CN116023867A - Laminate, hard coat film comprising same, and window and image display device using same - Google Patents
Laminate, hard coat film comprising same, and window and image display device using same Download PDFInfo
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- CN116023867A CN116023867A CN202211254338.0A CN202211254338A CN116023867A CN 116023867 A CN116023867 A CN 116023867A CN 202211254338 A CN202211254338 A CN 202211254338A CN 116023867 A CN116023867 A CN 116023867A
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Abstract
The present invention provides a laminate comprising a transparent polyimide base layer and an easy-to-adhere layer formed on at least one surface of the base layer and formed of a cured product of an easy-to-adhere composition, wherein the easy-to-adhere layer does not contain a C-F bond on the surface, and a hard coat film comprising the laminate is excellent in adhesion, solvent resistance and bendability, and the contact angle of the easy-to-adhere layer after normal pressure plasma treatment is 35 DEG or less, and a window and an image display device using the same.
Description
Technical Field
The present invention relates to a laminate comprising a transparent polyimide base material layer and an easy-to-adhere layer, a hard coat film comprising the laminate, and a window and an image display device using the same.
Background
In recent years, thinning and flexibility of image display devices such as liquid crystal display (liquid crystal display: LCD) devices and organic light emitting display (organic light emitting display: OLED) devices have been continued. As such, the above-described image display apparatus is widely applied to various smart devices (smart devices) characterized by portability, from smart phones (smart phones), tablet PCs (tablet PCs), to various wearable devices (wearable devices).
For this reason, studies have been made on plastic films for optical use which can replace window films made of conventional tempered glass materials. The plastic film for optical use may contain, for example, a resin material such as polyethylene terephthalate (PET), polyether sulfone (PES), polyethylene naphthalate (PEN), polyacrylate (PAR), polycarbonate (PC), polyimide (PI), or the like. Among them, polyimide has excellent physical properties such as excellent mechanical properties, chemical resistance, high heat resistance, and electrical insulation properties, and is therefore used as a heat resistant film for electric/electronic use, a liquid crystal alignment film, a material for semiconductors, a material for molded parts, an adhesive, and the like.
However, such polyimide films have a characteristic of absorbing light in a short wavelength region by formation of an intramolecular charge transfer complex (Charge Transfer Complex) and thus exhibiting a characteristic yellow light. Such a high Yellowness (YI) not only reduces the transmittance but also causes a problem of distortion of the color inherent to the display, and thus is difficult to use as an outermost film for the display.
Therefore, the polymer film is transparent and has durability against foldingIt is required to develop a transparent polyimide base material film in which the yellow color of the conventional yellow polyimide base film is suppressed. In order to produce such a transparent polyimide base film having suppressed yellow color, it is known that CF is contained 1 、CF 2 Or CF (CF) 3 And a technique of introducing a substituent of a C-F bond into a substrate in an equal volume. However, this case has an advantage that the yellow color of the polyimide film can be suppressed and the transparency can be ensured, but has a problem that the bond energy of the c—f bond is large and the c—f bond is not easily decomposed, and the polyimide film has an F element with a large contact angle and is not suitable for bonding to other substrates.
In this regard, korean registered patent publication No. 10-0601308 discloses a method of performing normal pressure plasma treatment on the surface of a polyimide film, which realizes excellent adhesion characteristics with metal, and japanese registered patent publication No. 10-2019-0081823 provides a polyimide substrate which is excellent in curling characteristics and impact resistance by heat curing treatment, thereby being effectively used as an exterior substrate of a flexible electronic device, and a display substrate module including the same.
However, in the case of the conventional polyimide-based substrate film, there is a problem that the yellow color is not sufficiently suppressed or the contact angle is not sufficiently lowered, and the peeling phenomenon between substrates may occur.
Therefore, in practice, as a transparent polyimide base material in which yellow color in a yellow polyimide base film is suppressed, development of a hard coat film which ensures a sufficiently low contact angle even when plasma treatment is performed at the time of bonding with another base material, is excellent in interfacial adhesion at the time of bonding with another base material or a panel, and has appropriate durability for realizing flexible characteristics has been demanded.
Prior art literature
Patent literature
Patent document 1: korean registered patent publication No. 10-0601308
Patent document 2: korean laid-open patent publication No. 10-2019-0081823
Disclosure of Invention
Problems to be solved
In order to solve the above problems, an object of the present invention is to provide a laminate for a hard coating film, which has excellent adhesion, solvent resistance and bendability, and has a contact angle of 35 ° or less on the surface after normal pressure plasma treatment.
Another object of the present invention is to provide a hard coat film comprising the above laminate, and a window and an image display device to which the hard coat film is applied.
However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.
Means for solving the problems
In order to achieve the above technical object, the present invention relates to a laminate comprising a transparent polyimide base material layer and an easy-to-adhere layer formed on at least one surface of the base material layer and formed of a cured product of an easy-to-adhere composition, wherein the easy-to-adhere layer does not contain a substituent containing a c—f bond on the surface.
The present invention relates to a laminate characterized in that the contact angle of the adhesive layer after normal pressure plasma treatment is 35 DEG or less.
The present invention relates to a laminate, wherein the thickness of the adhesive layer is 40nm to 3 μm.
The present invention relates to a laminate, wherein the adhesive composition contains at least one or more of a photopolymerizable compound, a solvent and an initiator.
The present invention relates to a laminate characterized in that the photopolymerizable compound contains at least one or more selected from the group consisting of a polyfunctional acrylate monomer and a polyfunctional acrylate oligomer which do not dissolve the transparent polyimide-based substrate.
The present invention relates to a laminate, wherein the adhesive composition further comprises an additive.
The present invention relates to a laminate wherein the above-mentioned C-F bond is C-F X The bond represented, x is 1 to 3.
The present invention relates to a laminate for a hard coat film.
The present invention also relates to a hard coat film comprising a hard coat layer formed on a surface of the base material layer different from the easy-to-adhere layer.
Furthermore, the present invention relates to a hard coat film for a flexible display.
In addition, the present invention relates to a window comprising the above hard coat film.
In addition, the invention relates to an image display device which comprises the window.
Effects of the invention
The laminate of the present invention and the hard coat film comprising the same exhibit the following characteristics: the adhesive layer has excellent adhesion, solvent resistance and flexibility, and the contact angle of the adhesive layer after normal pressure plasma treatment is less than 35 degrees.
Therefore, the image display device including the laminate of the present invention exhibits improved mechanical reliability and flexibility, has excellent durability for a hard coat film for a flexible display, and can greatly improve the process speed.
Drawings
Fig. 1 schematically illustrates a cross-sectional view of a hard coat film including a laminate for explaining an embodiment of the present invention.
Fig. 2 schematically illustrates a structure of an XPS device according to an embodiment of the present invention.
Symbol description
100: hard coat film 110: easy-to-adhere layer
120: substrate layer 130: hard coat layer
200: XPS device 210: laminate sample
221: x-ray 222: detector for detecting a target object
Detailed Description
The present invention relates to a laminate comprising a transparent polyimide-based substrate layer and an easy-to-adhere layer formed on at least one surface of the substrate layer and containing no C-F bond on the surface thereof, the laminate being suitable for a hard coat film of a flexible display, and a window and an image display device using the hard coat film.
Hereinafter, preferred embodiments of the present invention will be described in detail.
< laminate >
The laminate of the present invention includes an easy-to-adhere layer 110 on one side of a transparent polyimide base material layer 120. Fig. 1 shows a hard coat film comprising a laminate according to an embodiment of the present invention, and as illustrated in fig. 1, the laminate according to the present invention may have a structure in which an easy-to-adhere layer 110 is formed on the opposite surface of a base material layer 120 on which a hard coat layer 130 is laminated.
The above-mentioned easily adhesive layer of the laminate of the present invention is characterized in that the surface does not contain a C-F bond. In the present invention, the term "surface does not include a C-F bond" means that the surface does not include a substituent containing a C-F bond, and the meaning of the term "surface element content" when measured may mean that the surface element does not include an F element. The term "not including" is intended to include a concept which does not substantially include, and means that the content is 0.5% or less based on 100% by weight of the total element content measured on the surface of the easy-to-adhere layer.
In the present invention, the total element measured on the surface of the easy-to-adhere layer means an element that can be measured by a known device for measuring the element content of the surface, and as an example, means an element that can be measured by an XPS device or the like, but is not limited thereto.
The above-mentioned C-F bond is formed from C-F X The bond represented, x, may be 1 to 3. For example, by C-F X The bond represented may be CF 1 、CF 2 Or CF (CF) 3 The substituents containing the above C-F bond include-CH 2 F 1 、-CHF 2 、-CF 3 And the like, but is not limited thereto.
The laminate of the present invention has an angle of contact of 35 ° or less with respect to the adhesive layer after normal pressure plasma treatment, and in this case, has an advantage of excellent durability against external stimuli such as repeated folding and the like and less tendency to cause peeling phenomenon when used by being attached to other substrates or panels.
The laminate of the present invention can be used for a hard coat film.
Substrate layer
The base material layer 120 may be a polyimide base material layer, preferably a transparent polyimide base material layer, for supporting the easy-to-be-described adhesive layer 110 and other base materials or panels instead of the conventional glass substrate.
In the present invention, the term "transparent" means that the transmittance of visible light is 70% or more or 80% or more.
Specifically, the polyimide base film used as the base layer is a polymer film which is transparent and has durability against folding, and a transparent polyimide base film in which yellow is suppressed from the conventional yellow polyimide base film can be used.
In the case of a transparent polyimide film in which yellow is suppressed, there is a considerable part of c—f bonds, and therefore there is a problem in that the water contact angle is not greatly reduced after plasma treatment. During plasma treatment, the c—c bond having a bond energy of 284.8eV is separated and reacts with oxygen radicals or the like to form a bond such as c— O, C = O, COOH, whereby the surface is converted to hydrophilicity, and the water contact angle is lowered. However, the C-F bond having a bond energy of up to 290eV or more may cause a problem that it is not easy to obtain a sufficiently low contact angle because the plasma treatment efficiency is relatively low, and a high ratio of C-F bonds is maintained even after the plasma treatment.
If the contact angle is not sufficiently reduced, there is a problem that when the adhesive or the optical adhesive film (OCA) adheres to another substrate or panel and is subjected to durability evaluation such as repeated folding, the interfacial adhesion force is insufficient and peeling phenomenon occurs.
Accordingly, the present invention solves the problems of such a transparent polyimide-based substrate layer by including an easy-to-adhere layer, which will be described later, on one surface of the substrate layer. Specifically, the transparent polyimide-based substrate layer of the present invention contains a specific easy-to-adhere layer on one surface and contains no substituent group containing a c—f bond on the surface, and thus has excellent durability and can exhibit a sufficiently low contact angle after normal pressure plasma treatment.
Easy-to-adhere layer
The easy-to-adhere layer 110 may be formed by applying an easy-to-adhere composition to one surface of the transparent polyimide base material layer 120, and then irradiating the composition with ultraviolet light to cure the composition. The above-mentioned adhesive composition contains at least one of an adhesive compound, a solvent and an initiator, and may further contain an additive.
In this case, the method of applying the adhesive composition is not particularly limited as long as it can be applied in the technical field of the present technology, and for example, a bar coating method, a doctor blade coating method, a roll coating method, a blade coating method, a die coating method, a micro gravure coating method, a corner bead coating method, a slit die coating method, a lip die coating method, a solution casting method, and the like can be used.
The thickness of the above-mentioned easy-to-adhere layer is 40nm to 3 μm, preferably 50nm to 1 μm, which is preferable from the viewpoints of adhesion and durability. If the thickness is less than 40nm, the C-F bond of the substrate cannot be sufficiently prevented, and there is a possibility that the contact angle is not significantly reduced, and if the thickness is more than 3. Mu.m, there is a concern that the flexibility is reduced and internal cracks are generated at the time of folding.
The above-mentioned easily adhesive compound is a compound capable of photopolymerization, and is not particularly limited as long as it does not have a substituent group containing a c—f bond, and may contain a multifunctional acrylate monomer, a multifunctional acrylate oligomer, and the like.
The polyfunctional acrylate monomer is preferably not dissolved in the transparent polyimide base material, because when the transparent polyimide base material is dissolved, the base material component may be mixed into the easy-to-adhere layer, and the F concentration on the surface of the easy-to-adhere layer may be increased.
The above-mentioned polyfunctional acrylate monomer may be a photocurable polyfunctional acrylate monomer, and specifically, examples thereof include: acrylates or methacrylates having substituents such as methyl, ethyl, propyl, butyl, pentyl, hexyl, pentyl, 2-ethylhexyl, octyl, nonyl, dodecyl, isodecyl, lauryl, cetyl, cyclohexyl, benzyl, methoxyethyl, ethoxyethyl, butoxyethyl, phenoxyethyl, allyl, methallyl, glycidyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-chloro-2-hydroxypropyl, dimethylaminohexyl, diethylaminohexyl, isobornyl, and the like; and multifunctional acrylates and methacrylates such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, tripropylene glycol, butanediol, tetramethylene glycol, hexamethyleneglycol, neopentyl glycol, butanediol, hexanediol, trimethylolpropane, pentaerythritol, and dipentaerythritol, and derivatives thereof.
The photocurable polyfunctional acrylate monomer is not particularly limited as long as it is generally used in the art, and among them, polyfunctional (urethane) acrylate is more preferable. The above-mentioned polyfunctional acrylate monomer is a monomer having 3 to 10 functional groups, which is preferable from the viewpoint of forming a crosslinked structure layer. Monomers having 1 or 2 functional groups may also be used in combination therewith.
The above-mentioned multifunctional acrylate oligomer may be a photocurable multifunctional acrylate oligomer, and epoxy (meth) acrylate, urethane (meth) acrylate, polyhedral oligomeric silsesquioxane (meth) acrylate, or the like is usually used, and one or more kinds may be selected and used. The above-mentioned multifunctional acrylate oligomer is a monomer having 3 to 18 functional groups, which is preferable in view of forming a crosslinked structural layer. Oligomers of 1 or 2 functional groups may also be used in combination therewith.
The content of the easy-to-adhere compound is not particularly limited, but is preferably 1 to 20 parts by weight based on 100 parts by weight of the entire easy-to-adhere composition. When the content is less than 1 part by weight, sufficient hardness improvement is not easily achieved, and when the content is more than 20 parts by weight, a problem of difficulty in coating a film having a thickness of 1 μm or less may occur.
The solvent serves to mix the adhesive compound with an initiator, an additive, or the like, and is not particularly limited as long as the viscosity of the composition can be kept low and film coating can be achieved. In particular, a poor solvent in which the transparent polyimide base material is not easily dissolved is preferable, so that the transparent polyimide component does not swell or dissolve due to the solvent and moves to the surface of the adhesion-facilitating compound layer when the transparent polyimide base material is coated thereon.
As the poor solvent in which the transparent polyimide-based substrate is not easily dissolved, typically, alcohol-based solvents such as methanol, ethanol, isopropanol, butanol, methyl cellosolve, and ethyl cellosolve can be preferably used; ether systems such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and propylene glycol monomethyl ether; and the like, the above-exemplified solvents may be used each alone or in combination of two or more. Among these, an alcohol-based solvent is particularly preferable, and isopropyl alcohol is particularly most preferable, because not only the coating property of the composition for forming an adhesive layer can be improved due to low surface tension, but also the above-mentioned mixing of the base material component into the adhesive layer can be minimized due to one of the solvents having the lowest solubility of the polyimide component.
In order to secure adhesion between the adhesion-promoting compound and the transparent polyimide base material, a mixed solvent in which a good solvent in which the transparent polyimide base material is easily dissolved is mixed with a poor solvent may be used. The good solvent and the poor solvent may be appropriately selected according to the material of the transparent film. As good solvents in which the transparent polyimide base material is easily dissolved, ketone solvents such as methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, propyl acetate, n-butyl acetate, t-butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; etc.
Finally, the composition in which the mixing ratio and the content of the C-F bond are optimized so that the level of the C-F bond is not detected on the surface of the adhesive layer after the application by mixing the solvents can be used without limitation.
The content of such a solvent is preferably 10 to 98 parts by weight, more preferably 20 to 85 parts by weight, relative to 100 parts by weight of the entire adhesive composition. If the content of the solvent is less than 20 parts by weight, not only the viscosity is high and the handleability is lowered, but also the adhesion may be lowered. On the other hand, in the case of more than 98 parts by weight, there is a problem in that the time required in the drying process is much, the economical efficiency is deteriorated, and Haze (Haze) may be generated due to severe swelling of the transparent substrate film. For this reason, it is preferable to appropriately use a solvent within the above range.
The initiator may be used without limitation as long as it is used in the art, and a radical initiator, a cationic initiator, and the like are preferably used.
Specifically, irgacure 184, irgacure 369, irgacure 651, irgacure 819, irgacure 907, benzoin alkyl ether (Benzionworkbench), benzophenone (Benzophenone), benzyl dimethyl acetal (Benzyl dimethyl katal), hydroxycyclohexylphenyl acetone (Hydroxycyclohexyl phenylacetone), chloroacetophenone (Chloro acetophenone), 1-dichloroacetophenone (1, 1-Dichloro acetophenone), diethoxyacetophenone (Diethoxy acetophenone), hydroxyacetophenone (Hydroxy Acetophenone), 2-chlorothioxanthone (2-Choro thioxanthone), 2-ETAQ (2-Ethyl Anthraquinone: 2-ethylanthraquinone), 1-Hydroxy-cyclohexyl-phenyl-ketone (1-Hydroxy-cyclohexenyl-ketone), 2-Hydroxy-2-methyl-1-phenyl-1-propanone (2-Hydroxy-2-methyl-1-propanone), 2-Hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methyl-1-propanone (2-Hydroxy ethoxy) phenyl ] -2-Hydroxy-1-propanone (2-Hydroxy-phenyl-2-methyl-propanone), 2-Hydroxy-phenyl-1-propanone (2-Hydroxy-methyl-2-phenyl-propanone), 2-Hydroxy-phenyl-1-methyl-2-Hydroxy-1-propanone (2-Hydroxy-phenyl-2-methyl-1-Hydroxy-phenyl-1-propanone), they may be used alone or in combination of two or more.
Such an initiator may be used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the entire adhesive composition. In the present invention, if the content is less than 0.1 part by weight, the curing speed of the composition is low, and the mechanical properties may be lowered due to uncured state, whereas if it exceeds 10 parts by weight, cracks may be generated in the coating film due to over-curing.
In one embodiment of the present invention, the above composition may further comprise an additive. As the additive, an acrylic leveling agent, a silicone leveling agent, or the like may be additionally used, and the effect of improving the surface leveling property can be achieved. When the easy-to-adhere composition contains the leveling agent, there is an advantage that it can be formed uniformly by preventing aggregation in the composition during formation of a coating film, and smoothness and coatability can be imparted.
The leveling agent may be one commonly used in the art. Among them, silicone leveling agents are more preferable, and for example, silicone diacrylate compounds, silicone polyacrylate compounds, and the like can be used, and these may be used alone or in combination of two or more, but these leveling agents are not necessarily limited thereto.
The above-mentioned additives may be added by appropriately adjusting the content within a range that does not hinder the effects of the present invention.
< hard coating film >
The hard coat film of the present invention is not particularly limited as long as it contains the laminate.
As illustrated in fig. 1, the hard coat film 100 according to the embodiment of the present invention may include the above-described laminate and the hard coat layer 130 formed on the opposite side of the easy-to-adhere layer 110 of the base material layer 120.
The hard coat layer may be manufactured by a method known in the art. The thickness of the hard coat layer is not particularly limited, and may be, for example, 5 to 100 μm. When the thickness is within the above range, more excellent hardness and flexibility can be exhibited, and curling phenomenon can be prevented.
The step of drying the hard coat film may be performed by a heating means such as a hot plate, a hot air circulation furnace, or an infrared furnace, and may be performed at a temperature of 50 to 150 ℃ or 50 to 100 ℃.
In the step of curing the hard coat film, active rays such as UV rays of 190nm to 450nm, for example, 200nm to 500nm, are irradiated. As a light source used for irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon laser, or the like can be used, and X-rays, electron beams, or the like can be used as appropriate.
In the step of subjecting the easy-to-adhere layer of the hard coat film to normal pressure plasma treatment, the easy-to-adhere layer is set as a plasma-treated surface, and then plasma treatment is performed with an output of 0.5 to 3KW in a state of blowing nitrogen and air, whereby the surface is subjected to hydrophilic treatment. In particular, the surface energy can be adjusted to meet desired process conditions by a process of treating the surface by generating plasma at an atmospheric pressure of 1atm (760 Torr) instead of vacuum.
< image display device >
Embodiments of the present invention provide windows and image display devices comprising the above hardcoat films.
For example, the film may be used as a window or a window laminate including the hard coat film, and at this time, at least one of a polarizing layer and a touch sensor layer may be laminated on one surface of the window formed by the hard coat film. Such a window or a window laminate may be used as a window film formed on the outermost surface of the image display device. The hard coat film may be inserted into the image display device, for example.
The image display device includes various image display devices such as a liquid crystal display device, an electroluminescence display device, a plasma display device, and a field emission display device, and may be a flexible display device having flexibility and bending characteristics.
In this case, the hard coat laminate of the embodiment of the present invention can be more effectively used as a window or window laminate of the above-described flexible display device. The interaction of the substrate layer and the easy-to-adhere layer contained in the hard coating film can simultaneously improve the flexibility and the durability of the window and can also simultaneously realize the antistatic performance. This can improve impact resistance and abrasion resistance of the flexible display device, and prevent damage such as cracking and peeling at the time of bending and bending (bending), for example.
In the following, experimental examples including specific examples and comparative examples are provided for the purpose of facilitating the understanding of the present invention, but this is merely for illustrating the present invention and does not limit the scope of the appended claims, and it is obvious to those skilled in the art that various changes and modifications may be made to the embodiments within the scope and technical spirit of the present invention, and that such changes and modifications are also within the scope of the appended claims. In addition, unless otherwise noted, the contents "%" and "parts" are expressed below on a weight basis.
Synthesis example: manufacture of an easy-to-adhere composition
Production example 1
An adhesive composition was prepared by mixing 19 parts by weight of urethane acrylic oligomer (RSP-1, mirae Nanotech), 1 part by weight of 1-hydroxycyclohexyl phenyl ketone, and 80 parts by weight of isopropyl alcohol with a stirrer.
Production example 2
An adhesive composition was prepared by blending 18.9 parts by weight of 6-functional urethane acrylate (Kyoeisha, co., ltd., UA-306I), 80 parts by weight of isopropyl alcohol, 1 part by weight of 1-hydroxycyclohexyl phenyl ketone, and 0.1 part by weight of a silicone-based additive (BYK Co., BYK-310) with a stirrer.
Production example 3
An adhesive composition was prepared by blending 18.9 parts by weight of 6-functional urethane acrylate (co-Rong, UA-306I), 80 parts by weight of isopropyl alcohol, 1 part by weight of 1-hydroxycyclohexyl phenyl ketone, and 0.1 part by weight of a silicone-based additive (BYK Co., BYK-333) with a stirrer.
Production example 4
An adhesive composition was prepared by mixing 19 parts by weight of urethane acrylate oligomer (RSP-1, meilin nanotechnology Co., ltd.), 1 part by weight of 1-hydroxycyclohexyl phenyl ketone, and 80 parts by weight of methyl ethyl ketone with a stirrer.
Production example 5
An adhesive composition was prepared by blending 18.9 parts by weight of 6-functional urethane acrylate (co-Rong, UA-306I), 80 parts by weight of methyl ethyl ketone, 1 part by weight of 1-hydroxycyclohexyl phenyl ketone, and 0.1 part by weight of a silicone-based additive (BYK Co., BYK-333) with a stirrer.
Production example 6
An adhesive composition was prepared by mixing 30 parts by weight of a fluorinated acrylate (LINC-3A, co., ltd.), 1 part by weight of 1-hydroxycyclohexyl phenyl ketone, and 69 parts by weight of methyl ethyl ketone with a stirrer.
Examples, comparative examples and reference examples: manufacture of laminate
Example 1
The adhesive composition of preparation example 1 was applied to a polyimide-based substrate (Sumitomo chemical Co., ltd., 50 μm) at a thickness of 800nm, and dried at 80℃for 2 minutes at 500mJ/cm 2 After UV curing to prepare a transparent polyimide film having an easily adhesive layer, the film was subjected to normal pressure plasma treatment, and then physical properties were confirmed.
Example 2
The adhesive composition of preparation example 1 was applied to a polyimide-based substrate at a thickness of 450nm, and dried at 80℃for 2 minutes at 500mJ/cm 2 After UV curing to prepare a transparent polyimide film having an easily adhesive layer, the film was subjected to normal pressure plasma treatment, and then physical properties were confirmed.
Example 3
The adhesive composition of preparation example 1 was applied to a polyimide-based substrate at a thickness of 200nm, and dried at 80℃for 2 minutes at 500mJ/cm 2 After UV curing to prepare a transparent polyimide film having an easily adhesive layer, the film was subjected to normal pressure plasma treatment, and then physical properties were confirmed.
Example 4
The adhesive composition of preparation example 1 was applied to a polyimide-based substrate at a thickness of 80nm, and dried at 80℃for 2 minutes at 500mJ/cm 2 After UV curing to prepare a transparent polyimide film having an easily adhesive layer, the film was subjected to normal pressure plasma treatment, and then physical properties were confirmed.
Example 5
The adhesive composition of preparation example 2 was applied to a polyimide-based substrate at a thickness of 450nm, and dried at 80℃for 2 minutes at 500mJ/cm 2 After UV curing to prepare a transparent polyimide film having an easily adhesive layer, the film was subjected to normal pressure plasma treatment, and then physical properties were confirmed.
Example 6
The adhesive composition of preparation example 3 was applied to a polyimide-based substrate at a thickness of 450nm, and dried at 80℃for 2 minutes at 500mJ/cm 2 After UV curing to prepare a transparent polyimide film having an easily adhesive layer, the film was subjected to normal pressure plasma treatment, and then physical properties were confirmed.
Comparative example 1
The adhesive composition of preparation example 4 was applied to a polyimide-based substrate at a thickness of 450nm, and dried at 80℃for 2 minutes at 500mJ/cm 2 After UV curing to prepare a transparent polyimide film having an easily adhesive layer, the film was subjected to normal pressure plasma treatment, and then physical properties were confirmed.
Comparative example 2
The adhesive composition of preparation example 5 was applied to a polyimide-based substrate at a thickness of 450nm, and dried at 80℃for 2 minutes at 500mJ/cm 2 After UV curing to prepare a transparent polyimide film having an easily adhesive layer, the film was subjected to normal pressure plasma treatment, and then physical properties were confirmed.
Comparative example 3
The adhesive composition of preparation example 6 was applied to a polyimide-based substrate at a thickness of 800nm, and dried at 80℃for 2 minutes at 500mJ/cm 2 After UV curing to prepare a transparent polyimide film having an easily adhesive layer, the film was subjected to normal pressure plasma treatment, and then physical properties were confirmed.
Reference example 1
The preparation example 2 was carried outThe adhesive composition was applied to a polyimide-based substrate at a thickness of 30nm, and dried at 80℃for 2 minutes at 500mJ/cm 2 After UV curing to prepare a transparent polyimide film having an easily adhesive layer, the film was subjected to normal pressure plasma treatment, and then physical properties were confirmed.
Reference example 2
The adhesive composition of preparation example 2 was applied to a polyimide-based substrate at a thickness of 5. Mu.m, and dried at 80℃for 2 minutes at 500mJ/cm 2 After UV curing to prepare a transparent polyimide film having an easily adhesive layer, the film was subjected to normal pressure plasma treatment, and then physical properties were confirmed.
Experimental example
(1) Element content of the surface of the easy-to-bond layer of the laminate
After preparing samples by shearing the laminates produced in examples 1 to 6 and comparative examples 1 to 3 into a size of 2cm×2cm, the elemental content of the surface of the laminate samples was measured using a quanta ii (Ulvac-PHI) XPS apparatus 200. Specifically, referring to fig. 2, the laminate sample 210 was placed in the Intro of the XPS apparatus 200 to a vacuum of 1×10 -4 Pa is maintained for more than 1 hour, and then the mixture is moved to a main chamber (main chamber) and then the mixture is subjected to vacuum degree of 1 multiplied by 10 -7 Pa is maintained for more than 1 hour. Then, X-rays 221 were irradiated onto the surface under conditions of an area of 200 μm in the transverse direction and 200 μm in the longitudinal direction, 25W and 15kV, and the content of constituent elements on the surface was calculated by measuring the average value 3 times at any position on the outermost surface of the sample, and the results are shown in Table 1. At this time, the average free path of photoelectrons emitted from the surface of the sample due to the above-described irradiated X-rays to be incident on the detector (detector) 222 is set to form an angle of 5 ° with the surface of the sample.
TABLE 1
Physical properties of the laminate produced in examples 1 to 6, comparative examples 1 to 3 and reference examples 1 to 2 were measured by the following methods, and the results are shown in table 2.
(2) Adhesion of
After the base film was bonded to the glass with the transparent adhesive so that the easy-to-adhere layer became the upper part, a dicing mark was formed on the laminate surface in the form of 100 squares in the lateral and longitudinal directions at 1mm intervals by a dicing blade, and then 3 times of adhesion test were performed by using the milpa adhesive tape. The result is expressed by "number of quadrangles qualified after the adhesion test/100".
(3) Solvent resistance
1 drop of isophorone was dropped on the easy-to-adhere layer at normal temperature, and after standing for 30 minutes, the change of the easy-to-adhere layer was confirmed, thereby performing the test. If the easy-to-adhere layer surface has no change, the easy-to-adhere layer surface is marked as qualified, and if the easy-to-adhere layer surface has the change, the easy-to-adhere layer surface is marked as unqualified.
(4) Initial contact angle determination
After 2ml of a water drop was dropped onto the easily adhesive surface at normal temperature (25 ℃) and 1 minute later, the contact angle with respect to the water drop was measured by a contact angle meter (DSA 100 of KRUSS Co.). The contact angle was measured 5 times with the same sample for the left and right contact angles of the water drop, and the average value was used.
(5) Contact angle measurement after plasma treatment
The easy-to-bond layer was subjected to plasma treatment using a plasma processor (Bar (MPPH 02) from MAK company) to output 1.5KW, nitrogen flow rate 310Lpm, air (Air) flow rate 3Lpm, speed 55mm/sec, and treatment Gap (Gap) 2.5 mm. After 2ml of a water drop was dropped onto the plasma-treated sample of the easy-to-adhere layer, the contact angle with respect to the water drop was measured by a contact angle meter (DSA 100 of KRUSS). The contact angle was measured 5 times with the same sample for the left and right contact angles of the water drop, and the average value was used.
(6) Flexibility of
The film was repeatedly folded and unfolded 20 ten thousand times at 1mm radius intervals in the direction in which the easy-adhesive layer was elongated, thereby performing a bending test.
< evaluation criterion >
O: no fracture or crack occurs
X: fracture or crack
TABLE 2
Referring to table 2, the laminate of the examples of the present invention showed excellent results in adhesion, solvent resistance and flexibility tests. Further, the laminates of the examples of the present invention showed contact angles of 35 ° or less after the atmospheric pressure plasma treatment. On the other hand, the laminate of the comparative example using methyl ethyl ketone as a ketone-based solvent as the solvent for the easily adhesive composition had a contact angle of 39.7 ° or more after normal pressure plasma treatment, and did not exhibit physical properties to an extent suitable for the use of flexible films.
For reference, the composition of example 5 was the same as that of the adhesive composition, but the contact angle of the laminate of reference examples 1 and 2, in which the thickness of the adhesive composition applied was 30nm or 5 μm (5,000 nm), was 35 ° or more after atmospheric pressure plasma treatment.
Therefore, it is found that the laminate of the present invention, in which the thickness of the adhesive composition applied is 40nm to 3 μm, more preferably 50nm to 1 μm, has excellent physical properties and a contact angle of 35 ° or less after normal pressure plasma treatment, as compared with the laminates of the comparative examples and the reference examples, which deviate from the above-mentioned constitution and range.
Claims (12)
1. A laminate, comprising:
a transparent polyimide base material layer; and
an easy-to-adhere layer formed on at least one surface of the base material layer and formed of a cured product of the easy-to-adhere composition,
the easy-to-adhere layer does not contain a substituent group containing a C-F bond on the surface.
2. The laminate according to claim 1, wherein the contact angle of the easy-to-adhere layer after atmospheric pressure plasma treatment is 35 ° or less.
3. The laminate according to claim 1, wherein the thickness of the easy-to-adhere layer is 40nm to 3 μm.
4. The laminate according to claim 1, wherein the easy-to-adhere composition comprises one or more of a photopolymerizable compound, a solvent, and an initiator.
5. The laminate according to claim 4, wherein the photopolymerizable compound comprises at least one selected from the group consisting of a polyfunctional acrylate monomer and a polyfunctional acrylate oligomer that does not dissolve the transparent polyimide-based substrate.
6. The laminate of claim 4, the easy-to-adhere composition further comprising an additive.
7. The laminate according to claim 1, wherein the C-F bond is formed by C-F X The bond represented, x is 1 to 3.
8. The laminate according to claim 1, which is used for a hard coat film.
9. A hardcoat film comprising:
the laminate of claim 1; and
and a hard coat layer formed on a surface of the base material layer different from the easy-to-adhere layer.
10. The hardcoat film of claim 9 for a flexible display.
11. A window comprising the hardcoat film of claim 9 or 10.
12. An image display device comprising the window of claim 11.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20210144647 | 2021-10-27 | ||
| KR10-2021-0144647 | 2021-10-27 | ||
| KR1020220005350A KR20230060423A (en) | 2021-10-27 | 2022-01-13 | A laminate structure, hardcoat film including the same, window and display device using the same |
| KR10-2022-0005350 | 2022-01-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116023867A true CN116023867A (en) | 2023-04-28 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211254338.0A Pending CN116023867A (en) | 2021-10-27 | 2022-10-13 | Laminate, hard coat film comprising same, and window and image display device using same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2023065333A (en) |
| CN (1) | CN116023867A (en) |
| TW (1) | TW202330284A (en) |
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2022
- 2022-09-21 TW TW111135693A patent/TW202330284A/en unknown
- 2022-10-13 CN CN202211254338.0A patent/CN116023867A/en active Pending
- 2022-10-26 JP JP2022171406A patent/JP2023065333A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| TW202330284A (en) | 2023-08-01 |
| JP2023065333A (en) | 2023-05-12 |
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