethane-based composition comprising a urethane acrylate, an acrylic monomer and a photoinitiator; coating the composition on the base film to form an adhesive layer; and ultraviolet curing the adhesive layer.
The method of manufacturing a surface protective film according to an embodiment of the present invention may further include the steps of: a release layer is additionally laminated on the adhesive layer.
According to an embodiment of the present invention, the ultraviolet curing type urethane acrylate is preferably an aliphatic urethane acrylate, and more preferably may be a 2-functional to 5-functional aliphatic urethane acrylate.
According to an embodiment of the present invention, in the step of preparing the ultraviolet curing type polyurethane-based composition, a mixture of 30 to 90 parts by weight of urethane acrylate, 10 to 70 parts by weight of an acrylic monomer, and 0.01 to 10 parts by weight of a photoinitiator may be prepared.
Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. However, it should be understood that the following embodiments are merely examples provided to demonstrate the effects of the present invention, and the scope of the present invention is not limited by the following embodiments. In the following examples and comparative examples, the properties of the produced surface protective films were evaluated as follows.
Example 1: surface protective film made of UV-curable adhesive composition
An ultraviolet curable adhesive composition was manufactured by combining 70 parts by weight of a 2-functional aliphatic urethane acrylate oligomer and 30 parts by weight of lauryl acrylate, and additionally adding 0.7 parts by weight of a photoinitiator (1-hydroxy-cyclohexyl-phenyl ketone (IRGACURE 184, manufactured by gasoline corporation)) and mixing and defoaming the same.
Next, the composition was coated to a thickness of about 70 μm on a polyester base film using a bar coater to form an adhesive layer, and at this time, in order to prevent the adhesive layer from contacting oxygen, after a release film was coated on the formed adhesive layer, a mercury lamp was used at 2000mJ/cm2The composition is cured by irradiating ultraviolet rays with the light quantity of (1) to produce a surface protective film.
Example 2: surface protective film made of UV-curable adhesive composition
A surface protective film was produced in the same manner as in example 1, except that a uv-curable adhesive composition was produced by combining 65 parts by weight of a 2-functional aliphatic urethane acrylate oligomer, 25 parts by weight of lauryl acrylate and 10 parts by weight of isobornyl acrylate, and additionally adding 0.7 part by weight of a photoinitiator (IRGACURE 184, 1-hydroxycyclohexyl phenyl ketone), mixing and defoaming the same.
Example 3: surface protective film made of UV-curable adhesive composition
A surface protective film was produced in the same manner as in example 1, except that an ultraviolet-curable adhesive composition was produced by combining 55 parts by weight of a 2-functional aliphatic urethane acrylate oligomer and 45 parts by weight of tetradecyl acrylate, and additionally adding 5 parts by weight of 1, 6-hexanediol diacrylate (HDDA) and a photoinitiator (IRGACURE 184, 1-hydroxycyclohexyl phenyl ketone), mixing and defoaming the same.
Comparative example 1: surface protective film produced by using heat-curable adhesive composition
The heat-curable adhesive composition was prepared by mixing 10 parts by weight of a hexamethylene diisocyanate curing agent with 100 parts by weight of a urethane resin and defoaming the mixture.
Next, the composition was dried, the composition was coated to a thickness of about 70 μm on a polyester base film using a bar coater to form an adhesive layer, and after drying in an oven at 120 ℃ for 5 minutes, a release film was coated, and left in a curing oven at 50 ℃ for 48 hours to be thermally cured, thereby manufacturing a surface protective film.
Test examples evaluation of characteristics
1. Adhesive force
The surface protective films manufactured in the one example and the comparative example were cut and manufactured into sample pieces of a width of 25mm and a length of 200 mm. After the adhesive layer of the sample piece was attached on a glass plate as a medium using a 2kg roller, a sample placed in an oven at 85 ℃ for 2 hours (normal temperature peel force) and a sample placed in an oven at normal temperature for 7 days (high temperature peel force) were measured for normal temperature peel force and high temperature peel force, respectively, at a peel speed of 5mm/sec and a peel angle of 180 degrees using a tensile tester.
2. Wettability
The surface protective films manufactured in the one example and the comparative example were attached using a 2kg roller on a glass plate molded with a terminal difference of 5 μm so that the adhesive layer was in surface contact with the terminal difference. Subsequently, the wettability was evaluated by the following evaluation criteria.
< evaluation criteria >
O: no bubble in end difference
X: there are bubbles along the end difference.
3. Measuring optical properties
The surface protection films manufactured in the one example and the comparative example were coated on a glass plate, and transmittance and haze were measured in the structures of the glass plate and the surface protection film according to JIS K7105.
As described above, the adhesive force, wettability and optical characteristics of the surface protective films manufactured in the examples of the present invention and the comparative examples were evaluated, respectively, and the results thereof were collated and shown in table 1.
[ TABLE 1 ]
As shown in table 1, the surface protective films manufactured in the examples of the present invention have excellent normal temperature adhesive force and also have excellent peeling force under a high temperature environment, compared to the surface protective films manufactured in the comparative examples.
In particular, when example 1 and comparative example 1 exhibiting similar levels of wettability, transmittance and haze were compared, it was observed that the room-temperature adhesive force of comparative example 1 exhibited a significantly low level as compared to example 1, however, the high-temperature adhesive force became high to about 4.3 times the room-temperature adhesive force, and thus the peel force was greatly increased.
In contrast, example 1 exhibited excellent room-temperature adhesion, and the high-temperature adhesion also exhibited a level similar to the room-temperature adhesion. That is, the surface protective film manufactured in the embodiment of the present invention can maintain the adhesive force of a level similar to that of the normal temperature environment even in the high temperature environment, and thus exhibits excellent peeling force.
The foregoing description focuses on a preferred embodiment of the present invention. It will be appreciated by those skilled in the art that the present invention can be embodied in modified forms without departing from the essential characteristics thereof.
Claims (11)
1. A surface protective film comprising an adhesive layer on a base film, wherein the adhesive layer is made of an ultraviolet-curable polyurethane-based composition comprising 30 to 90 parts by weight of 2 to 5 functional aliphatic urethane acrylate, 10 to 70 parts by weight of an acrylic monomer, and 0.01 to 10 parts by weight of a photoinitiator;
the acrylic monomer is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, ethylene glycol phenyl ether (meth) acrylate, polyethylene glycol (degree of polymerization: 2 to 8) phenyl ether (meth) acrylate, ethylene glycol methyl (meth) acrylate, propylene glycol (styrene (meth) acrylate, styrene (styrene) acrylate), styrene (styrene) acrylate), styrene (styrene) acrylate), styrene (styrene) acrylate), styrene (styrene) acrylate), styrene (styrene) acrylate), styrene (styrene) acrylate), styrene (styrene) acrylate), styrene (styrene) acrylate), styrene (styrene) acrylate), styrene) acrylate), styrene (styrene) acrylate), styrene (styrene) acrylate), styrene (styrene) acrylate), styrene (, Ethylene glycol nonylphenyl ether (meth) acrylate, polyethylene glycol (degree of polymerization: 2 to 8) nonylphenyl ether (meth) acrylate, isoborane (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholinyl (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified di (meth) acrylate, and mixtures thereof, Di (meth) acryloyloxyethyl isocyanurate, allylated cyclohexyl di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, ethylene oxide-modified hexahydrophthalic acid di (meth) acrylate, neopentyl glycol-modified trimethylpropane di (meth) acrylate, adamantane di (meth) acrylate, 9-bis [4- (2-acryloyloxyethoxy) phenyl ] fluorene, trimethylolpropane tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tri (meth) acryloyloxyethyl isocyanurate, diglycerin tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, propionic acid-modified dipentaerythritol penta (meth) acrylate, allylated cyclohexyl di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, trimethylolpropane tetra (meth) acrylate, or mixtures thereof, At least one of dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and isobornyl acrylate;
the surface protection film has a peel force of 10gf/in or less.
2. The surface protective film according to claim 1, further comprising:
a release layer on the adhesive layer.
3. The surface protective film according to claim 1, wherein the ultraviolet-curable polyurethane-based composition further comprises one or more additives selected from the group consisting of a plasticizer, a wetting agent, an antioxidant and an antistatic agent.
4. The surface protective film according to claim 3, wherein the additive comprises 0.01 to 45 parts by weight of the ultraviolet-curable polyurethane-based composition per 100 parts by weight.
5. The surface protective film according to claim 1, wherein the base film comprises at least one resin selected from the group consisting of a polyester resin, a polycarbonate resin, a polyimide resin, a polystyrene resin, a polyethersulfone resin, a polyamide resin, a polyamideimide resin, a poly (meth) acrylate resin, a silicone resin, a cyclic olefin polymer, and a mixture thereof.
6. The surface protective film according to claim 5, wherein the polyester resin comprises at least one selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, and a mixture thereof.
7. The surface protective film according to claim 1, wherein the photoinitiator comprises at least one selected from the group consisting of a benzo system, a hydroxyketone system, an aminoketone system, a peroxide system, and a phosphine oxide system.
8. The surface protective film according to claim 1, wherein the adhesive layer has a thickness of 5 to 90 μm.
9. The surface protective film according to claim 1, wherein the haze is 5% or less.
10. A method for producing a surface protective film for use in producing the surface protective film according to any one of claims 1 to 9, comprising the steps of:
preparing a basement membrane;
preparing an ultraviolet curing type polyurethane-based composition comprising 30 to 90 parts by weight of 2 to 5 functional aliphatic urethane acrylate, 10 to 70 parts by weight of acrylic monomer, and 0.01 to 10 parts by weight of photoinitiator;
coating the composition on the base film to form an adhesive layer; and
and carrying out ultraviolet curing on the adhesive layer to obtain the surface protection film.
11. The method for manufacturing a surface protective film according to claim 10, further comprising the steps of:
a release layer is additionally laminated on the adhesive layer.
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| KR10-2019-0055710 | 2019-05-13 | ||
| KR1020190055710A KR102246121B1 (en) | 2019-05-13 | 2019-05-13 | UV-curable urethane-based pressure-sensitive adhesive and surface protective film using the same |
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| CN111925766A CN111925766A (en) | 2020-11-13 |
| CN111925766B true CN111925766B (en) | 2022-06-07 |
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| KR20120073088A (en) * | 2010-12-24 | 2012-07-04 | 디아이씨 가부시끼가이샤 | Resin composition for uv-curable pressure sensitive adhesive, pressure sensitive adhesive and laminate |
| CN108977161A (en) * | 2018-06-26 | 2018-12-11 | 江阴通利光电科技有限公司 | A kind of preparation method and AB glue protective film of optical adhesive |
| CN109423251A (en) * | 2017-09-04 | 2019-03-05 | 荒川化学工业株式会社 | Protective film ultraviolet-curing adhesive composition, adhesive phase, protection board |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100826420B1 (en) | 2006-12-29 | 2008-04-29 | 제일모직주식회사 | Bonding film composition for semiconductor assembly and bonding film therefrom |
| JP2010241917A (en) * | 2009-04-03 | 2010-10-28 | Nippon Kayaku Co Ltd | Resin composition |
| JP5834606B2 (en) * | 2011-08-05 | 2015-12-24 | Dic株式会社 | UV-curable adhesive resin composition, adhesive and laminate |
| KR101628435B1 (en) * | 2013-01-21 | 2016-06-08 | 제일모직주식회사 | Adhesive film, adhesive composition for the same and display member comprising the same |
| JP5822052B1 (en) * | 2013-12-25 | 2015-11-24 | Dic株式会社 | UV-curable adhesive composition, adhesive film, and method for producing adhesive film |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20120073088A (en) * | 2010-12-24 | 2012-07-04 | 디아이씨 가부시끼가이샤 | Resin composition for uv-curable pressure sensitive adhesive, pressure sensitive adhesive and laminate |
| CN102533205B (en) * | 2010-12-24 | 2015-05-06 | Dic株式会社 | Resin composition for ultraviolet ray solidifying agglutinant, agglutinant, and laminating body |
| CN109423251A (en) * | 2017-09-04 | 2019-03-05 | 荒川化学工业株式会社 | Protective film ultraviolet-curing adhesive composition, adhesive phase, protection board |
| CN108977161A (en) * | 2018-06-26 | 2018-12-11 | 江阴通利光电科技有限公司 | A kind of preparation method and AB glue protective film of optical adhesive |
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| CN111925766A (en) | 2020-11-13 |
| KR102246121B9 (en) | 2021-07-26 |
| KR20200131023A (en) | 2020-11-23 |
| KR102246121B1 (en) | 2021-04-29 |
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