CN113004809B - Adhesive composition with variable adhesive force for display and adhesive sheet for display - Google Patents
Adhesive composition with variable adhesive force for display and adhesive sheet for display Download PDFInfo
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- CN113004809B CN113004809B CN202011520168.7A CN202011520168A CN113004809B CN 113004809 B CN113004809 B CN 113004809B CN 202011520168 A CN202011520168 A CN 202011520168A CN 113004809 B CN113004809 B CN 113004809B
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
The present invention relates to a variable adhesion composition for display and an adhesive sheet for display comprising the same, and more particularly, to the following variable adhesion composition for display and an adhesive sheet for display comprising the same: the adhesive sheet for display is easily peeled off again in the step of attaching the adhesive sheet for display to a display device because of low adhesive force before irradiation with ultraviolet rays or heat treatment, and easily removed in part by laser punching, and has excellent adhesive force with the display device after irradiation with ultraviolet rays or heat treatment, low fluidity of the variable adhesive layer of the adhesive sheet for display, no generation of bubbles during bonding, and excellent bending property, and thus can be applied to not only a display or a flexible display having a difference in height, but also an excellent adhesion to a base film and a low reduction rate of adhesive force after being left under high temperature and high humidity conditions.
Description
Technical Field
The present invention relates to a variable adhesive composition for display and an adhesive sheet for display comprising the same, and more particularly, to the following variable adhesive composition for display and an adhesive sheet for display comprising the same: the adhesive sheet for display device is easily peeled off again in the step of attaching the adhesive sheet for display device to a display device because the adhesive force is low before irradiation with Ultraviolet (UV) or thermal energy treatment, and the adhesive sheet for display device is easily removed by a laser punching step, and has excellent adhesive force with the display device after irradiation with Ultraviolet (UV) or thermal energy treatment, low fluidity of a variable adhesive layer of the adhesive sheet for display device, no bubble generation during bonding, and excellent bending property, and thus can be applied to not only a display or a flexible display having a difference in height, but also exhibit an effect of excellent adhesion with a base film and a low reduction rate of adhesive force after being left under high temperature and high humidity conditions.
Background
Recently, with the rapid development of information communication technology and the expansion of the market, flat Panel Display devices (Flat Panel displays) have attracted attention as Display devices. Representative flat Panel Display devices include Liquid Crystal Display devices (Liquid Crystal displays), plasma Display devices (Plasma displays), organic Light Emitting devices (Organic Light Emitting Diodes), and the like.
Organic light emitting devices have advantages of fast response speed and being light, thin, short, and small, with low power consumption, self-light emission, flexibility, and the like, and thus, recently, demands thereof in lighting and the like including new-generation display devices, flexible displays, and the like are also increasing.
The organic light emitting device is formed by sequentially evaporating a transparent electrode, a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, an electron injection layer and a metal electrode on a glass substrate, and the principle of the organic light emitting device is that electrons and holes provided from the electrodes on two sides are combined and released energy in the organic light emitting layer to emit light.
The organic light emitting device may be deteriorated by external factors such as external moisture and oxygen or ultraviolet rays, and thus a packaging (packing) technique for sealing the organic light emitting device is very important, and the organic light emitting display device needs to be manufactured thin in order to be suitable for various applications.
On the other hand, the display device lower portion includes an adhesive sheet for protecting the display device from an external force, and in the process of attaching the adhesive sheet, there is a possibility that the adhesive sheet may be removed due to a failure, but the adhesive sheet may not be removed due to a high adhesive force of the adhesive sheet, so that there is a problem that it is difficult to reuse the display device. Further, the adhesive sheet has a problem of damaging the display device in a process of removing a part of the adhesive sheet attached to the large-area display device by laser punching due to high adhesive force of the adhesive sheet.
Therefore, the present invention has been completed by studying the following adhesive sheet for display: by providing the adhesive sheet with a variable adhesive force property, the adhesive sheet has a low adhesive force before being irradiated with ultraviolet light or subjected to a thermal energy treatment, and thus is easily peeled off again in a step of attaching the adhesive sheet to a display device, and a part of the adhesive sheet is easily removed in a laser punching step.
Documents of the prior art
Patent document
Patent document 1: korean granted patent No. 10-0252953 (published: 1999 year 02, 25)
Disclosure of Invention
The present invention has been made in view of the above problems, and an object thereof is to provide a variable adhesive strength adhesive composition for a display and an adhesive sheet for a display including the same: since the adhesive strength is low before the ultraviolet irradiation or the thermal energy treatment, the adhesive sheet for display is easily peeled off again in the step of attaching the adhesive sheet for display to the display device, and the part of the adhesive sheet for display is easily removed in the laser punching step.
Another object of the present invention is to provide a variable adhesive strength adhesive composition for display and an adhesive sheet for display comprising the same: the pressure-sensitive adhesive sheet for display has excellent adhesion to a display device after irradiation with ultraviolet rays or thermal energy treatment, has low fluidity of the variable pressure-sensitive adhesive layer, does not generate bubbles during bonding, and has excellent bending properties, and thus can be suitably used for a display having a level difference or a flexible display.
Another object of the present invention is to provide a variable adhesion composition for display and an adhesive sheet for display including the same, wherein: the adhesive layer has excellent adhesion to the base film of the pressure-sensitive adhesive layer, and can exhibit the effect of reducing the rate of decrease in adhesion even after being placed under high-temperature and high-humidity conditions.
In order to solve the above problems, the adhesive composition with variable adhesive force for display according to the present invention may comprise: a (meth) acrylic polymer containing, as a main component, a (meth) acrylic monomer having an alkyl group with a carbon number of 1 to 14; (meth) acrylic compounds having an oxyalkylene chain; and a photoinitiator.
In a preferred embodiment of the present invention, the (meth) acrylic polymer may include a carboxyl group or a hydroxyl group as a functional group.
In a preferred embodiment of the present invention, the number of acrylic functional groups of the (meth) acrylic compound having an oxyalkylene chain may be 1 or more and less than 6.
In a preferred embodiment of the present invention, the (meth) acrylic compound having an oxyalkylene chain may include a compound represented by the following chemical formula 1.
Chemical formula 1:
in the above chemical formula 1, A is-CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 -，R 1 And R 2 Are each independently C 1 ～C 5 N is a rational number satisfying 100 to 1000.
In a preferred embodiment of the present invention, the variable adhesion composition according to the present invention may include 5 to 15 parts by weight of a (meth) acrylic compound having an oxyalkylene chain and 0.1 to 1 part by weight of a photoinitiator, based on 100 parts by weight of a (meth) acrylic polymer.
In a preferred embodiment of the present invention, the variable adhesion composition of the present invention may further comprise one or more selected from a crosslinking agent and a solvent.
In a preferred embodiment of the present invention, the variable adhesion composition according to the present invention may include 0.1 to 10 parts by weight of the crosslinking agent and 10 to 30 parts by weight of the solvent, based on 100 parts by weight of the (meth) acrylic polymer.
On the other hand, the adhesive sheet for display of the present invention may include a variable adhesive layer comprising the aforementioned adhesive composition of variable adhesive force type for display.
In a preferred embodiment of the present invention, the pressure-sensitive adhesive sheet for display of the present invention satisfies the following conditions (1) and (2).
(1)A≤100
In the above condition (1), a represents the adhesive force (gf/25 mm) of the variable adhesive layer measured by adhering the adhesive sheet for display to a polyimide film, leaving the adhesive sheet at a temperature of 25 ℃ for 1 hour, and then peeling the adhesive sheet at a speed of 300mm per minute and at an angle of 180 °.
(2)300≤B
In the above condition (2), B represents that the pressure-sensitive adhesive sheet for display is attached to a polyimide film at 300mJ/cm 2 The adhesion force (gf/25 mm) of the pressure-sensitive adhesive layer was measured by peeling at a rate of 300mm per minute and an angle of 180 degrees after irradiation with ultraviolet rays.
In a preferred embodiment of the present invention, the adhesive sheet for display of the present invention may further include a base film laminated on one side of the variable adhesive layer.
In a preferred embodiment of the present invention, the base film of the present invention may include an antistatic layer on at least one side.
Further, the present invention provides a display comprising the aforementioned adhesive sheet for a display.
In the adhesive composition with variable adhesive force for display and the adhesive sheet for display including the same of the present invention, the adhesive force is low before irradiation with ultraviolet light or heat treatment, so that the adhesive sheet for display is easily peeled off again in the step of attaching the adhesive sheet for display to a display device, and the part of the adhesive sheet for display is easily removed by the laser punching step.
In addition, the adhesive composition for display with variable adhesive force and the adhesive sheet for display including the same according to the present invention have good adhesive force with a display device after irradiation with ultraviolet rays or thermal energy treatment, have low fluidity of the variable adhesive layer of the adhesive sheet for display, do not generate bubbles during bonding, and have excellent bending performance, and thus can be applied to displays with height differences or flexible displays.
In addition, the adhesive composition with variable adhesive force for display and the adhesive sheet for display including the same according to the present invention have excellent adhesion to the base film of the variable adhesive layer, and can exhibit an effect of reducing the rate of decrease in adhesive force even after being left under high temperature and high humidity conditions.
Drawings
Fig. 1 is a schematic sectional view showing a display adhesive sheet of the present invention as a preferred embodiment of the present invention.
Description of reference numerals
11: antistatic layer
10: base film
20: variable adhesive layer
30: lining film
31: silicon layer。
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 to which the present invention pertains can easily carry out the embodiments. The invention can be implemented in many different ways and is not limited to the embodiments described herein. In order to clearly explain the present invention, portions that are not relevant to the explanation will be omitted in the drawings, and the same reference numerals will be given to the same or similar structural elements throughout the specification.
The variable adhesion composition for display use of the present invention comprises a (meth) acrylic polymer, a (meth) acrylic compound having an oxyalkylene chain, and a photoinitiator.
First, the (meth) acrylic polymer of the present invention is a base material for imparting adhesive strength to the adhesive composition of variable adhesive strength for display, and may contain, as a main component, (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms.
Also, the (meth) acrylic polymer of the present invention may contain a carboxyl group or a hydroxyl group as a functional group.
Also, the (meth) acrylic polymer of the present invention may contain 30 to 50% of a solid content, preferably 35 to 45% of a solid content, may have a bonding force of 1200 to 2000g/25mm, preferably 1500 to 1700g/25mm (180 °, peel strength (peel Strength)), and may contain 0.1 to 20% by weight, preferably 0.2 to 10% by weight of a curing agent, relative to the total weight.
Further, the (meth) acrylic polymer of the present invention may contain 20% to 40% of solid content, preferably 25% to 35% of solid content, may have a viscosity of 4000 to 10000 mPas (30 ℃), preferably 6000 to 7500 mPas (30 ℃), and may have a weight average molecular weight of 50 to 90 ten thousand g/mol, preferably 60 to 80 ten thousand g/mol.
Next, the (meth) acrylic compound having an oxyalkylene chain of the present invention is a substance capable of causing the adhesion force variable type adhesive composition for display of the present invention to express a function of varying the adhesion force characteristic, and the number of acrylic acid functional groups may be 1 or more and less than 6, preferably 1 or more and less than 3, and preferably, may contain a compound represented by the following chemical formula 1.
Chemical formula 1:
in the above chemical formula 1, A may be-CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 -, preferably, may be-CH 2 -or-CH 2 CH 2 -。
And, in the above chemical formula 1, R 1 And R 2 May each independently be C 1 ～C 5 Preferably, each may be independently C 1 ～C 3 The alkyl group of (1).
Also, in the above chemical formula 1, n may be a rational number satisfying 100 to 1000, and preferably, may be a rational number satisfying 300 to 700.
On the other hand, the adhesion force variable type adhesive composition for display of the present invention may include 5 to 15 parts by weight of the (meth) acrylic compound having an oxyalkylene chain, preferably 7 to 13 parts by weight of the (meth) acrylic compound having an oxyalkylene chain, more preferably 9 to 11 parts by weight of the (meth) acrylic compound having an oxyalkylene chain, and if the content of the (meth) acrylic compound having an oxyalkylene chain is less than 5 parts by weight, the adhesion force may increase before irradiation with ultraviolet rays, and if it exceeds 15 parts by weight, the adhesion force between the variable adhesive layer and the base film may decrease, and the variable adhesive layer may be peeled off.
Thereafter, the photoinitiator according to the present invention may use a photoinitiator capable of ultraviolet light curing, which is generally used in the related art, and preferably, may include one or more selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 1-hydroxy-2-methyl-1-phenyl-propane-1-one, dimethyl 2,4, 6-trimethylbenzoylphosphine oxide, and 2, 2-dimethoxy-2-phenyl acetophenone, and more preferably, may include 2, 2-dimethoxy-2-phenyl acetophenone.
The variable adhesion composition for display of the present invention may contain 0.1 to 1 part by weight of a photoinitiator, preferably 0.1 to 0.8 part by weight of a photoinitiator, more preferably 0.2 to 0.5 part by weight of a photoinitiator, based on 100 parts by weight of the (meth) acrylic polymer, and when the photoinitiator is contained in an amount of less than 0.1 part by weight, the adhesion to the display device may be deteriorated due to a poor increase in adhesion after irradiation with ultraviolet rays, and when the photoinitiator is contained in an amount of more than 1 part by weight, the photoinitiator may be decomposed by a weak amount of ultraviolet rays emitted from a fluorescent lamp, a Light Emitting Diode (LED) lighting, or the like to form a low molecular weight polymer, and thus the adhesion may not reach a desired level when irradiated with ultraviolet rays.
The variable cohesive force type adhesive composition for displays according to the present invention may further contain one or more selected from a crosslinking agent and a solvent, and preferably, may further contain a crosslinking agent and a solvent.
The crosslinking agent of the present invention may use a crosslinking agent capable of performing a crosslinking action of various components, which is generally used in the related art, and preferably, may include a compound having a 4-functional epoxy functional group, and more preferably, may include a compound represented by the following chemical formula 2.
Chemical formula 2:
in the above chemical formula 2, B 1 、B 2 、B 3 And B 4 May each independently be-CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 -, preferably, may be-CH 2 -or-CH 2 CH 2 -。
The variable adhesion composition for display use according to the present invention may include 0.1 to 10 parts by weight of a crosslinking agent, preferably 0.5 to 8 parts by weight of a crosslinking agent, more preferably 3 to 6 parts by weight of a crosslinking agent, based on 100 parts by weight of the (meth) acrylic polymer, and if the amount of the crosslinking agent is less than 0.1 part by weight, the variable adhesive layer may not be cured at an intended level, the flowability of the variable adhesive layer may be increased as the crosslinking density is decreased, the adhesion performance may be reduced due to the generation of air bubbles during bonding, and if the amount of the crosslinking agent is more than 10 parts by weight, the variable adhesive layer may be excessively cured, the problems of the decrease in the adhesion and the bending performance as the gel fraction is saturated, and an unreacted crosslinking agent may remain.
The solvent of the present invention may use various solvents commonly used in the related art, preferably, may include one or more selected from the group consisting of methyl ethyl ketone, toluene, ethyl acetate, and Tetrahydrofuran (THF), and more preferably, may include methyl ethyl ketone.
The variable adhesion composition for display of the present invention may include 10 to 30 parts by weight of a solvent, preferably 15 to 25 parts by weight of a solvent, more preferably 18 to 22 parts by weight of a solvent, based on 100 parts by weight of (meth) acrylic polymer, and if the solvent is included in an amount of less than 10 parts by weight, the viscosity is high, and the mixture is not uniform when preparing a crude solution, and there is a problem in achieving desired physical properties after adhesion at a desired level, and if the solvent is included in an amount of more than 30 parts by weight, the viscosity is low, and when the adhesive composition is applied to a base film, the adhesive composition is difficult to prepare to a desired level of thickness of the adhesive sheet due to the flow of the adhesive composition, and when dried after application, there is a problem in that surface defects such as orange peel (orange) occur on the surface of the variable adhesive layer due to excessive solvent volatilization.
On the other hand, referring to fig. 1, the adhesive sheet for display of the present invention may include a variable adhesive layer 20. The pressure-sensitive adhesive sheet may further include a base film 10 laminated on one surface of the variable pressure-sensitive adhesive layer 20, and a liner film 30 laminated on the other surface of the variable pressure-sensitive adhesive layer 20.
The variable adhesive layer 20 of the present invention is configured to exhibit adhesive force by irradiation with ultraviolet rays and to adhere the base film 10 to the lower portion of the display device, and may include the aforementioned adhesive force variable adhesive composition for display device.
The thickness of the variable adhesive layer 20 may be 5 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 20 μm, and if the thickness of the variable adhesive layer 20 is less than 5 μm, problems may occur in expression of a desired level of adhesion after ultraviolet irradiation, and if it is more than 100 μm, a part is not cleanly removed after laser blanking, and a part of the variable adhesive layer 20 remains in the display device and problems may occur in driving the display device.
The base film 10 of the present invention is directly attached to a display device, and functions to protect the lower portion of the display device. The base film may include materials commonly used as an adhesive sheet in the related art without limitation, and preferably, may include polyethylene terephthalate (PET). The thickness of the base film 10 is not limited as long as it is a thickness of a base film generally used as an adhesive sheet, and is preferably 65 to 85 μm, and more preferably 70 to 80 μm, but is not limited thereto.
In order to prevent the occurrence of static electricity, the base film 10 may include an antistatic layer 11 on at least one side, and preferably, may include the antistatic layer 11 only on the outer side of the base film 10.
Specifically, the base film 10 may include an antistatic layer 11 on an opposite side to the variable adhesive layer 20, and the antistatic layer 11 may include a substance in which a binder (binder) is added to a conductive substance including one or more of Indium Tin Oxide (ITO), carbon Nanotube (CNT), polyaniline (polyaniline), and polythiophene (polythiophene), and preferably, may include poly (3, 4-ethylenedioxythiophene)/sodium polystyrene sulfonate (PEDOT/PSS).
The liner film 30 of the present invention functions to protect the variable adhesive layer 20 and the base film 10. In the display device manufacturing process, the display adhesive sheet is used by being attached to the lower portion of the display device, and when the display adhesive sheet is attached to the lower portion of the display device, one surface of the variable adhesive layer 20 is attached to the display device after the glass liner film 30 is used.
The liner film 30 may use materials generally used for liner films in the related art without limitation, and preferably, may include a polyethylene terephthalate film. The thickness of the liner film 30 is not limited as long as the liner film 30 is generally usable as a pressure-sensitive adhesive sheet, and is preferably 15 to 35 μm, more preferably 20 to 30 μm, but is not limited thereto.
In order to function to protect the variable adhesive layer 20, the liner film 30 may include a silicon layer 31 on at least one side, and preferably, may include the silicon layer 31 only on the side contacting the variable adhesive layer 20.
On the other hand, the adhesive sheet for display of the present invention can satisfy all of the conditions (1) and (2) below.
(1) A.ltoreq.100, preferably 1. Ltoreq.A.ltoreq.50, more preferably 1. Ltoreq.A.ltoreq.10
In the above condition (1), a represents the adhesive force (gf/25 mm) of the pressure-sensitive adhesive layer measured by adhering the pressure-sensitive adhesive sheet for display to a polyimide film, leaving the sheet at a temperature of 25 ℃ for 1 hour, and then peeling the sheet at a speed of 300mm per minute and at an angle of 180 °.
(2) 300 ≦ B, preferably 500 ≦ B ≦ 1000, more preferably 600 ≦ B ≦ 800
In the above condition (2), B represents that the pressure-sensitive adhesive sheet for display is attached to a polyimide film at 300mJ/cm 2 The adhesive force (gf/25 mm) of the pressure-sensitive adhesive layer was measured by peeling at a rate of 300mm per minute and at an angle of 180 degrees after irradiation with ultraviolet rays.
Further, the method for producing an adhesive sheet for display of the present invention includes the first to third steps.
First, the first step of the method for producing an adhesive sheet for display of the present invention may be to produce an adhesive composition of variable adhesive force type for display.
The variable adhesion composition for display use of the first step may be prepared by mixing and stirring the (meth) acrylic polymer, the (meth) acrylic compound having an oxyalkylene chain, and the photoinitiator, and preferably, may be prepared by mixing a crosslinking agent and a solvent in addition to the (meth) acrylic polymer, the (meth) acrylic compound having an oxyalkylene chain, and the photoinitiator.
In this case, 5 to 15 parts by weight of the (meth) acrylic compound having an oxyalkylene chain may be mixed with 100 parts by weight of the (meth) acrylic polymer, preferably 7 to 13 parts by weight of the (meth) acrylic compound having an oxyalkylene chain, more preferably 9 to 11 parts by weight of the (meth) acrylic compound having an oxyalkylene chain, 0.1 to 1 part by weight of the photoinitiator may be mixed, preferably 0.1 to 0.8 part by weight of the photoinitiator may be mixed, more preferably 0.2 to 0.5 part by weight of the photoinitiator may be mixed, 0.1 to 10 parts by weight of the crosslinking agent may be mixed, preferably 0.5 to 8 parts by weight of the crosslinking agent may be mixed, more preferably 4 to 6 parts by weight of the crosslinking agent may be mixed, 10 to 30 parts by weight of the solvent may be mixed, preferably 15 to 25 parts by weight of the solvent may be mixed, more preferably 18 to 22 parts by weight of the solvent may be mixed.
The mixing and stirring in the first step may be performed at a temperature of 10 to 40 ℃ and 20 to 30 ℃ for 10 to 60 minutes, preferably 20 to 40 minutes.
Then, in the second step of the method for producing an adhesive sheet for display of the present invention, the adhesive composition having a variable adhesive force for display produced in the first step is applied to the other surface of the base film having the antistatic layer formed on one surface thereof, and the variable adhesive layer can be formed on the other surface of the base film by heating. In this case, the heating may be performed at a temperature of 100 to 200 ℃, preferably at a temperature of 110 to 150 ℃ for 1 to 5 minutes, preferably 1 to 3 minutes.
Finally, in the third step of the method for producing a pressure-sensitive adhesive sheet for display of the present invention, a liner film is bonded to one surface of the variable pressure-sensitive adhesive layer formed in the second step, and the liner film is cured to produce a pressure-sensitive adhesive sheet for display. In this case, the lamination may be performed using a laminator, and the curing may be performed at a temperature of 30 to 70 ℃, preferably 40 to 60 ℃, for 1 to 5 days, preferably 1 to 3 days. A silicon layer may be formed on the surface of the liner film bonded to the variable pressure-sensitive adhesive layer.
The present invention has been described above mainly by way of examples, but these are merely illustrative and not limitative of the examples of the present invention, and it will be apparent to those skilled in the art to which embodiments of the present invention pertain that various modifications and applications can be made without departing from the essential characteristics of the present invention, which are not illustrated in the foregoing description. For example, each of the components specifically shown in the examples of the present invention may be modified and implemented. Moreover, differences in these modifications and applications should be construed as being included in the scope of the present invention as defined in the claims.
Example 1: preparation of adhesive sheet for display
(1) First, a (meth) acrylic polymer having a carboxyl group as a functional group (POA-4700, 40% solid content) was mixed with methyl ethyl ketone as a solvent, and a compound represented by the following chemical formula 1-1 (Miwon M286) as a (meth) acrylic compound having an oxyalkylene chain, a compound represented by the following chemical formula 2-1 (Tetrad-X) as a crosslinking agent, and 2, 2-dimethoxy-2-phenylacetophenone (Omnirad-651, inc. as a photoinitiator were mixed and stirred at a temperature of 25 ℃ for 30 minutes, thereby preparing a bonding force variable type adhesive composition for a display. The solvent, the (meth) acrylic compound having an oxyalkylene chain, the crosslinking agent, and the photoinitiator were mixed in an amount of 20 parts by weight, 10 parts by weight, and 0.3 part by weight, respectively, based on 100 parts by weight of the (meth) acrylic polymer.
Chemical formula 1-1:
in the above chemical formula 1-1, A is-CH 2 -，R 1 And R 2 Is methyl and n is 600.
Chemical formula 2-1:
(2) An adhesive composition of variable adhesive force for display was coated on the other side of a polyethylene terephthalate base film (SKC HT & M Co., TU63A, thickness: 75 μ M) having an antistatic layer formed on one side thereof, and heated at a temperature of 130 ℃ for 1 minute to form a variable adhesive layer (thickness: 15 μ M) on the other side of the base film.
(3) One side of the variable pressure-sensitive adhesive layer and one side of a polyethylene terephthalate liner film (thickness: 25 μm) subjected to silicon treatment were bonded using a laminator and aged at a temperature of 50 ℃ for 2 days to prepare a pressure-sensitive adhesive sheet for a display.
Example 2
An adhesive sheet for display was prepared in the same manner as in example 1. However, unlike example 1, a pressure-sensitive adhesive sheet for display was finally prepared using a compound represented by the following chemical formula 1-2 (Miwon, miramer M2040) as a (meth) acrylic compound having an oxyalkylene chain.
Chemical formulas 1 to 2:
in the above chemical formula 1-2, A is-CH 2 -，R 1 And R 2 Is methyl and n is 400.
Example 3
An adhesive sheet for display was prepared in the same manner as in example 1. However, unlike example 1, a (meth) acrylic polymer having a carboxyl group as a functional group was not used, but a (meth) acrylic polymer having a hydroxyl group as a functional group (Saiden, X-312-252S, solid content 30%) was used, and an isocyanurate-containing hexamethylene diisocyanate-based modified polyisocyanate (HDI based modified polyisocyanate, associating isocyanate) (manufactured by japan polyurethane corporation, colonate HX) was used as a crosslinking agent, and 0.5 parts by weight of the crosslinking agent was used with respect to 100 parts by weight of the (meth) acrylic polymer to finally prepare an adhesive sheet for display.
Example 4
An adhesive sheet for display was prepared in the same manner as in example 1. However, unlike example 1, a compound represented by the following chemical formula 3 (Miwon corporation, miramer M164) was used as a (meth) acrylic compound having an oxyalkylene chain to finally prepare a pressure-sensitive adhesive sheet for display.
Chemical formula 3:
example 5
An adhesive sheet for display was prepared in the same manner as in example 1. However, unlike example 1, 12 parts by weight of a (meth) acrylic compound having an oxyalkylene chain was mixed with 100 parts by weight of a (meth) acrylic polymer to finally prepare a pressure-sensitive adhesive sheet for display.
Example 6
An adhesive sheet for display was prepared in the same manner as in example 1. However, unlike example 1, a compound represented by the following chemical formula 4 (Miwon corporation, miramer M2100) was used as a (meth) acrylic compound having an oxyalkylene chain to finally prepare a pressure-sensitive adhesive sheet for display.
Chemical formula 4:
example 7
An adhesive sheet for display was prepared in the same manner as in example 1. However, unlike example 1, a compound represented by the following chemical formula 5 (Miwon, miramer M2300) was used as a (meth) acrylic compound having an oxyalkylene chain to finally prepare a pressure-sensitive adhesive sheet for display.
Chemical formula 5:
comparative example 1
An adhesive sheet for display was prepared in the same manner as in example 1. However, unlike example 1, a pressure-sensitive adhesive sheet for display was finally prepared using a compound represented by the following chemical formula 6 (Miwon, miramer M262) as a (meth) acrylic compound having an oxyalkylene chain.
Chemical formula 6:
comparative example 2
An adhesive sheet for display was prepared in the same manner as in example 1. However, unlike example 1, a pressure-sensitive adhesive sheet for display was finally prepared using a compound represented by the following chemical formula 7 (Miwon, miramer M121) as a (meth) acrylic compound having an oxyalkylene chain.
Chemical formula 7:
in the above chemical formula 7, R 3 is-C 12 H 25 or-C 13 H 27 。
Comparative example 3
An adhesive sheet for display use was prepared in the same manner as in example 1. However, unlike example 1, an ethoxylated methyl behenyl methacrylate (Solvay company,
BEM) as a (meth) acrylic compound having an oxyalkylene chain, finally preparing an adhesive sheet for display.
Experimental example 1
The adhesive sheets for display prepared in each example and comparative example were evaluated based on the following physical property evaluation methods, and the results are shown in table 1.
(1) Adhesion force (gf/25 mm) of variable adhesive layer
After the adhesive sheet for display was cut into a size of 25mm × 200mm in width, the liner film was removed, and one surface of a polyimide film (thickness: 25 μm) was attached with a variable adhesive layer at a speed of 3m/min using a 2kg hand roller. After the attachment, the pressure-sensitive adhesive layer was left at room temperature (25 ℃) for 1 hour, and peeled at an angle of 180 ° at a speed of 300mm per minute to measure the adhesive strength of the pressure-sensitive adhesive layer.
(2) Adhesion force (gf/25 mm) of variable adhesive layer after irradiation with ultraviolet ray
After the adhesive sheet for display was cut into a size of 25mm × 200mm in width, the liner film was removed, and the side to which the variable adhesive layer was attached to a polyimide film (thickness: 25 μm) at a speed of 3m/min using a 2kg hand roller. After the adhesion, ultraviolet rays were irradiated in the vertical direction of the base film using a high-pressure mercury lamp, and then peeled at an angle of 180 ° at a speed of 300mm per minute to measure the adhesive force of the variable adhesive layer.
* Ultraviolet irradiation conditions
(1) Wavelength: 250-450 nm
(2) Light amount: 300mJ/cm 2
(3) Output power: 80mW
(3) Adhesion of variable adhesive layer to base film
The liner film of the adhesive sheet for display was removed, one side of the variable adhesive layer was Cross-cut (Cross cut), and then rubbed 5 times with a finger to visually evaluate the degree of peeling. ( Evaluation criteria (number of rubs): the number of peeling is 1 to 3 times represented by X, the number of peeling is 4 to 5 times represented by Delta, and the number of peeling is 5 or more times represented by O )
(4) Turbidity (Haze,%), transmittance (%)
The haze and transmittance of the pressure-sensitive adhesive sheet for display after peeling off the liner film were measured using a penetrometer (Hazemeter) (NDH 7000).
(5) Measurement of Change in adhesive force of variable adhesive layer after standing at high temperature and high humidity
After removing the liner film of the pressure-sensitive adhesive sheet for display, the surface of the polyimide film (thickness: 25 μm) to which the pressure-sensitive adhesive layer was attached was irradiated with ultraviolet rays in the direction perpendicular to the base film using a high-pressure mercury lamp, and then the sheet was left at 60 ℃ and 95% relative humidity for 500 hours. After the pressure-sensitive adhesive layer was sufficiently left at normal temperature (25 ℃), the pressure-sensitive adhesive layer was peeled at a rate of 300mm per minute at an angle of 180 ° to measure the adhesive strength, and the rate of change in the adhesive strength was measured with the initial adhesive strength of each layer being 100%. The case where the rate of change in the adhesive force satisfies the range of. + -. 20% is indicated by. Smallcircle., and the case where it does not satisfy it is indicated by. Smallcircle.).
* Conditions of ultraviolet irradiation
(1) Wavelength: 250-450 nm
(2) Light amount: 300mJ/cm 2
(3) Output power: 80mW
(6) Evaluation of bending Properties
After removing the liner film of the adhesive sheet for display, one side of the polyimide film (thickness: 25 μm) to which the variable adhesive layer was attached was irradiated with ultraviolet rays in the vertical direction of the base film using a high pressure mercury lamp, and then cut into pieces each having a size of 25mm × 150mm in the horizontal direction. Then, both ends of the polyimide film to which the adhesive sheet for display was attached were brought into contact, and after 10000 times of bending (bending) was performed by setting a curvature radius 3R, the case where no abnormality was caused was indicated by o, and the case where any abnormality such as interlayer peeling and/or peeling from the attached surface in the adhesive sheet for display was caused was indicated by x, thereby evaluating the bending performance.
* Conditions of ultraviolet irradiation
(1) Wavelength: 250-450 nm
(2) Light amount: 300mJ/cm 2
(3) Output power: 80mW
TABLE 1
As can be seen from table 1, in the adhesive sheets for display prepared in examples 1 to 3, the adhesive sheet was easily peeled off again in the step of attaching the adhesive sheet to a display device because the adhesive force was low by irradiation with ultraviolet rays, and the adhesive force was orderly after the irradiation with ultraviolet rays, and the adhesive sheet not only had excellent adhesion between the variable adhesive layer and the base film, but also had excellent transmittance, small change rate of adhesive force, and excellent bending property while maintaining a low haze value.
Those skilled in the art to which the invention pertains will readily appreciate that numerous modifications and variations of the present invention are possible and can be readily devised by those skilled in the art.
Claims (8)
1. A variable-adhesion adhesive composition for displays, comprising:
a (meth) acrylic polymer containing, as a main component, (meth) acrylic monomers having an alkyl group with a carbon number of 1 to 14;
(meth) acrylic compounds having an oxyalkylene chain; and
a photo-initiator,
the (meth) acrylic compound having an oxyalkylene chain includes a compound represented by the following chemical formula 1,
chemical formula 1:
in the above chemical formula 1, A is-CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 -，R 1 And R 2 Are each independently C 1 ～C 5 N is a rational number satisfying 100 to 1000.
2. The variable adhesion composition for display according to claim 1, wherein the (meth) acrylic polymer contains a carboxyl group or a hydroxyl group as a functional group.
3. The variable adhesion composition for display according to claim 1, wherein the variable adhesion composition comprises 5 to 15 parts by weight of a (meth) acrylic compound having an oxyalkylene chain and 0.1 to 1 part by weight of a photoinitiator, based on 100 parts by weight of the (meth) acrylic polymer.
4. The variable adhesion composition for display use according to claim 1, further comprising at least one selected from a crosslinking agent and a solvent.
5. The variable adhesion composition for display according to claim 4, wherein the variable adhesion composition comprises 0.1 to 10 parts by weight of the crosslinking agent and 10 to 30 parts by weight of the solvent, based on 100 parts by weight of the (meth) acrylic polymer.
6. An adhesive sheet for display use comprising a variable adhesive layer comprising the adhesive composition having variable adhesive force for display use according to any one of claims 1 to 5,
the adhesive sheet for display satisfies the following conditions (1) and (2):
(1)A≤100，
(2)300≤B，
in the above condition (1), A represents the adhesive force of the pressure-sensitive adhesive layer measured by adhering the pressure-sensitive adhesive sheet for display to a polyimide film, leaving the sheet at 25 ℃ for 1 hour, and peeling the sheet at a speed of 300mm per minute and an angle of 180 DEG, and the unit of the adhesive force is gf/25mm,
in the above condition (2), B represents that the pressure-sensitive adhesive sheet for display is adhered to a polyimide film at 300mJ/cm 2 The bonding force of the pressure-sensitive adhesive layer was measured by peeling at a rate of 300mm per minute and at an angle of 180 degrees after irradiation with ultraviolet rays, and the unit of the bonding force was gf/25mm.
7. The adhesive sheet for display according to claim 6, further comprising a base film laminated on one surface of the variable adhesive layer.
8. The adhesive sheet for display use according to claim 7, wherein at least one side of the base film comprises an antistatic layer.
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| KR1020190172072A KR102315065B1 (en) | 2019-12-20 | 2019-12-20 | Adhesion variable adhesive composition for display and Adhesive sheet for display comprising the same |
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| JP2008001739A (en) * | 2006-06-20 | 2008-01-10 | Bridgestone Corp | Adhesive composition for electronic display, adhesive layer for electronic display and adhesive filter for electronic display |
| JP2015157913A (en) * | 2014-02-25 | 2015-09-03 | 積水化学工業株式会社 | Adhesive composition for optical use, adhesive sheet for optical sheet, and optical laminate |
| CN109971410A (en) * | 2017-12-14 | 2019-07-05 | 三星Sdi株式会社 | Adhesive composition, its solution, adhesive phase and surface protection film |
| WO2019199085A1 (en) * | 2018-04-12 | 2019-10-17 | 주식회사 엘지화학 | Adhesive sheet for temporary attachment and semiconductor device producing method using same |
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| KR100252953B1 (en) | 1997-07-31 | 2000-04-15 | 구자홍 | Organic electroluminescence device |
| JP2014111705A (en) * | 2012-03-30 | 2014-06-19 | Nitto Denko Corp | Pressure sensitive adhesive sheet |
| JP6267854B2 (en) * | 2012-04-06 | 2018-01-24 | 日東電工株式会社 | Adhesive composition, adhesive sheet, and optical member |
| KR102050620B1 (en) * | 2015-10-30 | 2019-11-29 | 주식회사 엘지화학 | Adhesive composition and polarizing plate comprising adhesive layer formed by using the same |
| JP6895250B2 (en) * | 2016-12-28 | 2021-06-30 | 日東電工株式会社 | Surface protective film |
| JP6952497B2 (en) * | 2017-05-31 | 2021-10-20 | 日東電工株式会社 | Adhesive composition, surface protective sheet, and optical member |
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| JP2008001739A (en) * | 2006-06-20 | 2008-01-10 | Bridgestone Corp | Adhesive composition for electronic display, adhesive layer for electronic display and adhesive filter for electronic display |
| JP2015157913A (en) * | 2014-02-25 | 2015-09-03 | 積水化学工業株式会社 | Adhesive composition for optical use, adhesive sheet for optical sheet, and optical laminate |
| CN109971410A (en) * | 2017-12-14 | 2019-07-05 | 三星Sdi株式会社 | Adhesive composition, its solution, adhesive phase and surface protection film |
| WO2019199085A1 (en) * | 2018-04-12 | 2019-10-17 | 주식회사 엘지화학 | Adhesive sheet for temporary attachment and semiconductor device producing method using same |
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