CN115895491A - Protective film for OLED panel manufacturing process - Google Patents

Protective film for OLED panel manufacturing process Download PDF

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Publication number
CN115895491A
CN115895491A CN202210641831.1A CN202210641831A CN115895491A CN 115895491 A CN115895491 A CN 115895491A CN 202210641831 A CN202210641831 A CN 202210641831A CN 115895491 A CN115895491 A CN 115895491A
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protective film
temperature
glass
adhesive layer
adhesive
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花国栋
郭文磊
尹英允
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Ty Cooperation Co
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Ty Cooperation Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2427/00—Presence of halogenated polymer

Abstract

The present invention relates to a protective film for use in a process for manufacturing an OLED panel, and more particularly, to a protective film for use in a process for manufacturing an OLED panel, which has excellent adhesion retention and excellent impact resistance even in a high temperature of 50 to 100 ℃ or a high humidity environment of 80% or more.

Description

Protective film for OLED panel manufacturing process
[ technical field ] A method for producing a semiconductor device
The present invention relates to a protective film for use in a process for manufacturing an OLED panel, and more particularly, to a protective film for use in a process for manufacturing an OLED panel, which has excellent adhesion retention and impact resistance even in a high temperature of 5 to 100 ℃ or a high humidity environment of 80% or more.
[ background of the invention ]
Recently, with the dramatic development of information communication technology and the expansion of the market, flat Panel Display devices (Flat Panel displays) have attracted attention as Display devices for image Display apparatuses. Typical examples of such flat panel Display devices include Liquid Crystal Display devices (Liquid Crystal displays), plasma Display devices (Plasma Display P anel), organic Light Emitting Devices (OLEDs), and the like.
Organic light emitting devices have advantages of fast response speed, light weight, small size, low power consumption, self-luminescence, flexibility, etc., and recently, demands for new generation display devices, flexible display devices, illumination, etc. are increasing.
The organic light emitting device is formed by sequentially depositing 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 is that electrons and holes supplied by two end electrodes are combined on the organic light emitting layer to release energy to emit light.
Since the organic light emitting device is deteriorated by external factors such as external moisture, oxygen, ultraviolet rays, etc., a packaging (packing) technique for sealing the organic light emitting device is very important, and the organic light emitting display device is required to be thin in order to be applied to various applications.
On the other hand, in manufacturing the OLED panel, a protective film for protecting the OLED panel is included at a lower portion or/and an upper portion of the OLED panel. For example, if a method for manufacturing an OLED panel is briefly described, a protective film for manufacturing the OLED panel is attached to a lower portion of a substrate, a packaging operation is performed on an upper portion of the substrate, a plurality of cells spaced apart from each other by a predetermined interval are manufactured, the protective film for manufacturing the OLED panel is covered on the substrate on which the cells are manufactured, and then the substrate is cut into the cells to complete the plurality of OLED panels.
In this case, as for the lower protective film for protecting the OLED panel in the lower portion of the OLED panel, the conventional lower protective film for the OLED panel can be applied to a flexible display device due to elasticity and impact resistance characteristics, but the adhesion holding force under different environments is not good, and thus there is a problem that the adhesion force with the OLED panel is low, and the durability is not good.
[ Prior art documents ]
[ patent document ]
( Patent document 0001) korean patent laid-open No. 10-2014-0142240 (publication date: 2014.12.11 )
[ summary of the invention ]
[ technical problem ] to provide a method for producing a semiconductor device
The present invention has been made in view of the above problems, and an object of the present invention is to provide a protective film for use in a process for producing an OLED panel, which has excellent adhesion retention and impact resistance even in a high temperature of 50 to 100 ℃ or a high humidity environment of 80% or more.
Further, it is an object to provide a protective film for an OLED panel production process, which has a low moisture permeability (WVTR), is excellent in adhesion retention not only in a low temperature environment of-10 to-50 ℃ and a high temperature environment of 50 to 100 ℃ but also in a thermal shock environment, and is also excellent in elasticity.
[ technical solution ] A
In order to solve the above problems, the protective film for use in the process of manufacturing an OLED panel according to the present invention includes a base film and an adhesive layer laminated on one surface of the base film.
In a preferred embodiment of the present invention, the adhesive layer may contain a fluorine-substituted urethane acrylate copolymer as a main agent resin.
In a preferred embodiment of the present invention, the protective film for an OLED panel manufacturing process of the present invention may satisfy all of the conditions (4) and (5).
(4)0.5≤A/E≤1.0
In the above condition (4), a represents the adhesive force of the adhesive layer measured by peeling the protective film base film at 180 ° at a rate of 5mm per second at a temperature of 25 ℃ after the adhesive layer of the protective film is adhered to the glass (glass), and E represents the adhesive force of the adhesive layer measured by adhering the adhesive layer of the protective film to the glass (glass), exposing for 500 hours at a temperature of 60 ℃ and a humidity of 90%, aging (aging) for 4 hours at a temperature of 25 ℃, and peeling the protective film base film at a rate of 5mm per second at a temperature of 25 ℃ after the adhesive layer of the protective film is adhered to the glass (glass).
(5)1.0≤A/F≤2.0
In the above condition (5), a represents the adhesive force of the adhesive layer measured by peeling the protective film base film at 180 ° at a rate of 5mm per second at a temperature of 25 ℃ after the adhesive layer of the protective film is adhered to glass (glass), and F represents the adhesive force of the adhesive layer measured by adhering the adhesive layer of the protective film to glass (glass), exposing for 500 hours at a temperature of 85 ℃ and a humidity of 85%, aging (aging) for 4 hours at a temperature of 25 ℃, and peeling the protective film base film at a rate of 5mm per second at a temperature of 25 ℃ after the adhesive layer of the protective film is adhered to glass (glass).
In a preferred embodiment of the present invention, the protective film for use in the process of manufacturing an OLED panel according to the present invention does not generate bubbles between the adhesive layer of the protective film and glass (glass) even if an impact is applied to the base film of the protective film after the adhesive layer of the protective film is attached to the glass.
In a preferred embodiment of the present invention, the weight average molecular weight of the fluorine-substituted urethane acrylate copolymer may be 5000 to 1000000.
In a preferred embodiment of the present invention, the fluoro-substituted urethane acrylate copolymer may comprise repeating units derived from hydroxyl-terminated perfluoropolyether.
In a preferred embodiment of the present invention, the hydroxyl-terminated perfluoropolyether can contain 2 to 10 fluorines.
In a preferred embodiment of the present invention, the adhesive layer may further include an acrylate monomer.
In a preferred embodiment of the present invention, the acrylate monomer may include a compound represented by the following chemical formula 1, a compound represented by the following chemical formula 2, a compound represented by the following chemical formula 3, and Isobornyl acrylate (Isobornyl acrylate).
[ chemical formula 1]
Figure BDA0003682434480000051
In the above chemical formula 1, B 1 is-CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 CH 2 -，R 1 And R 2 Are respectively and independently C1-C12 straight-chain alkyl, C3-C12 branched-chain alkyl, phenyl or alkyl phenyl.
[ chemical formula 2]
Figure BDA0003682434480000052
In the above chemical formula 2, B 3 is-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 -、- CH 2 CH 2 CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -。
[ chemical formula 3]
Figure BDA0003682434480000053
In the above chemical formula 3, B 2 is-CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 -、- CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -。
In a preferred embodiment of the present invention, the adhesive layer may include 1 to 10 parts by weight of the compound represented by the above chemical formula 1, 1 to 10 parts by weight of the compound represented by the above chemical formula 2, 1 to 10 parts by weight of the compound represented by the above chemical formula 3, and 15 to 35 parts by weight of Isobornyl acrylate (Isobornyl acrylate) with respect to 100 parts by weight of the main agent resin.
In a preferred embodiment of the present invention, the base film may be a permanent antistatic film comprising a permanent antistatic agent and a plastic resin.
In a preferred embodiment of the present invention, the base film and the adhesive layer of the protective film for an OLED panel manufacturing process of the present invention may have a thickness of 1: a thickness ratio of 0.13 to 0.66.
In a preferred embodiment of the present invention, the adhesive layer may further include a photoinitiator and an antistatic agent.
In a preferred embodiment of the present invention, the protective film for an OLED panel manufacturing process of the present invention may further satisfy the conditions (6) and (7).
(6)0.8≤A/W≤1.5
In the above condition (6), a represents the adhesive force of the adhesive layer measured by peeling the protective film base film at 180 ° at a speed of 5mm per second at a temperature of 25 ℃ after the adhesive layer of the protective film is attached to the glass (glass), and W represents the adhesive holding force of the adhesive layer measured by peeling the protective film base film at 180 ° at a speed of 5mm per second at a temperature of 0 ℃ after the adhesive layer of the protective film is attached to the glass (glass).
(7)0.8≤A/Y≤1.5
In the above condition (7), a represents the adhesive force of the adhesive layer measured by peeling the protective film base film at a rate of 5mm per second at a temperature of 25 ℃ after the adhesive layer of the protective film is attached to the glass (glass), and Y represents the adhesive force of the adhesive layer measured by peeling the protective film base film at a rate of 180 ° per second at a temperature of 25 ℃ after exposure to the glass (glass) at a temperature of 0 ℃ for 1000 hours, aging (aging) at a temperature of 25 ℃ for 4 hours, and then peeling the protective film base film at a rate of 5mm per second at a temperature of 25 ℃.
In a preferred embodiment of the present invention, the protective film for an OLED panel manufacturing process of the present invention may further satisfy the conditions (8) and (9).
(8)0.4≤A/H≤1.5
In the above condition (8), a represents the adhesive force of the adhesive agent layer measured by peeling the base film of the protective film at 180 ° at a rate of 5mm per second at a temperature of 25 ℃ after the adhesive agent layer of the protective film is adhered to the glass (glass), and H represents the adhesive force of the adhesive agent layer measured by peeling the base film of the protective film at 180 ° at a rate of 5mm per second at a temperature of 25 ℃ after exposure to-30 ℃ for 500 hours and aging (aging) at a temperature of 25 ℃ for 4 hours after the adhesive agent layer of the protective film is adhered to the glass (glass).
(9)0.4≤A/Z≤1.0
In the above condition (9), a represents the adhesive force of the adhesive layer measured by peeling the base film of the protective film at 180 ° at a rate of 5mm per second at a temperature of 25 ℃ after the adhesive layer of the protective film is attached to the glass (glass), and Z represents the adhesive force of the adhesive layer measured by peeling the base film of the protective film at 180 ° at a rate of 5mm per second at a temperature of 25 ℃ after the adhesive layer of the protective film is attached to the glass (glass), exposed for 1000 hours at a temperature of 60 ℃, aged (aging) at a temperature of 25 ℃ for 4 hours, and then peeled at a temperature of 25 ℃ for 5mm per second.
[ Effect of the invention ]
The protective film for the OLED panel manufacturing process has excellent adhesion retention and impact resistance under the high temperature of 50-100 ℃ and high humidity environment of more than 80%.
In addition, the protective film for the OLED panel manufacturing process is excellent in adhesion retention and elasticity under the thermal shock environment, not only in the low temperature of-10 to-50 ℃ and the high temperature of 50 to 100 ℃.
[ description of the drawings ]
Fig. 1 is a schematic cross-sectional view of a protective film for an OLED panel manufacturing process according to the present invention, as a preferred embodiment of the present invention.
[ detailed description ] embodiments
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings so that those skilled in the art can easily implement the embodiments of the present invention. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In the drawings, in order to clearly describe the present invention, portions irrelevant to the description are omitted, and the same reference numerals are given to the same or similar constituent elements throughout the specification.
Referring to fig. 1, the protective film for an OLED panel manufacturing process of the present invention includes a base film (10) and an adhesive layer (20) laminated on one surface of the base film (10).
In addition, a release film (30) can be laminated on one surface of the adhesive layer (20), and the protective film for the OLED panel manufacturing process can be formed by sequentially laminating a base film (10), the adhesive layer (20) and the release film (30).
The base film (10) is directly attached to the surface of the OLED panel and takes on the function of protecting the surface of the OLED panel. The base film (10) may include materials generally available in the industry for protective films without limitation, and preferably, may be a permanent antistatic film comprising a permanent antistatic agent and a plastic resin. In other words, the base film of the present invention is not in a form in which an antistatic agent is coated on a film that can be removed by physical force, but is a film that is permanently provided with an antistatic effect and is formed by mixing a permanent antistatic agent into the film during film processing. At this time, the permanent antistatic agent may include any antistatic agent used in the industry, and preferably, may include one or more selected from the group consisting of PEO, nylon-co-PEO, butadiene-co-PEO, PET-co-PEO, styrene-co-PEO, and IDP (interferometric dispersive Polymer). In addition, the plastic resin may include, but is not limited to, one or more selected from PP resin, PET resin, and PE resin.
The thickness of the base film (10) is not limited as long as it is a thickness that can be generally used for a protective film, and may be preferably 50 to 100 μm, more preferably 70 to 80 μm, but is not limited thereto.
The adhesive layer (20) exerts a predetermined adhesive force for allowing the base film (10) to be attached to the upper and/or lower portion of the OLED panel, preferably, to the lower portion, and the adhesive layer (20) of the present invention may contain a fluorine-substituted urethane acrylate copolymer (fluorinated-urethane acrylate copolymer) as a main agent resin. In this case, the main agent resin is a base material for allowing the adhesive agent layer (20) to have an adhesive force, in other words, a component accounting for 50 wt% or more of the acrylate constituting the adhesive agent layer.
The weight average molecular weight of the fluorine-substituted urethane acrylate copolymer of the present invention may be 5000 to 1000000, preferably 10000 to 500000, more preferably 10000 to 200000, and if the weight average molecular weight is less than 5000, there is a problem of low adhesive force, and if it exceeds 1000000, reactivity is lowered, and there is a problem of generation of unreacted oligomer.
In addition, the fluoro-substituted urethane acrylate copolymer of the present invention may include a repeating unit derived from hydroxyl-terminated perfluoropolyether (hydroxyl-terminated perfluoropolyether). In other words, in synthesizing the fluorine-substituted urethane acrylate copolymer of the present invention, a hydroxyl-terminated perfluoropolyether may be used, and the hydroxyl-terminated perfluoropolyether may be introduced into the main chain of the fluorine-substituted urethane acrylate copolymer of the present invention.
On the other hand, the hydroxyl-terminated perfluoropolyether may include 2 to 10 fluorines, preferably, 3 to 8 fluorines, and more preferably, 3 to 6 fluorines, and if the number of fluorines is less than 2, there is a problem that the moisture permeability is increased or the adhesive holding power under different environments is lowered, and if the number of substituted fluorines exceeds 10, there is a problem that the adhesive holding power under different environments is lowered.
On the other hand, the adhesive layer (20) may contain an acrylate monomer in addition to the main agent resin.
At this time, as the acrylate monomer, one or more selected from the group consisting of a compound represented by the following chemical formula 1, a compound represented by the following chemical formula 2, a compound represented by the following chemical formula 3, and Isobornyl acrylate (Isobornyl acrylate) may be included, and preferably, a compound represented by the following chemical formula 1, a compound represented by the following chemical formula 2, a compound represented by the following chemical formula 3, and Isobornyl acrylate (Isobornyl acrylate) may be included.
[ chemical formula 1]
Figure BDA0003682434480000101
/>
In the above chemical formula 1, B 1 is-CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 CH 2 -, preferably, -CH 2 -、-CH 2 CH 2 -or-CH 2 CH 2 CH 2 -。
In addition, in the chemical formula 1, R 1 And R 2 Are respectively independentIs a C1-C12 straight-chain alkyl group, a C3-C12 branched-chain alkyl group, a phenyl group or an alkylphenyl group, preferably is a C1-C12 straight-chain alkyl group, more preferably R 1 Is ethyl, R 2 Is butyl.
[ chemical formula 2]
Figure BDA0003682434480000111
In the above chemical formula 2, B 3 is-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 -、- CH 2 CH 2 CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -, preferably, -CH 2 -、-CH 2 CH 2 -or-CH 2 CH 2 CH 2 -。
[ chemical formula 3]
Figure BDA0003682434480000112
In the above chemical formula 3, B 2 is-CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 -、- CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -, preferably, -CH 2 CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -。
Specifically, the adhesive layer (20) may contain 1 to 10 parts by weight, preferably 3 to 7 parts by weight, of the compound represented by the above chemical formula 1, based on 100 parts by weight of the main agent resin, and if the amount is outside the above range, the physical properties desired in the present invention may not be satisfied.
The adhesive layer (20) may contain 1 to 10 parts by weight, preferably 3 to 7 parts by weight, of the compound represented by the above chemical formula 2, based on 100 parts by weight of the main agent resin, and if the amount is outside the above range, the physical properties desired in the present invention may not be satisfied.
The adhesive agent layer (20) may contain 1 to 10 parts by weight, preferably 3 to 7 parts by weight, of the compound represented by the above chemical formula 3, based on 100 parts by weight of the main agent resin, and if the amount is outside the above range, the desired physical properties of the present invention may not be satisfied.
The adhesive layer (20) may contain 15 to 35 parts by weight, preferably 20 to 30 parts by weight of Isobornyl acrylate (Isobornyl acrylate) per 100 parts by weight of the main resin, and if the amount is outside the above range, the desired physical properties of the present invention may not be satisfied.
Further, the adhesive layer (20) of the present invention may further contain one or more selected from a photoinitiator and an antistatic agent, and preferably, may further contain a photoinitiator and an antistatic agent.
The photoinitiator is a substance that absorbs energy from an ultraviolet light source and accelerates a curing reaction, and is not limited as long as it is a photoinitiator that is generally used for a protective film in the industry. Preferably, a compound represented by the following chemical formula 4 may be included.
[ chemical formula 4]
Figure BDA0003682434480000121
In the above chemical formula 4, R 3 、R 4 、R 5 、R 7 And R 8 Are respectively and independently-H, C1-C12Is a linear alkyl group of C3 to C12, preferably-H or a linear alkyl group of C1 to C12.
The antistatic agent is a substance that can prevent static electricity, and is not limited as long as it is an antistatic agent that is generally used for a protective film in the industry.
The adhesive layer (20) may contain 0.1 to 5 parts by weight, preferably 0.5 to 1.5 parts by weight of a photoinitiator per 100 parts by weight of the main agent resin.
The adhesive layer (20) may contain 0.01 to 1 part by weight, preferably 0.1 to 0.4 part by weight, of an antistatic agent per 100 parts by weight of the main agent resin.
The thickness of the adhesive layer (20) is not limited by the thickness of the base film, and may be preferably 5 to 30 μm, more preferably 10 to 20 μm, but is not limited thereto.
On the other hand, the base film (10) and the adhesive layer (20) of the protective film for an OLED panel manufacturing process of the present invention may have a thickness of 1: a thickness ratio of 0.13 to 0.66, preferably, may have a thickness ratio of 1:0.15 to 0.4, more preferably, may have a thickness ratio of 1: a thickness ratio of 0.15 to 0.3.
Further, the adhesive layer (20) of the present invention can have a moisture vapor transmission rate (WVTR) of 15g/m as measured in accordance with ASTM E-398 test specification 2 Less than day, preferably, 1 to 10g/m 2 Day, more preferably, it may be 2 to 8 g/m 2 It may be more preferably 3 to 5g/m 2 Day.
The release film (30) may be included without limitation as long as it is a material generally used for release films in the industry, and preferably, may include a PET (polyethylene terephthalate) film, and more preferably, may include a PET film subjected to a silicon release treatment. The thickness of the release film (30) is not limited as long as the thickness of the release film (30) can be generally used for a protective film, and preferably, it may be 10 to 50 μm, and more preferably, it may be 20 to 30 μm, but is not limited thereto.
Further, the protective film for an OLED panel manufacturing process of the present invention may satisfy the following condition (1).
(1) 0.8. Ltoreq. A/B. Ltoreq.5.0, preferably 0.9. Ltoreq. A/B. Ltoreq.2.0, more preferably 1.2. Ltoreq. A/B. Ltoreq.1.6, even more preferably 1.3. Ltoreq. A/B. Ltoreq.1.5
In the above condition (1), a represents the adhesive force of the adhesive layer measured by peeling the protective film base film at 180 ° at a speed of 5mm per second at a temperature of 25 ℃ after the adhesive layer of the protective film is attached to glass (glass).
In the above condition (1), B represents the adhesive holding power of the adhesive layer measured by peeling the protective film base film at 180 ℃ at a rate of 5mm per second at a temperature of-30 ℃ after the adhesive layer of the protective film is adhered to glass (glass).
In addition, the protective film for an OLED panel manufacturing process of the present invention may further satisfy the following condition (2).
(2) 0.8. Ltoreq. A/C.ltoreq.2.5, preferably 0.9. Ltoreq. A/C.ltoreq.2.0, more preferably 1.0. Ltoreq. A/C.ltoreq.1.5, still more preferably 1.1. Ltoreq. A/C.ltoreq.1.3
In the above condition (2), a represents the adhesive force of the adhesive layer measured by peeling the protective film base film at 180 ° at a temperature of 25 ℃ at a speed of 5mm per second after the adhesive layer of the protective film is adhered to glass (glass).
In the above condition (2), C represents the adhesive holding power of the adhesive layer measured by peeling the protective film base film at 180 ° at a speed of 5mm per second at a temperature of 60 ℃ after the adhesive layer of the protective film is attached to glass (glass).
In addition, the protective film for an OLED panel manufacturing process of the present invention may further satisfy the following condition (3).
(3) 0.3. Ltoreq. A/D. Ltoreq.1.5, preferably 0.5. Ltoreq. A/D. Ltoreq.1.2, more preferably 0.7. Ltoreq. A/D. Ltoreq.1.0, even more preferably 0.8. Ltoreq. A/D. Ltoreq.0.9
In the above condition (3), a represents the adhesive force of the adhesive layer measured by peeling the base film of the protective film at 180 ° at a speed of 5mm per second at a temperature of 25 ℃ after the adhesive layer of the protective film is adhered to glass (glass).
In the above condition (3), D represents the adhesive force of the adhesive layer measured by attaching the adhesive layer of the protective film to glass (glass), repeating the process of exposure to-20 ℃ for 30 minutes and 60 ℃ for 30 minutes, aging (taping) at 25 ℃ for 4 hours, and peeling the protective film base film at 180 ° at a rate of 5mm per second at 25 ℃.
In addition, the protective film for an OLED panel manufacturing process of the present invention may further satisfy the following condition (4).
(4) 0.5. Ltoreq. A/E.ltoreq.1.0, preferably 0.5. Ltoreq. A/E.ltoreq.0.9, more preferably 0.5. Ltoreq. A/E.ltoreq.0.8, even more preferably 0.55. Ltoreq. A/E.ltoreq.0.7
In the above condition (4), a represents the adhesive force of the adhesive layer measured by peeling the protective film base film at 180 ° at a temperature of 25 ℃ at a speed of 5mm per second after the adhesive layer of the protective film is adhered to glass (glass).
In the above condition (4), E represents the adhesive force of the adhesive layer measured by adhering the adhesive layer of the protective film to glass (glass), exposing for 500 hours at a temperature of 6 ℃ and a humidity of 90%, aging (aging) for 4 hours at a temperature of 25 ℃, and peeling the protective film base film at a speed of 5mm per second at a temperature of 25 ℃ at 180 °.
In addition, the protective film for an OLED panel manufacturing process of the present invention may further satisfy the following condition (5).
(5) 1.0. Ltoreq. A/F. Ltoreq.2.0, preferably 1.0. Ltoreq. A/F. Ltoreq.1.6, more preferably 1.1. Ltoreq. A/F. Ltoreq.1.4, still more preferably 1.2. Ltoreq. A/F. Ltoreq.1.3
In the above condition (5), a represents the adhesive force of the adhesive layer measured by peeling the protective film base film at 180 ° at a speed of 5mm per second at a temperature of 25 ℃ after the adhesive layer of the protective film is attached to glass (glass).
In the above condition (5), F represents the adhesive force of the adhesive layer measured by adhering the adhesive layer of the protective film to glass (glass), exposing for 500 hours at a temperature of 8 ℃ and a humidity of 85%, aging (aging) for 4 hours at a temperature of 25 ℃, and peeling the protective film base film at a speed of 5mm per second at a temperature of 25 ℃ at 180 °.
In addition, the protective film for an OLED panel manufacturing process of the present invention may further satisfy the following condition (6).
(6) 0.8. Ltoreq. A/W.ltoreq.1.5, preferably 1.0. Ltoreq. A/W.ltoreq.1.4, more preferably 1.1. Ltoreq. A/W.ltoreq.1.3, even more preferably 1.15. Ltoreq. A/W.ltoreq.1.25
In the above condition (6), a represents the adhesive force of the adhesive layer measured by peeling the protective film base film at 180 ° at a temperature of 25 ℃ at a speed of 5mm per second after the adhesive layer of the protective film is adhered to glass (glass).
In the above condition (6), W represents the adhesive holding power of the adhesive layer measured by peeling the protective film base film at 180 ° at a temperature of 0 ℃ at a speed of 5mm per second after the adhesive layer of the protective film is attached to glass (glass).
In addition, the protective film for an OLED panel manufacturing process of the present invention may satisfy the following condition (7).
(7) 0.8. Ltoreq. A/Y.ltoreq.1.5, preferably 0.8. Ltoreq. A/Y.ltoreq.1.3, more preferably 0.9. Ltoreq. A/Y.ltoreq.1.2, further more preferably 1.0. Ltoreq. A/Y.ltoreq.1.1
In the above condition (7), a represents the adhesive force of the adhesive layer measured by peeling the protective film base film at 180 ° at a speed of 5mm per second at a temperature of 25 ℃ after the adhesive layer of the protective film is attached to glass (glass).
In the above condition (7), Y represents the adhesive force of the adhesive layer measured by adhering the adhesive layer of the protective film to glass (glass), exposing the adhesive layer at a temperature of 0 ℃ for 1000 hours, aging (imaging) the adhesive layer at a temperature of 25 ℃ for 4 hours, and peeling the protective film base film at a rate of 5m m/sec at a temperature of 25 ℃ at 180 °.
In addition, the protective film for an OLED panel manufacturing process of the present invention may further satisfy the following condition (8).
(8) 0.4. Ltoreq. A/H. Ltoreq.1.5, preferably 0.8. Ltoreq. A/H. Ltoreq.1.4, more preferably 1.0. Ltoreq. A/H. Ltoreq.1.3, even more preferably 1.05. Ltoreq. A/H. Ltoreq.1.25
In the above condition (8), a represents the adhesive force of the adhesive layer measured by peeling the protective film base film at 180 ° at a temperature of 25 ℃ at a speed of 5mm per second after the adhesive layer of the protective film is adhered to glass (glass).
In the above condition (8), H represents the adhesive force of the adhesive layer measured by adhering the adhesive layer of the protective film to glass (glass), exposing at a temperature of-30 ℃ for 500 hours, aging at a temperature of 25 ℃ for 4 hours, and peeling the protective film base film at a rate of 5mm per second at a temperature of 25 ℃ at 180 °.
In addition, the protective film for an OLED panel manufacturing process of the present invention may further satisfy the following condition (9).
(9) 0.4. Ltoreq. A/Z.ltoreq.1.0, preferably 0.4. Ltoreq. A/Z.ltoreq.0.9, more preferably 0.4. Ltoreq. A/Z.ltoreq.0.8, even more preferably 0.5. Ltoreq. A/Z.ltoreq.0.7
In the above condition (9), a represents the adhesive force of the adhesive layer measured by peeling the protective film base film at 180 ° at a speed of 5mm per second at a temperature of 25 ℃ after the adhesive layer of the protective film is attached to glass (glass).
In the above condition (9), Z represents the adhesive force of the adhesive layer measured by adhering the adhesive layer of the protective film to glass (glass), exposing the adhesive layer at a temperature of 6 ℃ for 1000 hours, aging (aging) the adhesive layer at a temperature of 25 ℃ for 4 hours, and peeling the protective film base film at a rate of 5mm per second at a temperature of 25 ℃ at 180 °.
On the other hand, the protective film for the OLED panel manufacturing process of the present invention does not generate bubbles between the adhesive layer of the protective film and glass even if an impact is applied to the base film of the protective film after the adhesive layer of the protective film is attached to the glass (glass).
In addition, the protective film for the OLED panel manufacturing process of the present invention was evaluated by bending (bending) 10000 times with a curvature radius of 3.0mm after the adhesive layer of the protective film was attached to the polyimide film, and no crack occurred.
Further, the method for preparing the protective film for an OLED panel manufacturing process of the present invention may include first to third steps.
First, the first step of the method for preparing a protective film for an OLED panel manufacturing process of the present invention may prepare an adhesive composition.
The adhesive composition may be prepared by mixing an acrylate monomer in a main agent resin, and preferably, may be prepared by mixing an acrylate monomer, a photoinitiator, an antistatic agent, and a solvent in a main agent resin. In this case, the solvent is not limited as long as it is generally used as a solvent in the industry, and preferably, toluene may be used.
More specifically, the adhesive composition may be prepared by mixing 1 to 10 parts by weight, preferably 3 to 7 parts by weight of the compound represented by the above chemical formula 1, with respect to 100 parts by weight of the main agent resin.
The adhesive composition may be prepared by mixing 1 to 10 parts by weight, preferably 3 to 7 parts by weight of the compound represented by the above chemical formula 2 with 100 parts by weight of the base resin.
The adhesive composition may be prepared by mixing 1 to 10 parts by weight, preferably 3 to 7 parts by weight of the compound represented by chemical formula 3 with 100 parts by weight of the base resin.
The adhesive composition may be prepared by mixing 15 to 35 parts by weight, preferably 20 to 30 parts by weight of Isobornyl acrylate (Isobornyl acrylate) with 100 parts by weight of the main resin.
The adhesive composition may be prepared by mixing 0.1 to 5 parts by weight of a photoinitiator with respect to 100 parts by weight of the base resin, and preferably 0.5 to 1.5 parts by weight.
The adhesive composition may be prepared by mixing 0.01 to 1 part by weight, preferably 0.1 to 0.4 part by weight of an antistatic agent with respect to 100 parts by weight of the main resin.
The adhesive composition may be prepared by mixing 10 to 50 parts by weight of the solvent, preferably 20 to 40 parts by weight, with 100 parts by weight of the base resin.
Then, the second step of the method for preparing the protective film for an OLED panel manufacturing process of the present invention may coat the adhesive composition prepared in the first step on one side of the base film and dry. At this time, the drying may be performed at a temperature of 100 to 150 ℃, and preferably, may be performed at a temperature of 115 to 135 ℃.
Finally, the third step of the method for preparing a protective film for an OLED panel manufacturing process of the present invention may be to apply a release film to one side of the adhesive composition coated and dried in the second step and then cure the adhesive composition to prepare a base film, an adhesive layer formed by curing the adhesive composition, and a protective film for an OLED panel manufacturing process in which the release film is sequentially stacked.
In this case, the lamination can be performed by a laminator, and the curing after the lamination can be performed by irradiating a UV light amount of 500 to 1500mJ, preferably 800 to 1200 mJ.
The present invention has been described above mainly in terms of the embodiments, but these embodiments are merely examples and do not limit the embodiments of the present invention, and it will be understood by those skilled in the art that various modifications and applications not listed above can be implemented without departing from the essential characteristics of the present invention. For example, the constituent elements specifically shown in the embodiment of the present invention may be modified. Moreover, it is to be understood that variations and modifications related to such variations and applications are intended to be included within the scope of the invention as defined in the appended claims.
Example 1: preparation of protective film for OLED panel manufacturing process
(1) A fluorine-substituted urethane acrylate copolymer (weight average molecular weight: 16000, containing a repeating unit derived from a hydroxyl-terminated perfluoropolyether having 4 fluorine atoms, BNO-4.0F) was prepared as a base resin, and 5 parts by weight of a compound represented by the following chemical formula 1-1, 5 parts by weight of a compound represented by the following chemical formula 2-1, 5 parts by weight of a compound represented by the following chemical formula 3-1, 25 parts by weight of isobornyl acrylate, 1 part by weight of a compound represented by the following chemical formula 4-1 as a photoinitiator, 0.2 part by weight of an antistatic agent (BYK-ES-80, BYK chemical company) and 30 parts by weight of toluene as a solvent were mixed with 100 parts by weight of the base resin to prepare an adhesive composition.
[ chemical formula 1-1]
Figure BDA0003682434480000211
In the above chemical formula 1-1, B 1 is-CH 2 -，R 1 Is ethyl, R 2 Is butyl.
[ chemical formula 2-1]
Figure BDA0003682434480000212
[ chemical formula 3-1]
Figure BDA0003682434480000213
In the above chemical formula 3-1, B 2 is-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -。
[ chemical formula 4-1]
Figure BDA0003682434480000214
In the above chemical formula 4-1, R 3 、R 5 And R 7 Is methyl, R 4 And R 6 is-H.
(2) A permanent antistatic film (film formed by mixing a permanent antistatic agent with PET resin) having a thickness of 75 μm was prepared as a base film, and the prepared adhesive composition was applied to one surface of the base film by a slit coater and then hot air-dried at 125 ℃.
(3) A release film (a PET film having a release treated on one side) having a thickness of 25 μm was laminated on one side of the adhesive composition on which coating and hot air drying were performed using a laminating roller (= the release treated side of the release film was laminated opposite to the adhesive composition), and then irradiated with a UV light of 1000mJ to prepare a protective film for an OLED panel manufacturing process in which a base film, an adhesive layer having a thickness of 15 μm formed by curing the adhesive composition, and a release film were sequentially laminated.
Example 2: preparation of protective film for OLED panel manufacturing process
In the same manner as in example 1, a protective film for use in the OLED panel manufacturing process was prepared. However, unlike example 1, a protective film for an OLED panel manufacturing process was finally prepared using a fluorine-substituted urethane acrylate copolymer comprising a hydroxyl-terminated perfluoropolyether-derived repeating unit having 8 fluorines as a main agent resin.
Example 3: preparation of protective film for OLED panel manufacturing process
In the same manner as in example 1, a protective film for use in the OLED panel manufacturing process was prepared. However, unlike example 1, a protective film for an OLED panel manufacturing process was finally prepared using a fluorine-substituted urethane acrylate copolymer comprising a hydroxyl-terminated perfluoropolyether-derived repeating unit having 2 fluorines as a main agent resin.
Example 4: preparation of protective film for OLED panel manufacturing process
In the same manner as in example 1, a protective film for use in the OLED panel manufacturing process was prepared. However, unlike example 1, an adhesive composition was prepared by mixing 4.167 parts by weight of the compound represented by chemical formula 1-1, 4.167 parts by weight of the compound represented by chemical formula 2-1, 4.167 parts by weight of the compound represented by chemical formula 3-1, 20.833 parts by weight of isobornyl acrylate, 0.833 parts by weight of the compound represented by chemical formula 4-1 as a photoinitiator, 0.167 parts by weight of an antistatic agent (BYK-ES-80, BYK chemical company), and 25 parts by weight of toluene as a solvent, with respect to 100 parts by weight of the base resin, and a protective film for use in a process of manufacturing an OLED panel was finally prepared.
Example 5: preparation of protective film for OLED panel manufacturing process
In the same manner as in example 1, a protective film for an OLED panel manufacturing process was prepared. However, unlike example 1, tricyclodecane dimethanol Diacrylate (tricyclodecane dimethanol Diacrylate) was used instead of the compound represented by the above chemical formula 3-1, and a protective film for an OLED panel manufacturing process was finally prepared.
Example 6: preparation of protective film for OLED panel manufacturing process
In the same manner as in example 1, a protective film for use in the OLED panel manufacturing process was prepared. However, unlike example 1, the adhesive composition was prepared without mixing the antistatic agent, and finally the protective film for the OLED panel manufacturing process was prepared.
Example 7: preparation of protective film for OLED panel manufacturing process
In the same manner as in example 1, a protective film for an OLED panel manufacturing process was prepared. However, unlike example 1, the base film was not a permanent antistatic film having a thickness of 75 μm, but a PET film having antistatic layers formed on both sides by coating PEDOT/PSS (poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) was used to finally prepare a protective film for use in the OLED panel fabrication process.
Comparative example 1: preparation of protective film for OLED panel manufacturing process
In the same manner as in example 1, a protective film for use in the OLED panel manufacturing process was prepared. However, unlike example 1, a protective film for an OLED panel manufacturing process was finally prepared using a urethane acrylate copolymer not substituted with fluorine as a main agent resin.
Comparative example 2: preparation of protective film for OLED panel manufacturing process
In the same manner as in example 1, a protective film for an OLED panel manufacturing process was prepared. However, unlike example 1, a protective film for an OLED panel manufacturing process was finally prepared using polybutylmethacrylate (Polybutyl Methacrylate) as a main agent resin.
Comparative example 3: preparation of protective film for OLED panel manufacturing process
In the same manner as in example 1, a protective film for an OLED panel manufacturing process was prepared. However, unlike example 1, a protective film for an OLED panel manufacturing process was finally prepared using Epoxy Acrylate (Epoxy Acrylate) as a main agent resin.
Comparative example 4: preparation of protective film for OLED panel manufacturing process
In the same manner as in example 1, a protective film for an OLED panel manufacturing process was prepared. However, unlike example 1, in the case of preparing the adhesive composition, 10 parts by weight of the compound represented by the above chemical formula 1-1, 5 parts by weight of the compound represented by the above chemical formula 3-1, 25 parts by weight of isobornyl acrylate, 1 part by weight of the compound represented by the above chemical formula 4-1 as a photoinitiator, 0.2 parts by weight of an antistatic agent (BYK-ES-80, BYK chemical company) and 30 parts by weight of toluene as a solvent were mixed with respect to 100 parts by weight of the main agent resin to prepare the adhesive composition, and finally, the protective film for the OLED panel manufacturing process was prepared.
Comparative example 5: preparation of protective film for OLED panel manufacturing process
In the same manner as in example 1, a protective film for use in the OLED panel manufacturing process was prepared. However, unlike example 1, tricyclodecane dimethanol Diacrylate (tricyclodecane dimethanol Diacrylate) was used instead of the isobornyl acrylate, and a protective film for an OLED panel manufacturing process was finally prepared.
Experimental example 1
The protective films for the OLED panel production process prepared in examples 1 to 7 and comparative examples 1 to 5 were evaluated according to the following physical property evaluation methods, and the results are shown in tables 1 to 2.
(1) Adhesive force of adhesive layer (identified as A. In the following table)
The release film of the protective film was removed, and after the adhesive layer of the protective film was attached to Alkali-free Glass (Non Alkali Glass) at a temperature of 25 ℃ by a laminator and aged (aging) at a temperature of 25 ℃ for 24 hours, the base film of the protective film was peeled at 180 ° at a speed of 5mm per second at a temperature of 25 ℃ by UTM, and the adhesive force of the adhesive layer was measured.
(2) Adhesive holding force of adhesive layer (identified as B. In the following tables)
The release film of the protective film was removed, and after the adhesive layer of the protective film was attached to Alkali-free Glass (Non Alkali Glass) at a temperature of 25 ℃ by a laminator and aged (aging) at a temperature of 25 ℃ for 24 hours, the protective film base film was peeled at 180 ° at a temperature of-30 ℃ at a speed of 5mm per second by UTM, and the adhesion holding power of the adhesive layer was measured.
(3) Adhesive holding force of adhesive layer (identified as W in the following table)
The release film of the protective film was removed, and after the adhesive layer of the protective film was attached to Alkali-free Glass (Non Alkali Glass) at a temperature of 25 ℃ by a laminator and aged (aging) at a temperature of 25 ℃ for 24 hours, the protective film base film was peeled at 180 ° at a speed of 5mm per second at a temperature of 0 ℃ by UTM, and the adhesive holding power of the adhesive layer was measured.
(4) Adhesive Retention of adhesive layer (identified as C. In the following tables)
The release film of the protective film was removed, and after the adhesive layer of the protective film was attached to Alkali-free Glass (Non Alkali Glass) at a temperature of 25 ℃ by a laminator and aged (aging) at a temperature of 25 ℃ for 24 hours, the protective film base film was peeled at 180 ° at a speed of 5mm per second at a temperature of 60 ℃ by UTM, and the adhesive holding power of the adhesive layer was measured.
(5) Adhesive force of adhesive layer (identified as H in the following table)
The release film of the protective film was removed, and the adhesive layer of the protective film was attached to Alkali-free Glass (Non Alkali Glass) at a temperature of 25 ℃ by a laminator, exposed at a temperature of-30 ℃ for 500 hours, aged (aging) at a temperature of 25 ℃ for 4 hours, and then peeled off at 180 ° at a speed of 5mm per second at a temperature of 25 ℃ by UTM, and the adhesive force of the adhesive layer was measured.
(6) Adhesive force of adhesive layer (identified as Y in the following table)
The release film of the protective film was removed, and the adhesive layer of the protective film was attached to Alkali-free Glass (Non Alkali Glass) at a temperature of 25 ℃ by a laminator, exposed to a temperature of 0 ℃ for 1000 hours, aged (aging) at a temperature of 25 ℃ for 4 hours, and then peeled off at a speed of 5mm per second at a temperature of 25 ℃ at 180 ° by UTM to measure the adhesive force of the adhesive layer.
(7) Adhesive force of adhesive layer (identified as Z in the following table)
The release film of the protective film was removed, and the adhesive layer of the protective film was attached to Alkali-free Glass (Non Alkali Glass) at a temperature of 25 ℃ by a laminator, exposed at a temperature of 60 ℃ for 1000 hours, aged (aging) at a temperature of 25 ℃ for 4 hours, and then peeled off at 180 ° at a speed of 5mm per second at a temperature of 25 ℃ by UTM, and the adhesive force of the adhesive layer was measured.
(8) Adhesive force of adhesive layer (identified as D in the following table)
The release film of the protective film was removed, and the adhesive layer of the protective film was attached to Alkali-free Glass (Non Alkali Glass) at a temperature of 25 ℃ by a laminator, and after repeated 100 times of exposure to-20 ℃ for 30 minutes and 60 ℃ for 30 minutes, aging (taping) was performed at a temperature of 25 ℃ for 4 hours, and then the protective film base film was peeled off at a speed of 5mm per second at a temperature of 25 ℃ by UTM to measure the adhesive force of the adhesive layer.
(9) Adhesive force of adhesive layer (identified as E in the following table)
The release film of the protective film was removed, and after the adhesive layer of the protective film was attached to Alkali-free Glass (Non Alkali Glass) at a temperature of 25 ℃ by a laminator, exposed to a temperature of 60 ℃ and a humidity of 90% for 500 hours, aged (taping) at a temperature of 25 ℃ for 4 hours, the protective film base film was peeled off at a speed of 5mm per second at a temperature of 25 ℃ by UTM at 180 °, and the adhesive force of the adhesive layer was measured.
(10) Adhesive force of adhesive layer (identified as F. In the following tables)
The release film of the protective film was removed, and the adhesive layer of the protective film was attached to Alkali-free Glass (Non Alkali Glass) at a temperature of 25 ℃ by a laminator, exposed to 85 ℃ at a temperature of 85 ℃ and a humidity of 85% for 500 hours, aged (aging) at a temperature of 25 ℃ for 4 hours, and then peeled off at a speed of 5mm per second at a temperature of 25 ℃ by UTM at 180 ° to measure the adhesive force of the adhesive layer.
(11) Moisture permeability (WVTR)
The adhesive compositions prepared in examples 1 to 7 and comparative examples 1 to 5 were coated on one side of the silicon release-treated PET film, respectively, and dried in a drying oven at 125 c for 6 minutes. After the silicone release-treated PET film was laminated on one side of the adhesive composition on which coating and drying were performed by a laminating roller (= the side subjected to release treatment was laminated opposite to the adhesive composition), the adhesive composition was cured by irradiation with a UV light of 1000mJ to form an adhesive layer having a thickness of 100 μm. The moisture permeability of the formed adhesive layer was measured according to ASTM E-398 test specification using Permatran equipment of film Corgong.
(12) Stripping electrostatic voltage
The protective films were cut into pieces of 100mm × 100mm (length × width), and then the release films were peeled at a speed of 80mm per second at 180 °, and the peeling electrostatic voltage (V) of the adhesive layers was measured. The measurement was repeated 5 times, and the average value was 0.05kV or less, and evaluated as "O", and when it exceeded 0.05kV, it was evaluated as "X".
(13) Impact resistance
The release film from which the protective film was removed was attached to an Alkali-free Glass (Non Alkali Glass) at a temperature of 25 ℃ by a laminator, and after 24 hours, a 100g weight of a ball weight was dropped from a height of 10 cm in the vertical direction of the protective film onto the base film of the protective film, and when no bubble was generated between the adhesive layer and the Alkali-free Glass, the impact resistance was evaluated as "O" and when a bubble was generated, the impact resistance was evaluated as "X".
(14) Evaluation of bending Properties
The release film of the protective film was removed, and the adhesive layer of the protective film was attached to a polyimide film at a temperature of 25 ℃ by a laminator, and then cut into a size of 25mm × 150mm (length × width). After both ends of the cut polyimide film with the protective film attached thereto were placed in contact with each other, the film was bent 10000 times (bending) with a radius of curvature of 3.0mm, and when no crack occurred, the bending performance was evaluated as "good", and when a crack occurred, the film was evaluated as "x".
[ TABLE 1]
Categories Examples1 Example 2 Example 3 Example 4 Example 5 Example 6
A(gf/25mm) 1625 1532 1580 1335 1243 1600
B(gf/25mm) 1125 1132 1008 1285 714 1157
W(gf/25mm) 1344 1520 1250 1334 888 1320
C(gf/25mm) 1286 1090 1132 883 1225 1322
H(gf/25mm) 1414 1486 1217 1148 895 1408
Y(gf/25mm) 1544 1425 1438 1402 957 1497
Z(gf/25mm) 2633 2298 1975 1829 2113 2671
D(gf/25mm) 1918 1777 1517 1135 1492 1813
E(gf/25mm) 2649 2604 1754 2096 2026 2120
F(gf/25mm) 1305 1302 1153 1135 1032 1140
Condition (1) 1.44 1.35 1.44 1.04 1.74 1.38
Condition (2) 1.26 1.41 1.40 1.51 1.01 1.21
Condition (3) 0.85 0.86 1.04 1.18 0.83 0.88
Condition (4) 0.61 0.59 0.90 0.64 0.61 0.75
Condition (5) 1.25 1.18 1.37 1.18 1.20 1.40
Condition (6) 1.21 1.01 1.26 1.00 1.40 1.21
Condition (7) 1.05 1.08 1.10 0.95 1.30 1.07
Condition (8) 1.15 1.03 1.30 1.16 1.39 1.14
Condition (9) 0.62 0.67 0.80 0.73 0.59 0.60
Moisture permeability (g/m) 2 Sky) 3.9 2.5 11.5 3.8 8.8 3.9
Stripping electrostatic voltage ○ ○ ○ ○ ○ ○
Impact resistance ○ ○ ○ ○ ○ ○
Evaluation of bending Properties ○ ○ ○ ○ ○ ○
[ TABLE 2]
Categories Example 7 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
A(gf/25mm) 1643 1950 2283 1990 1950 800
B(gf/25mm) 1133 1475 1100 1360 1761 120
W(gf/25mm) 1401 1623 1719 1990 1970 104
C(gf/25mm) 1222 1560 1794 1900 716 1160
H(gf/25mm) 1240 1404 1489 1968 1701 448
Y(gf/25mm) 1614 1732 1672 1917 1627 384
Z(gf/25mm) 2373 1995 3881 1759 624 1101
D(gf/25mm) 1683 1354 833 442 1011 790
E(gf/25mm) 2251 1428 1114 299 1455 686
F(gf/25mm) 1368 821 735 406 421 640
Condition (1) 1.45 1.32 2.07 1.46 1.11 6.67
Condition (2) 1.34 1.25 1.27 1.05 2.72 0.69
Condition (3) 0.98 1.44 2.74 4.50 1.93 1.01
Condition (4) 0.73 1.37 2.05 6.65 1.34 1.17
Strip (5) 1.20 2.38 3.11 4.90 4.63 1.25
Condition (6) 1.17 1.20 1.33 1.00 0.99 7.69
Condition (7) 1.02 1.13 1.37 1.04 1.20 2.08
Condition (8) 1.33 1.39 1.53 1.01 1.15 1.79
Condition (9) 0.69 0.98 0.59 1.13 3.13 0.73
Moisture permeability (g/m) 2 Sky) 3.9 37 193 419 5.3 4.1
Stripping electrostatic voltage ○ ○ ○ ○ ○ ○
Impact resistance ○ ○ ○ ○ × ×
Evaluation of bending Properties ○ ○ ○ ○ ○ ×
As shown in tables 1 and 2, it was confirmed that the protective film for OLED panel manufacturing process prepared in example 1 has excellent adhesion retention and impact resistance even at low temperatures of-10 to-50 ℃ and high temperatures of 50 to 100 ℃, has a low moisture permeability (WVTR), is excellent in adhesion retention and also excellent in elastic force not only at high temperatures of 50 to 100 ℃ in a high humidity environment of 80% or more but also in a thermal shock environment.
Those skilled in the art can easily implement the simple modification or modification of the present invention, and such modification or modification can be considered as included in the present invention.
[ reference numerals ]
10: base film 20: adhesive layer 30: and (5) a release film.

Claims (10)

1. A protective film for use in a process for producing an OLED panel, as a protective film comprising a base film and an adhesive layer laminated on one surface of the base film,
the adhesive layer contains a fluorine-substituted urethane acrylate copolymer as a main agent resin,
the protective films all satisfy the conditions (4) and (5),
the protective film is characterized in that bubbles are not generated between the adhesive layer of the protective film and glass even if impact is applied to the base film of the protective film after the adhesive layer of the protective film is attached to the glass (glass).
(4)0.5≤A/E≤1.0
(5)1.0≤A/F≤2.0
In the above conditions (4) and (5), a represents the adhesive force of the adhesive agent layer measured by peeling the base film of the protective film at a rate of 5mm per second at a temperature of 25 ℃ after the adhesive agent layer of the protective film is adhered to glass (glass), E represents the adhesive force of the adhesive agent layer measured by adhering the adhesive agent layer of the protective film to glass (glass), after exposure for 500 hours at a temperature of 60 ℃ and a humidity of 90%, aging (taping) at a temperature of 25 ℃ for 4 hours, and peeling the base film of the protective film at a rate of 5mm per second at a temperature of 25 ℃ after aging (taping) at a temperature of 25 ℃ for 5mm per second, and F represents the adhesive force of the adhesive agent layer measured by adhering the adhesive agent layer of the protective film to glass (glass), after exposure for 500 hours at a temperature of 85 ℃ and a humidity of 85%, aging (taping) at a temperature of 25 ℃ for 4 hours, and peeling the base film of the protective film at a rate of 5mm per second at a temperature of 25 ℃ for 180 °.
2. The protective film for an OLED panel manufacturing process according to claim 1,
the weight average molecular weight of the fluorine-substituted urethane acrylate copolymer is 5000-1000000.
3. The protective film for an OLED panel manufacturing process according to claim 2,
the fluorine-substituted urethane acrylate copolymer comprises repeating units derived from hydroxyl-terminated perfluoropolyether (hydroxyl-terminated perfluoropolyether) containing 2 to 10 fluorine groups.
4. The protective film for an OLED panel manufacturing process according to claim 1,
the adhesive layer further comprises an acrylate monomer,
the acrylate monomer includes a compound represented by the following chemical formula 1, a compound represented by the following chemical formula 2, a compound represented by the following chemical formula 3, and Isobornyl acrylate (Isobornyl acrylate).
[ chemical formula 1]
Figure FDA0003682434470000021
[ chemical formula 2]
Figure FDA0003682434470000031
[ chemical formula 3]
Figure FDA0003682434470000032
In the chemical formula 1, B 1 is-CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 CH 2 -，R 1 And R 2 Are respectively and independently C1-C12 straight-chain alkyl, C3-C12 branched-chain alkyl, phenyl or alkyl phenyl,
in the chemical formula 2, B 3 is-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -，
In the chemical formula 3, B 2 is-CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -。
5. The protective film for an OLED panel manufacturing process according to claim 4,
the adhesive layer contains 1 to 10 parts by weight of the compound represented by chemical formula 1, 1 to 10 parts by weight of the compound represented by chemical formula 2, 1 to 10 parts by weight of the compound represented by chemical formula 3, and 15 to 35 parts by weight of Isobornyl acrylate (Isobornyl acrylate) per 100 parts by weight of the base resin.
6. The protective film for an OLED panel manufacturing process according to claim 1,
the base film is a permanent antistatic film comprising a permanent antistatic agent and a plastic resin.
7. The protective film for an OLED panel manufacturing process according to claim 1,
the base film and the adhesive layer of the protective film have 1: a thickness ratio of 0.13 to 0.66.
8. The protective film for an OLED panel manufacturing process according to claim 1,
the adhesive layer further includes a photoinitiator and an antistatic agent.
9. The protective film for an OLED panel manufacturing process according to claim 1,
the protective film also satisfies conditions (6) and (7).
(6)0.8≤A/W≤1.5
(7)0.8≤A/Y≤1.5
In the above conditions (6) and (7), a represents the adhesive force of the adhesive layer measured by peeling the base film of the protective film at 180 ° at a speed of 5mm per second at a temperature of 25 ℃ after the adhesive layer of the protective film is adhered to the glass (glass), W represents the adhesive holding force of the adhesive layer measured by peeling the base film of the protective film at 180 ° at a speed of 5mm per second at a temperature of 0 ℃ after the adhesive layer of the protective film is adhered to the glass (glass), Y represents the adhesive force of the adhesive layer measured by adhering the adhesive layer of the protective film to the glass (glass), after exposure for 1000 hours at a temperature of 0 ℃, aging (aging) at a temperature of 25 ℃ for 4 hours, and after aging (aging) at a temperature of 25 ℃ at a speed of 5mm per second, the protective film is peeled at a temperature of 180 ° after the adhesive layer of 25 ℃.
10. The protective film for an OLED panel manufacturing process according to claim 1,
the protective film also satisfies conditions (8) and (9).
(8)0.4≤A/H≤1.5
(9)0.4≤A/Z≤1.0
In the above conditions (8) and (9), a represents the adhesive force of the adhesive agent layer measured by peeling the protective film base film at a rate of 5mm per second at a temperature of 25 ℃ after the adhesive agent layer of the protective film is adhered to the glass (glass), H represents the adhesive force of the adhesive agent layer measured by peeling the protective film base film at a rate of 180 ° per second at a temperature of 25 ℃ after being exposed for 500 hours at a temperature of-30 ℃ and after being aged (aging) for 4 hours at a temperature of 25 ℃, and Z represents the adhesive force of the adhesive agent layer measured by peeling the protective film base film at a rate of 180 ° per second at a temperature of 25 ℃ after being exposed for 1000 hours at a temperature of 60 ℃, and after being aged (aging) for 4 hours at a temperature of 25 ℃, the adhesive agent layer measured by peeling the protective film at a rate of 5mm per second at a temperature of 25 ℃.
CN202210641831.1A 2021-06-25 2022-06-07 Protective film for OLED panel manufacturing process Pending CN115895491A (en)

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