CN111278944A - Adhesive film, adhesive composition for the same, and display member comprising the same - Google Patents
Adhesive film, adhesive composition for the same, and display member comprising the same Download PDFInfo
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- CN111278944A CN111278944A CN201880069317.7A CN201880069317A CN111278944A CN 111278944 A CN111278944 A CN 111278944A CN 201880069317 A CN201880069317 A CN 201880069317A CN 111278944 A CN111278944 A CN 111278944A
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- adhesive film
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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
- 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
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal 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
- C09J7/00—Adhesives in the form of films or foils
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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
Abstract
The invention provides an adhesive film, an adhesive composition for the same, and a display member including the same. The adhesive film is formed from an adhesive composition comprising a urethane resin, an isocyanate curing agent, a multifunctional (meth) acrylate monomer, a photoinitiator, and a thermal initiator. The adhesive film has a peel strength ratio of 0.1 or less than 0.1 calculated by equation 1, an initial peel strength of 30 grams force/25 mm or more than 30 grams force/25 mm, and a maximum load of 1 kg or more than 1 kg at which the adhesive film does not generate particles or burrs due to scattering when the scattering property is evaluated.
Description
Technical Field
The present invention relates to an adhesive film, an adhesive composition for the same, and a display member comprising the same.
Background
An Organic Light Emitting Display (OLED) includes an OLED panel. The OLED panel is easily damaged by external impact. Especially during manufacturing or transportation, the OLED panel may be subjected to external impacts. Therefore, the OLED panel may deteriorate in reliability and lifetime thereof. As is known in the related art, an OLED panel may be encapsulated by an encapsulation layer including an organic layer and an inorganic layer. However, the encapsulation layer has a limitation in protecting the OLED panel from external impact, and there is a limitation in protecting the OLED panel when the OLED panel is transported without the encapsulation layer.
In general, a protective film coated with an adhesive film is used to protect the surface of the OLED panel from foreign substances or contaminants, or to prevent the OLED panel from being damaged by external impact during the manufacture or transportation of the OLED panel. Although the protective film coated with the adhesive film must be sufficiently attached to the OLED or the encapsulation layer, since the protective film is temporarily used, it is also required that the protective film be easily removed from the OLED panel or the encapsulation layer. In particular, when applied to OLED panels having high surface roughness and which may be damaged, it is important for the encapsulating layer to exhibit sufficient adhesion and re-peeling properties.
On the other hand, the protection film stacked on the OLED panel may perform a cutting process according to the size of the OLED panel. When the protective film has poor scattering properties, aggregates and uneven cut surfaces may be generated when the adhesive film is cut, thereby providing poor workability.
The background art of the present invention is disclosed in unexamined Japanese patent publication No. 2015-010192.
Disclosure of Invention
Technical problem
One aspect of the present invention provides an adhesive film that exhibits a high peel strength (peel strength) with respect to an OLED panel or an inorganic layer stacked on the OLED panel before Ultraviolet (UV) irradiation to protect the OLED panel, and exhibits a low peel strength with respect to the OLED or the inorganic layer after the UV irradiation to ensure good re-peelability.
Another aspect of the present invention provides an adhesive film that allows the peel strength to be adjusted according to the handling of a user.
Still another aspect of the present invention provides an adhesive film having high peel strength before ultraviolet irradiation and ensuring good results of evaluation of scattering properties before ultraviolet irradiation.
Yet another aspect of the present invention provides an adhesive film exhibiting good wettability with respect to an OLED panel or an organic/inorganic layer stacked on the OLED panel and low haze, thereby ensuring good processability.
Technical scheme
According to one embodiment of the present invention, there is provided an adhesive film formed of an adhesive composition including a urethane resin (urethane resin), an isocyanate curing agent (isocyanate curing agent), a polyfunctional (meth) acrylate monomer (polyfunctionality monomer), a photoinitiator, and a thermal initiator. The adhesive film has an initial peel strength of 30 grams force/25 millimeters or more and a peel strength ratio of 0.1 or less than 0.1 calculated by equation 1 below:
< equation 1>
Peel strength ratio of A/B
(wherein B is the initial peel strength (unit: g force/25 mm) at 25 ℃ at which the adhesive film is peeled from the glass plate, and A is the peel strength (unit: g force/25 mm) at 25 ℃ at which the adhesive film is peeled from the glass plate after ultraviolet irradiation).
When the scattering property is evaluated by the following method, the adhesive film may have a maximum load of 1 kg or more than 1 kg at which the adhesive film does not generate particles or burrs due to scattering:
< method for evaluating Scattering Property >
A sample was prepared by providing a stack of the adhesive film having a thickness of 75 micrometers and not subjected to ultraviolet irradiation and a polyethylene terephthalate film (SUS) having a thickness of 75 micrometers on a glass plate such that the adhesive film was placed at the uppermost side, and a maximum load that does not generate particles or burrs due to scattering of the adhesive film was measured on the sample when the adhesive film was scribed using a stainless steel (SUS) pen under the following conditions:
cross section and diameter of stainless pen: circular cross section, diameter 1 mm
Atmospheric temperature when drawn with a stainless pen: 23 deg.C
Drawing angle of a stainless pen: is 45 DEG relative to the surface of the adhesive film
Drawing speed of a stainless pen: 60 mm/min.
According to another aspect of the present invention, an adhesive composition includes 100 parts by weight of a urethane resin, 5 to 10 parts by weight of an isocyanate curing agent, 15 to 40 parts by weight of a multifunctional (meth) acrylate monomer, 0.1 to 2.0 parts by weight of a photoinitiator, and 0.1 to 10 parts by weight of a thermal initiator.
According to still another mode of the present invention, a display member includes the adhesive film according to the present invention.
Advantageous effects
The present invention provides an adhesive film that exhibits high peel strength with respect to an OLED panel or an inorganic layer stacked on the OLED panel before ultraviolet irradiation to protect the OLED panel, and exhibits low peel strength with respect to the OLED or the inorganic layer after ultraviolet irradiation to ensure good re-peelability.
The present invention provides an adhesive film that allows the peel strength to be adjusted according to the handling of the user.
The invention provides an adhesive film which has high peeling strength before ultraviolet irradiation and ensures good scattering property evaluation result before ultraviolet irradiation.
The present invention provides an adhesive film exhibiting good wettability and low haze with respect to an OLED panel or an organic/inorganic layer stacked on the OLED panel, thereby ensuring good processability.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily accomplish the present invention. It is to be understood that the present invention is not limited to the following examples, but may be embodied in various forms.
The term "(meth) acrylic-based" as used herein refers to acrylic-based and/or methacrylic-based.
The term "initial peel strength" of the adhesive film as used herein means the peel strength of the adhesive film not subjected to ultraviolet irradiation.
The term "post-peel strength" of the adhesive film as used herein means the peel strength of the adhesive film after ultraviolet irradiation.
Hereinafter, an adhesive film according to an embodiment of the present invention will be described.
The adhesive film according to the embodiment is formed of an adhesive composition including a urethane resin, an isocyanate curing agent, a multifunctional (meth) acrylate monomer, a photo initiator, and a thermal initiator, and having an initial peel strength of 30 grams force/25 mm or more and a peel strength ratio (ratio of a to B) of 0.1 or less than 0.1, preferably 0.08 or less than 0.05, more preferably 0.05 or less than 0.05.
< equation 1>
Peel strength ratio of A/B
(wherein B is the initial peel strength (unit: g force/25 mm) at 25 ℃ at which the adhesive film is peeled from the glass plate, and
a is the peel strength (unit: gram force/25 mm) of the adhesive film from the glass plate after UV irradiation at 25 ℃.
Herein, the peel strength refers to a value measured on an adhesive film at 25 ℃ when the adhesive film is peeled from an adherend (e.g., a glass plate or an inorganic layer) at a peeling speed of 2,400 mm/min at a peeling angle of 180 ° according to JISZ 2037. The peel strength can be measured with an adhesive film having a thickness of 5 to 300 micrometers, preferably 10 to 200 micrometers, more preferably 50 to 75 micrometers. Herein, "ultraviolet irradiation" means irradiation of the adhesive film with ultraviolet light at a wavelength of 395 nm and a flux (flux) of 300 mj/cm. The "ultraviolet irradiation" may be performed using a Light Emitting Diode (LED) lamp, a metal halogen lamp, or the like.
Within the above range of the peel strength ratio of the post peel strength to the initial peel strength, the adhesive film may be used as an adhesive type protective film. In one embodiment, the adhesive film may be attached to the OLED panel to protect the OLED panel. The adhesive film is attached to the OLED panel during the manufacture of the OLED, and then cut according to the size of the OLED, and then peeled off again. By satisfying the peel strength ratio, the adhesive film may exhibit high peel strength before ultraviolet irradiation to be attached to the OLED panel to protect the OLED panel, and may be easily peeled from the OLED panel without damaging the OLED due to reduction of the peel strength by ultraviolet irradiation after cutting.
The adhesive film can have an initial peel strength B of 30 grams force/25 millimeters or greater than 30 grams force/25 millimeters, such as 30 grams force/25 millimeters to 70 grams force/25 millimeters, such as 30 grams force/25 millimeters to 50 grams force/25 millimeters at 25 ℃. Within this range, the adhesive film is not peeled off from the OLED panel when the OLED panel is manufactured, thereby protecting the OLED panel. The adhesive film can have a peel strength a of 3.0 grams force/25 millimeters or less than 3.0 grams force/25 millimeters at 25 ℃ after ultraviolet irradiation. Within this range, the adhesive can be easily peeled off from the OLED panel without damaging the OLED panel, thereby increasing process yield.
The adhesive film may be cut according to the size of the OLED after being attached to the OLED panel. The adhesive film may have a maximum load of 1 kg or more than 1 kg, for example, 1 kg to 3 kg, at which the adhesive film does not generate particles or burrs due to scattering of the adhesive film, when the scattering property of the adhesive film is evaluated by the following method. Within this range, the adhesive film may provide a precise cut (clean cut) when cutting the adhesive film according to the size of the OLED without generating aggregates.
< method for evaluating Scattering Property >
A sample was prepared by providing a stack of the adhesive film having a thickness of 75 micrometers and not subjected to ultraviolet irradiation and a polyethylene terephthalate film having a thickness of 75 micrometers on a glass plate such that the adhesive film was placed at the uppermost side, and a maximum load, at which particles or burrs were not generated due to scattering of the adhesive film, was measured on the sample when the adhesive film was scribed using a stainless steel (SUS) pen under the following conditions:
cross section and diameter of stainless pen: circular cross section, diameter 1 mm
Atmospheric temperature when drawn with a stainless pen: 23 deg.C
Drawing angle of a stainless pen: is 45 DEG relative to the surface of the adhesive film
Drawing speed of a stainless pen: 60 mm/min.
The cling film can have a haze of less than 2%, such as 1.9%, or less than 1.9%. Within this range, the adhesive film allows an adherend such as an OLED panel to be clearly observed through the adhesive film during a cutting process, a pixel testing process, and the like after being attached to the OLED panel, thereby improving workability.
The stack of the adhesive film and the substrate film (e.g., polyethylene terephthalate film) can have a haze of less than 2%, such as 1.9%, or less than 1.9%. Within this range, the adhesive film allows an adherend such as an OLED panel to be clearly observed during a cutting process, a pixel testing process, and the like after being attached to the OLED panel, thereby improving workability.
The adhesive film may have a thickness of 25 to 100 microns. Within this range, the adhesive film may be used as an adhesive type protective film.
The adhesive film may be prepared by depositing the adhesive composition on a base film, followed by drying and aging. The adhesive composition may include 100 parts by weight of a urethane resin, 5 to 10 parts by weight of an isocyanate curing agent, 15 to 40 parts by weight of a multifunctional (meth) acrylate monomer, and the balance of a photo initiator and a thermal initiator. The base film may be a polyester film such as, but not limited to, a polyethylene terephthalate film. Herein, "drying" includes heat-treating the coating of the adhesive composition at 50 ℃ to 130 ℃ for 1minute to 10 minutes. In addition, "aging" means a process of leaving a dried coating of the adhesive composition at 23 ℃ to 30 ℃ and 40% Relative Humidity (RH) to 60% RH for 1 day to 7 days.
In the adhesive film, the polyfunctional (meth) acrylate monomer may be present in an amount of 5 to 50 wt%, preferably 12 to 35 wt%, more preferably 15 to 35 wt%. Within this range, the multifunctional (meth) acrylate monomer can ensure that the adhesive film has a high peel strength before ultraviolet irradiation and has good re-peelability by reducing the peel strength of the adhesive film after ultraviolet irradiation.
In the adhesive film, the photoinitiator may be present in an amount of 0.1 to 2.0 wt%, preferably 0.2 to 1.5 wt%. Within this range, the photoinitiator may cure the multifunctional (meth) acrylate monomer to provide good re-peelability by reducing the peel strength of the adhesive film upon ultraviolet irradiation of the adhesive film.
In the adhesive film, the thermal initiator may be present in an amount of 0.1 to 2.0 wt%, preferably 0.3 to 1.0 wt%. Within this range, the thermal initiator may improve the scattering property and wettability of the adhesive film.
Now, an adhesive composition according to one embodiment of the present invention will be described.
The adhesive composition according to an embodiment may include 100 parts by weight of a urethane resin, 5 to 10 parts by weight of an isocyanate curing agent, 15 to 40 parts by weight of a multifunctional (meth) acrylate monomer, and the balance of a photo initiator and a thermal initiator.
Within these ranges of the isocyanate curing agent and the polyfunctional (meth) acrylate monomer, the adhesive composition can exhibit good wettability to an adherend, good scattering properties (workability), high initial peel strength, and low peel strength after ultraviolet irradiation to ensure good removability. Upon drying of the adhesive composition, a part of the polyfunctional (meth) acrylate monomer reacts with the thermal initiator to improve the scattering property of the adhesive film, and upon aging of the adhesive composition, the urethane resin reacts with the isocyanate curing agent to improve the adhesion to the adherend by increasing the initial peel strength.
Specifically, within these content ranges of the multifunctional (meth) acrylate monomer and the isocyanate curing agent, the scattering property secured when the adhesive composition is dried is not affected during aging of the adhesive composition, thereby improving the scattering property of the adhesive film when the adhesive film is cut. In addition, within these content ranges of the multifunctional (meth) acrylate monomer and the isocyanate curing agent, a portion of the multifunctional (meth) acrylate monomer may react with the thermal initiator while allowing the remaining multifunctional (meth) acrylate monomer to react with the photo initiator, thereby improving all wettability, processability and re-peelability of the adhesive film.
The urethane resin may improve wettability of the adhesive film when the adhesive composition is dried. As described above, when the adhesive composition is dried, a portion of the multifunctional (meth) acrylate monomer is crosslinked by the thermal initiator, and the urethane resin may improve wettability of the adhesive film regardless of the crosslinking reaction between the multifunctional (meth) acrylate monomer and the thermal initiator. In addition, the urethane resin is reacted with the isocyanate curing agent to improve the initial peel strength of the adhesive film during aging of the adhesive composition. In addition, the urethane resin forms a semi-Interpenetrating Polymer Network (IPN) structure together with the cured product between the multifunctional (meth) acrylate monomer and the thermal initiator, thereby improving the scattering property (processability) of the adhesive film.
The urethane resin may be a non- (meth) acrylate-based resin having no (meth) acrylate group. The urethane resin may contain a hydroxyl group to react with the isocyanate curing agent.
The urethane resin may be prepared by reacting a di-or higher functional polyol with a di-or higher functional isocyanate. As a catalyst for promoting formation of a urethane bond when preparing a urethane resin, the urethane resin may further include a tin compound (e.g., dibutyltin dilaurate), an amine compound (e.g., dimethylcyclohexylamine) or triethylenediamine), and the like. Typical components such as surfactants, flame retardants, fillers, and pigments may also be added in the preparation of the urethane resin.
The polyol may include at least one of an aromatic polyol, an aliphatic polyol, and a cycloaliphatic polyol. Preferably, the polyol is an aliphatic polyol. The polyol may include at least one of a polyester polyol, a polycarbonate polyol, a polyolefin polyol, a polyester polyol, a polythioether polyol, a polysiloxane polyol, a polyacetal polyol, and a polyesteramide polyol. Preferably, the polyol comprises a mixture of a polyester polyol and a polyether polyol.
The polyfunctional isocyanate may include at least one of an aliphatic isocyanate, a cycloaliphatic isocyanate, and an aromatic isocyanate. Preferably, the polyfunctional isocyanate comprises an aliphatic isocyanate. Specifically, the polyfunctional isocyanate may include at least one of: hexamethylene diisocyanate (hexamethylene diisocyanate); toluene diisocyanates (tolumen diisocynates) including 2,4-toluene diisocyanate (2, 4-tolumen diisocynate), 2,6-toluene diisocyanate and the like (2, 6-tolumen diisocynate); 4,4'-methylene diphenyl diisocyanate (4,4' -methylene diphenyl diisocyanate); xylene diisocyanates (xylylene diisocyanates) including 1,3-xylene diisocyanate (1,3-xylene diisocyanate), 1,4-xylene diisocyanate (1,4-xylene diisocyanate), and the like; hydrogenated toluene diisocyanate (hydrogenated toluene diisocyanate); isophorone diisocyanate (isophorone diisocyanate); 1, 3-diisocyanatomethylcyclohexane (1, 3-bisthiocyanomethylcyclohexane); tetramethylxylylene diisocyanate (tetramethylxylylene diisocyanate); 1,5-naphthalene diisocyanate (1,5-naphthalene diisocyanate); 2,2,4-trimethylhexamethylene diisocyanate (2,2,4-trimethylhexamethylene diisocyanate); 2,4,4-trimethylhexamethylene diisocyanate (2,4,4-trimethylhexamethylene diisocyanate); trimethylolpropane toluene diisocyanate (trimethyolpropane diisocyanate) adducts, including trimethylolpropane/toluene diisocyanate trimer adducts; xylene diisocyanate adduct of trimethylolpropane; triphenylmethane triisocyanate (triphenylmethane triisocyanate); and methylene bis triisocyanate (methylene bis isocyanurate), but is not limited thereto. Preferably, the polyfunctional isocyanate comprises hexamethylene diisocyanate.
The polyfunctional isocyanate may be present such that the molar ratio of the total moles of isocyanate groups in the polyfunctional isocyanate to the total moles of hydroxyl groups in the polyol is in the range of 0.1 to 0.8, preferably 0.4 to 0.6. Within this range, the adhesive film formed from the adhesive composition may exhibit high transparency and a good balance between adhesive strength and removability.
The urethane resin may have a weight average molecular weight of 30,000 to 500,000, preferably 50,000 to 400,000, and a polydispersity index (polydispersity index) of 2 to 10, preferably 5 to 10. Within these ranges, the urethane resin can ensure an improvement in surface stability upon coating. The urethane resin may have a glass transition temperature of-80 ℃ to-20 ℃, preferably-80 ℃ to-40 ℃. Within this range, the urethane resin can ensure good adhesion to an adherend.
The isocyanate curing agent reacts with the urethane resin to adjust the initial peel strength of the adhesive film during aging of the adhesive composition. For example, the adhesive film can have an initial peel strength of 30 grams force/25 millimeters or greater, such as 30 grams force/25 millimeters to 70 grams force/25 millimeters, specifically 30 grams force/25 millimeters to 50 grams force/25 millimeters, when measured according to jis z2037 at a peel angle of 180 ° relative to the glass sheet. Within this range, the adhesive film can exhibit good adhesion to an adherend (e.g., an OLED panel) to protect the OLED panel.
The isocyanate curing agent may be present in an amount of 5 to 10 parts by weight, based on 100 parts by weight of the urethane resin. Within this range, the isocyanate curing agent does not affect the reaction between the multifunctional (meth) acrylate monomer and the thermal initiator when the adhesive composition is dried, and may react with the urethane resin to increase the initial peel strength when the adhesive composition is aged after the adhesive composition is dried.
The isocyanate curing agent may include a difunctional or higher functional isocyanate curing agent, such as a difunctional or a hexafunctional isocyanate curing agent. For example, the isocyanate curing agent may include hexamethylene diisocyanate; toluene diisocyanate including 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and the like; 4,4' -methylene diphenyl diisocyanate; xylene diisocyanate including 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, and the like; hydrogenating toluene diisocyanate; isophorone diisocyanate; 1,3-bis isocyanatomethylcyclohexane; tetramethyl xylene diisocyanate; 1,5-naphthalene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; trimethylolpropane toluene diisocyanate adducts, including trimethylolpropane/toluene diisocyanate trimer adducts; xylene diisocyanate adduct of trimethylolpropane; triphenylmethane triisocyanate; methylene bis triisocyanate, and the like.
Preferably, the isocyanate curing agent has an isocyanurate (isocyanurate) structure. In the adhesive composition including the isocyanate curing agent having an isocyanurate structure, the isocyanate curing agent may improve initial peel strength together with the urethane resin while allowing the formation of an optically clear coating. The isocyanate curing agent having an isocyanurate structure may be a trifunctional isocyanate curing agent including an aliphatic, aromatic or cycloaliphatic diisocyanate trimer adduct. For example, the isocyanate curing agent having an isocyanurate structure may be a hexamethylene diisocyanate trimer adduct.
The adhesive composition may include a multifunctional (meth) acrylate monomer.
The polyfunctional (meth) acrylate monomer may be present in an amount of 15 to 40 parts by weight, preferably 15 to 35 parts by weight, based on 100 parts by weight of the urethane resin. Within this range, a portion of the multifunctional (meth) acrylate monomer may be crosslinked by a thermal initiator when the adhesive composition is dried. The crosslinked reaction product forms a semi-IPN together with the urethane resin, thereby improving the workability of the adhesive film without whitening phenomenon. In addition, the remaining polyfunctional (meth) acrylate monomer is cured by the photoinitiator at the time of ultraviolet irradiation to reduce the peel strength after ultraviolet irradiation to the adhesive film, thereby enabling easy removal of the adhesive film from an adherend while improving the scattering property of the adhesive film.
A part of the multifunctional (meth) acrylate monomer reacts with the thermal initiator when the adhesive composition is dried, and the remaining multifunctional (meth) acrylate monomer reacts with the photo initiator when the adhesive composition is irradiated with ultraviolet rays, thereby improving the workability (scattering property) and re-peelability of the adhesive film. The multifunctional (meth) acrylate monomer may provide poor scattering properties and re-peelability due to a higher rate of crosslinking with the thermal initiator than with the multifunctional (meth) acrylate monomer.
The polyfunctional (meth) acrylate monomer may be a non-isocyanate-based monomer having no isocyanate group. The multifunctional (meth) acrylate monomer includes difunctional to hexafunctional (meth) acrylate monomers. Specifically, the polyfunctional (meth) acrylate monomer may include a bifunctional (meth) acrylate such as 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, dicyclopentanyl di (meth) acrylate, lactone-modified dicyclopentenyl di (meth) acrylate, and lactone-modified dicyclopentenyl di (meth) acrylate, Di (meth) acryloyloxyethyl isocyanurate (di (meth) acrylate), allylated cyclohexyl di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, dimethyldimethyldicyclopentane di (meth) acrylate, ethylene oxide-modified hexahydrophthalate di (meth) acrylate (ethylene oxide-modified hexahydrophthalic acid di (meth) acrylate), tricyclodecane dimethanol (meth) acrylate, neopentylglycol-modified trimethylolpropane di (meth) acrylate (methacrylic-modified acrylate (meth) acrylate), diamyl-acrylate (methacrylate), and bis (2-adamantyl) acrylate [ 2- (4-ethoxy) acrylate [ 9- (2-adamantyl) acrylate ], 9-bis [4- (2-bis [4- (2-acryloyloxylthoxy) phenyl ] fluoroene); trifunctional acrylates, 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, trifunctional urethane (meth) acrylate, and tris (meth) acryloxyethyl isocyanurate (meth) acrylate; tetrafunctional acrylates, such as diglycerin tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate; pentafunctional acrylates, such as dipentaerythritol penta (meth) acrylate; and hexafunctional acrylates such as dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and urethane (meth) acrylates (e.g., a reaction product of an isocyanate monomer and trimethylolpropane tri (meth) acrylate), but are not limited thereto. Preferably, the multifunctional (meth) acrylate monomer includes a hexafunctional (meth) acrylate to provide good scattering properties and re-peelability.
The thermal initiator reacts with a portion of the multifunctional (meth) acrylate monomer to improve the scattering properties of the cling film. The thermal initiator may cure a portion of the multifunctional (meth) acrylate monomer during the drying of the adhesive composition after coating. Herein, "drying" may include heat-treating the coating of the adhesive composition at 50 ℃ to 130 ℃ for 1minute to 10 minutes. Thus, the thermal initiator may have a reaction initiation temperature of 50 ℃ to 130 ℃. The thermal initiator may have a half-life temperature of 1minute of 70 ℃ to 160 ℃, preferably 90 ℃ to 130 ℃. Within these ranges of the reaction initiation temperature and the half-life temperature of 1minute, the multifunctional (meth) acrylate monomer may be partially cured instead of fully cured, thereby improving the scattering property of the adhesive film while reducing the peel strength of the adhesive film after uv irradiation to improve the re-peelability of the adhesive film. The "reaction initiation temperature" and "half-life temperature for 1 minute" (half-life temperature for 1minute) can be measured by typical methods known in the art or by reference to the catalog of commercially available thermal starters.
The thermal initiator may include a peroxy initiator such as diisopropylperoxy dicarbonate, bis (2-ethylhexyl) peroxy dicarbonate, bis (4-t-butylcyclohexyl) peroxy dicarbonate, bis-sec-butylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxy pivalate, t-butylperoxyneovalerate, dilauroyl peroxide, bis-n-octyl peroxy 1, 3-tetramethylhexyl peroxy-1, 3-tetramethylhexyl peroxyacetate, 1-3-tetramethylhexyl peroxyacetate, 1,3, 3-tetramethylperoxyxy-2-ethylhexoate), bis (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxybutyrate, and the like. In particular, the thermal initiator may be bis (4-t-butylcyclohexyl) peroxydicarbonate.
The thermal initiator may be present in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.5 to 1.5 parts by weight, based on 100 parts by weight of the urethane resin. Within this range, the thermal initiator may react with a portion of the multifunctional (meth) acrylate monomer to form a crosslinked structure, thereby improving the scattering property of the adhesive film while reducing the haze of the adhesive film.
The photoinitiator may react with the remaining multifunctional (meth) acrylate monomer to improve the re-peelability of the adhesive film by reducing the peel strength of the adhesive film after ultraviolet irradiation.
The photoinitiator initiates the curing reaction by ultraviolet irradiation and may include an initiator capable of functioning at an absorption wavelength of 300 to 450 nanometers. Within this range, the photoinitiator can cure the adhesive layer and does not damage the molecular structure of the OLED device when applied to the OLED panel. For example, the photoinitiator may include benzoin, acetophenone, hydroxyketone, aminoketone, and phosphine oxide based photoinitiators, preferably phosphine oxide based photoinitiators.
The photoinitiator may be present in an amount of 0.1 to 2.0 parts by weight, preferably 0.2 to 1.5 parts by weight, based on 100 parts by weight of the urethane resin. Within this range, the photoinitiator may react with the remaining multifunctional (meth) acrylate monomer to form a crosslinked structure, thereby improving the re-peelability of the adhesive film by reducing the peel strength of the adhesive film after ultraviolet irradiation.
The adhesive composition may be a solvent-free composition, or may further include a solvent to ensure deposition of the adhesive composition. The solvent may include an organic solvent such as toluene, but is not limited thereto.
The adhesive composition may further comprise typical additives. The additives may include, but are not limited to, pigments, antioxidants, polymerization inhibitors, ultraviolet absorbers, and surfactants. In the adhesive composition, the additive may be present in an amount of 10 parts by weight or less than 10 parts by weight, based on 100 parts by weight of the urethane resin. Within this content range, the additive may exhibit its inherent effects without affecting wettability, scattering property and re-peelability of the adhesive film.
Next, a display member according to an embodiment of the present invention will be explained.
The display member may include a stack structure in which the adhesive film according to the present invention is stacked on the release film. The release film may include a polyester film, such as a polyethylene terephthalate film, but is not limited thereto. The display member may further include another release film and a silicone release layer on the adhesive film to prevent the adhesive film from being contaminated by contaminants.
The invention will be explained in more detail below with reference to some examples. It should be understood that these examples are provided for illustrative purposes only and should not be construed as limiting the invention in any way.
Preparation example: preparation of urethane resin
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer and a dropping funnel, 50 parts by weight of a polyester polyol (P-1010, Coloray Co., Ltd.) and 850 parts by weight of a polyester polyol (G700, number average molecular weight: 700, number of functional groups: 3, Adeka Co., Ltd.) were placed. Hexamethylene diisocyanate was added thereto until the molar ratio (total moles of NCO in hexamethylene diisocyanate)/(total moles of OH of polyester polyol and polyester polyol) became 0.5, and 650 parts by weight of toluene and 0.1 part by weight of a catalyst (dibutyl tin dilaurate, DBTDL) were further added thereto, and then the temperature of the flask was slowly raised to 90 ℃ and reacted for 2 hours. After confirming the decrease in the content of the remaining NCO by an Infrared (IR) spectrometer, the reaction was completed by cooling the resultant material, thereby obtaining a solution containing a urethane resin. In solution, the urethane resin had a solids content of 60%, a weight average molecular weight (Mw) of 150,000, a polydispersity index of 6, and a glass transition temperature of about-60 ℃.
The details of the components used in the examples and comparative examples are as follows:
(A) urethane resin: urethane resin prepared in preparation example
(B) Isocyanate curing agent: SC-100I (isocyanurate of hexamethylene diisocyanate trimer) (Samwha Paint Co., Ltd.)
(C) Multifunctional (meth) acrylate monomer: dipentaerythritol hexaacrylate (DPHA) (DPHA LT, SK Cytec Co., Ltd.)
(c) Multifunctional (meth) acrylate monomer: 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate, 2-HEMA) (2-HEMA, Sigma Aldrich)
(D) Photo initiator: daluodol's capsule
TPO (Ciba Chemical Co., Ltd.)
(E) Thermal initiator: palol (Peroyl)
TCP (NOF Co., Ltd., NOF, Ltd.), reaction initiation temperature 130 ℃ C., half-life temperature of 1minute 92 ℃ C.)
Example 1
An adhesive composition was prepared by: 100 parts by weight of urethane resin, 8.0 parts by weight of isocyanate curing agent, 20.0 parts by weight of polyfunctional (meth) acrylate monomer, 1.2 parts by weight of photoinitiator, and 0.5 part by weight of thermal initiator were mixed with 5.0 parts by weight of toluene, followed by stirring for 30 minutes.
An adhesive layer having a thickness of 75 μm was formed on a polyethylene terephthalate (PET) film (thickness: 75 μm, SKC corporation) in the following manner: the prepared adhesive composition was coated on a PET film and then dried at 130 ℃ for 4 minutes. A stacked structure of an adhesive layer 75 micrometers thick and a release film 25 micrometers thick was obtained by bonding a release film 25 micrometers thick (silicone release film) to the adhesive layer and then aging at room temperature for 1 week.
Examples 2 to 7
Each stacked structure was obtained in the same manner as in example 1, except that the content of the components of the adhesive composition was changed as shown in table 1 (unit: part by weight).
Comparative examples 1 to 7
Each stacked structure was obtained in the same manner as in example 1, except that the content of the components of the adhesive composition was changed as shown in table 2 (unit: part by weight).
The adhesive films prepared in examples and comparative examples were evaluated for the following properties, and the evaluation results are shown in tables 1 and 2.
(1) Initial peel strength: each of the stacked structures prepared in examples and comparative examples was cut into a size of 25 mm × 100 mm (width × length) to prepare a sample. The silicone release layer was removed from the sample at 23 ℃ and 50% RH to expose the adhesive film. In the case of attaching the PET film to the adhesive film, the adhesive film was bonded to an alkali-free glass plate, pressed by a 2-kilogram roller, and left at 23 ℃ and 50% RH for 72 hours. Then, the peel strength was measured while separating the adhesive film from the alkali-free glass plate at 25 ℃ and at a peel speed of 2,400 mm/min and a peel angle of 180 ° according to jis z2037 using a tensile tester (texture analyzer, TA Industry).
(2) Peel strength after ultraviolet irradiation (post peel strength): each of the stacked structures prepared in examples and comparative examples was cut into a size of 25 mm × 100 mm (width × length) to prepare a sample. The sample was illuminated with light from an LED lamp at a wavelength of 395 nm and a flux of 300 millijoules per square centimeter. The peel strength was measured in the same manner as in (1). That is, the peel strength was measured when the adhesive film was separated from the alkali-free glass plate at 25 ℃ and at a peel speed of 2,400 mm/min and a peel angle of 180 ° according to jis z2037 using a tensile tester (texture analyzer, TA industrial company).
(3) Wettability (adhesion): each of the stacked structures prepared in examples and comparative examples was cut into a size of 25 mm × 100 mm (width × length) to prepare a sample. After leaving the sample at 23 ℃ and 50% RH for 30 minutes, the silicone release layer was removed from the sample to expose the adhesive film. Herein, the structure in which the adhesive film is attached to the PET film will be referred to as an adhesive tape. After the center of the adhesive film exposed by gripping both ends of the adhesive tape with hands contacts the glass plate, the self-adhesive tape is taken off the hands. The wettability of the adhesive tape to the glass plate was then evaluated by measuring the time for which the entire adhesive tape was in intimate contact with the glass plate due to contact between the center of the adhesive tape and the glass plate. The shorter the time that the entire adhesive tape is in intimate contact with the glass sheet indicates the better the affinity of the adhesive tape for the glass sheet and thus means that the adhesive tape can more readily protect the display and the glass sheet in the process of making the display.
○ time to close contact is less than 3 seconds (excellent wettability)
△ time to close contact is 3 seconds to less than 5 seconds (good wettability)
X: the time of close contact is 5 seconds or longer than 5 seconds (unusable)
(4) Scattering properties (processability): each of the stacked structures prepared in examples and comparative examples was cut into a size of 25 mm × 100 mm (width × length) to prepare a sample. The silicone release layer was removed from the sample at 23 ℃ and 50% RH to provide an adhesive tape with an adhesive film formed on the PET film. The adhesive tape was placed on the glass plate so that the adhesive film was placed at the uppermost side. The maximum load that does not generate particles or burrs due to scattering of the adhesive film was measured on the sample when the surface of the adhesive film was scratched using a stainless pen under the following conditions. Higher loading indicates better scattering properties.
Cross section and diameter of stainless pen: circular cross section, diameter 1 mm
Atmospheric temperature when drawn with a stainless pen: 23 deg.C
Drawing angle of a stainless pen: is 45 DEG relative to the surface of the adhesive film
Drawing speed of a stainless pen: 60 mm/min
(5) Haze: samples were prepared by removing the silicone release layer from the stacked structures prepared in the examples and comparative examples. The haze of the sample was measured using NDH2000 (Nippon Denshoku co., Ltd.)).
TABLE 1
TABLE 2
As shown in table 1, the adhesive film according to the present invention exhibited good properties in terms of initial peel strength and wettability. In addition, the adhesive film according to the present invention has a low peel strength ratio calculated by equation 1, and thus has good re-peelability, good scattering properties, and low haze. Therefore, the adhesive film according to the present invention can be used as an adhesive type protective layer of an OLED panel.
In contrast, as shown in table 2, the adhesive film of comparative example 5 prepared without using the multifunctional acrylate monomer and the adhesive film of comparative example 6 prepared without using the thermal initiator had poor scattering properties. The adhesive film of comparative example 7 prepared without using a photoinitiator had a high peel strength ratio calculated by equation 1, and thus had poor re-peelability. In addition, the adhesive films of comparative examples 1 to 4 did not satisfy the peel strength ratio of the present invention or exhibited poor scattering properties.
It is to be understood that various modifications, alterations, adaptations, and equivalent embodiments may occur to one skilled in the art without departing from the spirit and scope of the present invention.
Claims (15)
1. An adhesive film formed of an adhesive composition comprising a urethane resin, an isocyanate curing agent, a polyfunctional (meth) acrylate monomer, a photo initiator and a thermal initiator,
the adhesive film has an initial peel strength of 30 grams force/25 millimeters or more and a peel strength ratio of 0.1 or less than 0.1 calculated by equation 1 below:
< equation 1>
The peel strength ratio is a/B,
wherein B is the initial peel strength (unit: gram force/25 mm) of the adhesive film peeled from the glass plate at 25 ℃, and
a is the peel strength (unit: g force/25 mm) of the adhesive film peeled from the glass plate after ultraviolet irradiation at 25 ℃,
the adhesive film has a maximum load of 1 kg or more than 1 kg at which the adhesive film does not generate particles or burrs due to scattering when the scattering property is evaluated by the following method:
a sample was prepared by providing a stack of the adhesive film having a thickness of 75 micrometers and not subjected to ultraviolet irradiation and a polyethylene terephthalate film having a thickness of 75 micrometers on a glass plate such that the adhesive film was placed at the uppermost side, and the maximum load of particles or burrs not generated due to scattering of the adhesive film was measured on the sample when the adhesive film was scribed using a stainless pen under the following conditions:
cross section and diameter of stainless pen: circular cross section, diameter 1 mm
Atmospheric temperature when drawn with a stainless pen: 23 deg.C
Drawing angle of a stainless pen: is 45 DEG relative to the surface of the adhesive film
Drawing speed of a stainless pen: 60 mm/min.
2. The adhesive film of claim 1, wherein B is 30 grams force/25 millimeters or greater than 30 grams force/25 millimeters and a is 3.0 grams force/25 millimeters or less than 3.0 grams force/25 millimeters.
3. The adhesive film of claim 1, wherein the adhesive film has a haze of less than 2%.
4. The adhesive film of claim 1, wherein the adhesive film comprises 5 to 50 wt% of the multifunctional (meth) acrylate monomer and 0.1 to 2.0 wt% of the photoinitiator.
5. The adhesive film of claim 1, wherein the thermal initiator has a reaction initiation temperature of 50 ℃ to 130 ℃ and a half-life temperature of 70 ℃ to 160 ℃ for 1 minute.
6. The adhesive film of claim 1, wherein the thermal initiator comprises a peroxy-based thermal initiator, and the thermal initiator is present in the adhesive film at a level of 0.1 wt.% to 2.0 wt.%.
7. The adhesive film of claim 1, wherein the urethane resin comprises a non- (meth) acrylate urethane resin.
8. The tack film of claim 1, wherein the isocyanate curing agent comprises an isocyanurate-type isocyanate curing agent.
9. The adhesive film of claim 1, wherein a portion of the multifunctional (meth) acrylate monomer is crosslinked by the thermal initiator.
10. The adhesive film of claim 1, wherein the adhesive composition comprises 100 parts by weight of the urethane resin, 5 to 10 parts by weight of the isocyanate curing agent, 15 to 40 parts by weight of the multifunctional (meth) acrylate monomer, 0.1 to 2.0 parts by weight of the photo initiator, and 0.1 to 10 parts by weight of the thermal initiator.
11. An adhesive composition comprising: 100 parts by weight of urethane resin; 5 to 10 parts by weight of an isocyanate curing agent; 15 to 40 parts by weight of a multifunctional (meth) acrylate monomer; 0.1 to 2.0 parts by weight of a photoinitiator; and 0.1 to 10 parts by weight of a thermal initiator.
12. The adhesive composition of claim 11, wherein the urethane resin comprises a non- (meth) acrylate urethane resin.
13. The adhesive composition of claim 11, wherein the isocyanate curing agent comprises an isocyanurate-type isocyanate curing agent.
14. The adhesive composition of claim 11, wherein the thermal initiator has a reaction initiation temperature of 50 ℃ to 130 ℃ and a half-life temperature of 70 ℃ to 160 ℃ for 1 minute.
15. A display member comprising the adhesive film according to any one of claims 1 to 10.
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| KR10-2017-0111193 | 2017-08-31 | ||
| KR1020170111193A KR102126046B1 (en) | 2017-08-31 | 2017-08-31 | Adhesive film, adhesive composition for the same and display member comprising the same |
| PCT/KR2018/009396 WO2019045332A2 (en) | 2017-08-31 | 2018-08-16 | Adhesive film, adhesive composition therefor and display member comprising same |
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| CN111278944A true CN111278944A (en) | 2020-06-12 |
| CN111278944B CN111278944B (en) | 2022-04-12 |
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| KR102347872B1 (en) * | 2019-11-21 | 2022-01-06 | 주식회사 엘지화학 | Surface protecting film |
| KR20210074014A (en) * | 2019-12-11 | 2021-06-21 | 주식회사 엘지화학 | Surface protecting film for a optical component |
| CN114430770B (en) * | 2020-03-24 | 2023-08-29 | 株式会社Lg化学 | Surface protective film |
| KR20230157749A (en) | 2022-05-10 | 2023-11-17 | 충남대학교산학협력단 | Ultra-low adhesion and low-residue temporary protective film to protect display devices |
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| Publication number | Publication date |
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| KR20190025190A (en) | 2019-03-11 |
| TW201920547A (en) | 2019-06-01 |
| TWI675902B (en) | 2019-11-01 |
| WO2019045332A2 (en) | 2019-03-07 |
| CN111278944B (en) | 2022-04-12 |
| WO2019045332A3 (en) | 2019-04-18 |
| KR102126046B1 (en) | 2020-06-24 |
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