WO2021235078A1 - 保護フィルム、フォルダブルデバイス、および、ローラブルデバイス - Google Patents

保護フィルム、フォルダブルデバイス、および、ローラブルデバイス Download PDF

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WO2021235078A1
WO2021235078A1 PCT/JP2021/012129 JP2021012129W WO2021235078A1 WO 2021235078 A1 WO2021235078 A1 WO 2021235078A1 JP 2021012129 W JP2021012129 W JP 2021012129W WO 2021235078 A1 WO2021235078 A1 WO 2021235078A1
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weight
protective film
acrylate
film according
layer
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PCT/JP2021/012129
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English (en)
French (fr)
Japanese (ja)
Inventor
浩司 設樂
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日東電工株式会社
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Priority to JP2021541695A priority Critical patent/JP6993543B1/ja
Priority to KR1020217029052A priority patent/KR102420775B1/ko
Priority to CN202180003857.7A priority patent/CN114008156B/zh
Publication of WO2021235078A1 publication Critical patent/WO2021235078A1/ja

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • 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]
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2461/00—Presence of condensation polymers of aldehydes or ketones
    • C09J2461/006—Presence of condensation polymers of aldehydes or ketones in the substrate
    • 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
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

Definitions

  • the present invention relates to a protective film.
  • the present invention also relates to a foldable device with such a protective film and a rollable device with such a protective film.
  • Protective films are used to reinforce members of various shapes and to protect the surface.
  • thermocompression bonding is usually performed with an anisotropic conductive film (ACF).
  • ACF anisotropic conductive film
  • a protective film may be previously attached to the back side of the substrate of the semiconductor element to reinforce it (for example, Patent Document 1).
  • a release layer and a flexible or rollable film substrate are formed on a support substrate such as glass, and the film substrate is formed.
  • a TFT substrate is formed on the surface, and an organic EL layer is formed on the TFT substrate.
  • the support substrate is peeled off to manufacture a flexible device or a rollable device, but since the flexible display layer and the rollable display layer are very thin, a problem occurs in the device due to handling or the like. Therefore, a protective film may be attached to the back side to reinforce it.
  • Such a conventional protective film has a base material layer and an adhesive layer, and a polyester film or an acrylic resin film is preferable as the base material layer, and a PET film is typically used (for example,).
  • Substrates of semiconductor devices, flexible devices, and rollable devices may be repeatedly bent, and if the bending characteristics of the protective film attached to the back side of the substrate are poor, the recoverability after bending deteriorates, or in the worst case, it is repeated. It may break due to bending. Specifically, when an attempt is made to attach a protective film to a bent portion (for example, a movable bent portion of a folding member), the following problems occur, for example.
  • a compressive force acts on the bent inner diameter side, so that the protective film itself is deformed in an attempt to alleviate the force. Specifically, for example, wrinkles are likely to occur.
  • the thickness of the bent part and the pulled part of the protective film changes greatly, and even in such a state, wrinkles are likely to occur and floating occurs. do.
  • the thickness of the protective film becomes significantly thin, and floating from the adherend is likely to occur.
  • a polyimide substrate is usually adopted as a substrate on which a display area and a terminal portion are formed.
  • This polyimide substrate is thin and has a thickness of about 10 ⁇ m to 20 ⁇ m (for example, the polyimide substrate of Patent Document 3).
  • a barrier is usually used on the surface of the polyimide substrate on the side where the display region and the terminal portion are formed in order to prevent deterioration of the organic EL layer due to moisture. Layers are provided.
  • this barrier layer is made of a brittle material such as SiO or SiN, it is extremely fragile, is extremely thin, and has a thickness of about 50 nm to 300 nm (for example, the barrier layer of Patent Document 3).
  • a conventional protective film is attached to the back side of a polyimide substrate provided with such a barrier layer, the polyimide substrate may be deformed, and the fragile and extremely thin barrier layer is destroyed by this deformation. There is a problem that it ends up.
  • thermocompression bonding to a semiconductor element substrate (for example, a TFT substrate)
  • a semiconductor element substrate for example, a TFT substrate
  • the protective film attached to the back side of the substrate is required to have transparency.
  • the protective film is inspected for foreign matter in the manufacturing process.
  • a filler is contained in the base material layer (typically PET film) to prevent blocking, etc., and the maximum length, which is a pass product level in foreign matter inspection, is 1 ⁇ m. Even for products in which only ultra-fine foreign substances of less than the level are present as foreign substances, the filler may be recognized as a foreign substance and may be judged as a rejected product, resulting in a decrease in productivity. be.
  • An object of the present invention is to provide a protective film which is excellent in bending recovery property, does not destroy the barrier layer even when attached to the back side of a polyimide substrate provided with a barrier layer, is excellent in transparency, and is excellent in foreign matter inspection. There is something in it.
  • An object of the present invention is also to provide a foldable device and a rollable device provided with such a protective film.
  • the present inventors conducted a study to solve the above problems. As a result, it was found that the cause of the destruction of the barrier layer when the protective film is attached to the back side of the polyimide substrate provided with the barrier layer is the particles present in the protective film. Then, the cause of the presence of the particles was considered, and it was considered to be a filler contained in the base material layer of the protective film to prevent blocking. It was also considered that if such particles could be eliminated, excellent transparency and excellent foreign matter inspection would be exhibited. Therefore, it is considered that the problem of the present invention can be solved by using a protective film that eliminates the above-mentioned particles and has excellent bending recovery property, and has completed the present invention.
  • the protective film according to the embodiment of the present invention is A protective film that is directly attached to a polyimide substrate. It has a base material layer and an adhesive layer, The substrate layer is substantially free of particles or agglomerates of particles having a Ferret diameter of 1 ⁇ m or larger.
  • the top coat layer is provided on the surface of the base material layer opposite to the surface having the adhesive layer.
  • the topcoat layer contains a binder containing at least one selected from polyester resin and urethane resin.
  • the binder contains a urethane resin.
  • the topcoat layer contains an antistatic component.
  • Young's modulus at 23 ° C. of the base layer is 6.0 ⁇ 10 7 Pa or higher.
  • the material of the base material layer is at least one selected from polyimide and polyetheretherketone.
  • the base coat layer has a top coat layer on the surface opposite to the surface having the adhesive layer, and the top coat layer contains a binder containing a urethane resin and an antistatic component.
  • the material of the base material layer is at least one selected from polyimide and polyetheretherketone.
  • the protective film of the present invention is bent at 6 ⁇ and held at 90 ° C. for 48 hours, then released from the bending and left at 23 ° C. and 50% RH for 24 hours.
  • the bending angle of is 60 to 180 degrees.
  • the protective film of the present invention has a total light transmittance of 40% or more.
  • the protective film of the present invention has a haze of 10% or less.
  • the adhesive force of the pressure-sensitive adhesive layer on a glass plate at a tensile speed of 300 mm / min and a peel of 180 degrees at 23 ° C. is 1 N / 25 mm or more.
  • the storage elastic modulus of the pressure-sensitive adhesive layer at 25 ° C. is 75 kPa or less.
  • the Tg of the pressure-sensitive adhesive layer is ⁇ 10 ° C. or lower.
  • the pressure-sensitive adhesive layer contains an acrylic pressure-sensitive adhesive
  • the acrylic pressure-sensitive adhesive contains an acrylic polymer as a base polymer
  • the content ratio of 2-ethylhexyl acrylate in the above-mentioned monomer component (M) is 15% by weight to 85% by weight.
  • the total content of the alkyl (meth) acrylate (m1) and the 2-ethylhexyl acrylate in the monomer component (M) is 65% by weight to 98% by weight.
  • R 2 in the above alkyl (meth) acrylate (m1) is a chain alkyl group of C10-13.
  • the alkyl (meth) acrylate (m1) is lauryl acrylate.
  • the monomer component (M) contains at least one selected from the group consisting of a hydroxyl group-containing monomer, a carboxy group-containing monomer, and a nitrogen-containing monomer.
  • the protective film of the present invention is attached to a foldable member.
  • the foldable member is an OLED.
  • the protective film of the present invention is attached to a rollable member.
  • the rollable member is an OLED.
  • the foldable device according to the embodiment of the present invention includes the above protective film.
  • the rollable device according to the embodiment of the present invention includes the above protective film.
  • a protective film which is excellent in bending recovery property, does not destroy the barrier layer even when attached to the back side of a polyimide substrate provided with a barrier layer, is excellent in transparency, and is excellent in foreign matter inspection property. be able to. According to the present invention, it is also possible to provide a foldable device and a rollable device provided with such a protective film.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of the foldable device of the present invention, and shows one usage mode of the protective film of the present invention.
  • FIG. 2 is a schematic cross-sectional view illustrating a method for evaluating bending recovery.
  • the protective film according to the embodiment of the present invention is typically a protective film that is directly bonded to a polyimide substrate. That is, the embodiment in which the protective film according to the embodiment of the present invention is directly bonded to the polyimide substrate forms a laminated structure of the polyimide substrate and the protective film ([polyimide substrate] / [protective film]).
  • any suitable polyimide substrate can be adopted as long as the effect of the present invention is not impaired.
  • a typical example of such a polyimide substrate is a polyimide substrate provided in an OLED.
  • the protective film according to the embodiment of the present invention has excellent bending recovery property, does not destroy the barrier layer even when attached to the back side of a polyimide substrate provided with a barrier layer, has excellent transparency, and has excellent foreign matter inspection property.
  • it is attached to a foldable member.
  • the foldable member any suitable member may be adopted as long as it is a member capable of repeated bending. Examples of such a foldable member include a foldable optical member, a foldable electronic member, and the like, and a typical example is a foldable OLED. Therefore, the protective film according to the embodiment of the present invention is typically directly attached to a polyimide substrate provided in a foldable OLED.
  • the protective film of the present invention is preferable because it has excellent bending recovery property, does not destroy the barrier layer even when attached to the back side of a polyimide substrate provided with a barrier layer, has excellent transparency, and has excellent foreign matter inspection property. It is attached to the rollable member.
  • the rollable member any suitable member can be adopted as long as it can be repeatedly wound and rewound. Examples of such a rollable member include a rollable optical member, a rollable electronic member, and the like, and a typical example is a rollable OLED. Therefore, the protective film according to the embodiment of the present invention is typically directly attached to a polyimide substrate provided in a rollable OLED.
  • the thickness of the polyimide substrate to which the protective film according to the embodiment of the present invention is directly bonded can be set to an arbitrary appropriate thickness according to the purpose of use of the polyimide substrate. In terms of further exhibiting the effects of the present invention, such a thickness is preferably 1 ⁇ m to 100 ⁇ m, more preferably 3 ⁇ m to 50 ⁇ m, still more preferably 5 ⁇ m to 25 ⁇ m, and particularly preferably 10 ⁇ m to. It is 20 ⁇ m.
  • the polyimide substrate to which the protective film according to the embodiment of the present invention is directly bonded is the polyimide substrate used for the OLED
  • the polyimide substrate tends to contain water inside, so that the organic EL layer is deteriorated by the water. It will be easier. Therefore, when the polyimide substrate to which the protective film according to the embodiment of the present invention is directly bonded is a polyimide substrate used for the OLED, it is opposite to the side of the polyimide substrate to which the protective film is directly bonded.
  • the side surface is preferably provided with a barrier layer. Since this barrier layer is made of a brittle material such as SiO or SiN, it is extremely fragile and extremely thin, typically having a thickness of about 50 nm to 300 nm.
  • the protective film according to the embodiment of the present invention has a base material layer and an adhesive layer. That is, the protective film according to the embodiment of the present invention may have any suitable other layer as long as it has a base material layer and an adhesive layer, as long as the effect of the present invention is not impaired.
  • the base material layer may be one layer or two or more layers.
  • the base material layer is preferably one layer in that the effects of the present invention can be more exhibited.
  • the pressure-sensitive adhesive layer may be one layer or two or more layers.
  • the pressure-sensitive adhesive layer is preferably one layer in that the effects of the present invention can be more exhibited.
  • the protective film according to the embodiment of the present invention may be provided with an arbitrary suitable release liner on the surface of the pressure-sensitive adhesive layer on the opposite side of the base material layer for protection until use.
  • the release liner for example, the surface of the base material (liner base material) such as paper or plastic film is treated with silicone, and the surface of the base material (liner base material) such as paper or plastic film is made of polyolefin resin.
  • the plastic film as the liner base material include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, and polybutylene terephthalate film.
  • examples thereof include a polyurethane film and an ethylene-vinyl acetate copolymer film.
  • the thickness of the release liner is preferably 1 ⁇ m to 500 ⁇ m, more preferably 3 ⁇ m to 450 ⁇ m, further preferably 5 ⁇ m to 400 ⁇ m, and particularly preferably 10 ⁇ m to 300 ⁇ m.
  • One embodiment of the protective film of the present invention comprises a laminate of a base material layer and an adhesive layer. Another embodiment of the protective film of the present invention comprises a laminated body in which a base material layer, an adhesive layer, and a release liner are laminated in this order. Another embodiment of the protective film of the present invention comprises a laminated body in which a top coat layer, a base material layer, and an adhesive layer are laminated in this order. Another embodiment of the protective film of the present invention comprises a laminated body in which a top coat layer, a base material layer, an adhesive layer, and a release liner are laminated in this order.
  • Another embodiment of the protective film of the present invention comprises a laminated body in which an antistatic layer, a base material layer, and an adhesive layer are laminated in this order.
  • Another embodiment of the protective film of the present invention comprises a laminated body in which an antistatic layer, a base material layer, an adhesive layer, and a release liner are laminated in this order.
  • Another embodiment of the protective film of the present invention comprises a laminated body in which a top coat layer, an antistatic layer, a base material layer, and an adhesive layer are laminated in this order.
  • Another embodiment of the protective film of the present invention comprises a laminated body in which a top coat layer, an antistatic layer, a base material layer, an adhesive layer, and a release liner are laminated in this order.
  • Another embodiment of the protective film of the present invention comprises a laminated body in which an antistatic layer, a top coat layer, a base material layer, and an adhesive layer are laminated in this order.
  • Another embodiment of the protective film of the present invention comprises a laminate in which an antistatic layer, a topcoat layer, a base material layer, an adhesive layer, and a release liner are laminated in this order. The top coat layer and antistatic layer will be described later.
  • the protective film according to the embodiment of the present invention has a total thickness d of preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 200 ⁇ m, still more preferably 10 ⁇ m to 150 ⁇ m, and particularly preferably 20 ⁇ m to 100 ⁇ m. Most preferably, it is 30 ⁇ m to 80 ⁇ m. If the total thickness d of the protective film according to the embodiment of the present invention is within the above range, the effect of the present invention can be more exhibited.
  • the protective film according to the embodiment of the present invention has a bending angle after being bent at 6 ⁇ and held at 90 ° C. for 48 hours, then released, and left at 23 ° C. and 50% RH for 24 hours. It is preferably 60 degrees to 180 degrees, more preferably 80 degrees to 180 degrees, further preferably 100 degrees to 180 degrees, particularly preferably 120 degrees to 180 degrees, and most preferably 150 degrees to 150 degrees. It is 180 degrees.
  • the bending angle of the protective film according to the embodiment of the present invention after being bent at 6 ⁇ and held at 90 ° C. for 48 hours, then released and left at 23 ° C. and 50% RH for 24 hours. , Is an index showing recovery after bending.
  • the method for measuring the bending angle after bending at 6 ⁇ and holding at 90 ° C. for 48 hours, releasing the bending and leaving at 23 ° C. and 50% RH for 24 hours will be described in detail later.
  • the protective film according to the embodiment of the present invention has a total light transmittance of preferably 40% or more, more preferably 50% or more, still more preferably 60% or more, and particularly preferably 70% or more. , Most preferably 80% or more. If the total light transmittance of the protective film according to the embodiment of the present invention is within the above range, excellent transparency can be further exhibited.
  • the protective film according to the embodiment of the present invention has a haze of preferably 10% or less, more preferably 8% or less, still more preferably 6% or less, particularly preferably 5% or less, and most preferably. Is less than 4%. If the haze of the protective film according to the embodiment of the present invention is within the above range, excellent transparency can be further exhibited.
  • the surface roughness Ra of the outermost layer surface on the side opposite to the pressure-sensitive adhesive layer when viewed from the base material layer may be large or small, and any value can be taken. This is because, in the protective film according to the embodiment of the present invention, the surface roughness Ra may be large even if the substrate layer does not substantially contain particles having a ferret diameter of 1 ⁇ m or more or aggregates of particles. Alternatively, in a protective film not an embodiment of the present invention, it means that the surface roughness Ra may be small even if particles having a Ferret diameter of 1 ⁇ m or more or agglomerates of particles are contained in the base material layer. .. That is, the surface roughness Ra means that there is no correlation with the amount of particles or agglomerates of particles having a ferret diameter of 1 ⁇ m or more in the base material layer.
  • the thickness of the base material layer is preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 300 ⁇ m, further preferably 10 ⁇ m to 100 ⁇ m, particularly preferably 15 ⁇ m to 80 ⁇ m, and most preferably 20 ⁇ m to 60 ⁇ m. .. When the thickness of the base material layer is within the above range, the effect of the present invention can be more exhibited.
  • the substrate layer has a Young's modulus at 23 ° C. of preferably 6.0 ⁇ 10 7 Pa or more, more preferably 1.0 ⁇ 10 8 Pa or more, and further preferably 5.0 ⁇ 10 8 Pa or more. It is particularly preferably 8.0 ⁇ 10 8 Pa or more, and most preferably 1.0 ⁇ 10 9 Pa or more.
  • the upper limit of Young's modulus of the base material layer at 23 ° C. is typically 1.0 ⁇ 10 11 Pa or less. If the Young's modulus of the substrate layer at 23 ° C. is within the above range, the effect of the present invention can be more exhibited. If the Young's modulus of the base material layer at 23 ° C.
  • the protective film is bent at an angle, the tension on the outer diameter side may not be sufficiently retained with respect to the compression on the inner diameter side, and the thickness changes. It becomes easy, and there is a possibility that floating from the adherend is likely to occur. If the Young's modulus of the substrate layer at 23 ° C. is too high, the protective film may not be easily deformed. The method for measuring Young's modulus will be described in detail later.
  • any suitable material can be adopted as long as the effect of the present invention is not impaired.
  • a typical example of the material of such a base material layer is a resin material.
  • the resin material as the material of the base material examples include polyimide (PI), polyether ether ketone (PEEK), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polymethyl methacrylate.
  • Acrylic resin such as (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA).
  • Polyamide (nylon), total aromatic polyamide (aramid), polyvinyl chloride (PVC), polyvinyl acetate, polyphenylene sulfide (PPS), fluororesin, cyclic olefin polymer and the like.
  • the resin material as the material of the base material is preferably polyimide (PI), polyetheretherketone (PEEK), polyethylene naphthalate (PEN), or cyclic olefin-based material in that the effects of the present invention can be more exhibited.
  • At least one selected from polymers is mentioned, more preferably at least one selected from polyimide (PI), polyetheretherketone (PEEK), polyethylene naphthalate (PEN), and even more preferably polyimide (PI).
  • PEEK polyetheretherketone
  • the substrate layer is preferably substantially free of particles or agglomerates of particles having a Ferret diameter of 1 ⁇ m or larger.
  • the term "substantially free” as used herein means that, ideally, the substrate layer does not contain any particles (even one) having a ferret diameter of 1 ⁇ m or more, and in reality, For example, when observing the inside of the base material layer using a digital microscope, the number of particles observed per unit area (0.02 mm 2 ) of particles having a ferret diameter of 1 ⁇ m or more is preferably 9 or less, more preferably 5. The case of 10 or less, more preferably 3 or less, particularly preferably 0 is referred to as "substantially free”.
  • the above-mentioned "substantially free” also includes that the base material layer does not contain particles or aggregates of particles having a ferret diameter of 1 ⁇ m or more that are “intentionally added”, for example, a group.
  • the presence of agglomerates can be included in "substantially free” as long as the effects of the present invention are not impaired.
  • the inside of the base material layer is observed using a digital microscope, and the number observed per unit area (0.02 mm 2) of particles having a Ferret diameter of 1 ⁇ m or more or agglomerates of particles.
  • the number is preferably 9 or less, more preferably 5 or less, still more preferably 3 or less, and particularly preferably 0.
  • Ferret diameter is an index of the size of target particles or agglomerates of particles, and is also called a directional diameter.
  • the Ferret diameter is the distance between parallel lines sandwiching the projected image of the particles in parallel lines in a certain direction, and is the length of the longest point in the straight line distance.
  • the ferret diameter can be observed and measured with a digital microscope or the like.
  • the shape of the particles or agglomerates of particles can take a wide variety of shapes such as spherical, spheroidal, needle-like, various geometric shapes, and various indefinite shapes.
  • the surface resistance value measured on the surface of the substrate layer is preferably 10 12 ⁇ or less, more preferably 10 4 ⁇ to 10 12 ⁇ , still more preferably 10 4 ⁇ to 10 11 ⁇ , and particularly. It is preferably 5 ⁇ 10 4 ⁇ to 10 10 ⁇ , and most preferably 10 4 ⁇ to 10 9 ⁇ .
  • a protective film exhibiting such a surface resistance value can be suitably used as a protective film used in a process of processing or transporting an article that dislikes static electricity, such as a liquid crystal cell or a semiconductor device.
  • the value of the surface resistance value on the surface of the base material layer can be measured by, for example, a resistivity meter.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 ⁇ m to 500 ⁇ m, more preferably 3 ⁇ m to 300 ⁇ m, further preferably 5 ⁇ m to 100 ⁇ m, particularly preferably 7 ⁇ m to 75 ⁇ m, and most preferably 10 ⁇ m to 50 ⁇ m. .. If the thickness of the pressure-sensitive adhesive layer is within the above range, the effect of the present invention can be more exhibited.
  • the adhesive force of the pressure-sensitive adhesive layer to the glass plate at a tensile speed of 300 mm / min and a peel of 180 degrees at 23 ° C. is preferably 1 N / 25 mm or more, more preferably 5 N / 25 mm or more, still more preferably. It is 10 N / 25 mm or more, particularly preferably 12 N / 25 mm or more, and most preferably 15 N / 25 mm or more.
  • the upper limit of the adhesive force of the pressure-sensitive adhesive layer on a glass plate at a tensile speed of 300 mm / min and a peel of 180 degrees at 23 ° C. is typically preferably 1000 N / 25 mm or less, more preferably 500 N / 25 mm.
  • the storage elastic modulus of the pressure-sensitive adhesive layer at 25 ° C. is preferably 75 kPa or less, more preferably 70 kPa or less, further preferably 65 kPa or less, particularly preferably 60 kPa or less, and most preferably 55 kPa or less. ..
  • the lower limit of the storage elastic modulus of the pressure-sensitive adhesive layer at 25 ° C. is preferably 1 kPa or more, more preferably 5 kPa or more, further preferably 10 kPa or more, particularly preferably 15 kPa or more, and most preferably 20 kPa or more. Is. If the storage elastic modulus of the pressure-sensitive adhesive layer at 25 ° C. is within the above range, the effect of the present invention can be further exhibited.
  • the glass transition temperature Tg of the pressure-sensitive adhesive layer can be, for example, ⁇ 80 ° C. or higher in that the effects of the present invention can be more exhibited, and in particular, the obtained protective film can exhibit excellent bending durability. ..
  • the Tg is designed to be preferably ⁇ 15 ° C. or lower from the viewpoint of enhancing the deformability of the pressure-sensitive adhesive layer in the shearing direction, and particularly from the viewpoint that the obtained protective film can exhibit excellent bending durability. ..
  • the Tg of the pressure-sensitive adhesive layer is, for example, preferably 10 ° C. or lower, more preferably 0 ° C. or lower, still more preferably ⁇ 10 ° C. or lower, still more preferably ⁇ 15 ° C. or lower.
  • the Tg of the pressure-sensitive adhesive layer is preferably -80 ° C or higher (more than -80 ° C), for example, from the viewpoint of enhancing cohesiveness and shape restoration, and particularly from the viewpoint that the obtained protective film can exhibit excellent bending durability. It is designed to be preferably ⁇ 70 ° C. or higher, more preferably ⁇ 60 ° C. or higher, and particularly preferably ⁇ 50 ° C. or higher).
  • the pressure-sensitive adhesive layer contains a base polymer.
  • the base polymer may be only one kind or two or more kinds.
  • the content of the base polymer in the pressure-sensitive adhesive layer is preferably 20% by weight to 100% by weight, more preferably 30% by weight to 95% by weight, and further, in that the effect of the present invention can be more exhibited. It is preferably 40% by weight to 90% by weight, particularly preferably 45% by weight to 85% by weight, and most preferably 50% by weight to 80% by weight.
  • the base polymer any suitable polymer can be adopted as long as the effect of the present invention is not impaired.
  • the base polymer is preferably at least one selected from an acrylic polymer, a rubber polymer, a silicone polymer, and a urethane polymer in that the effects of the present invention can be further exhibited.
  • the pressure-sensitive adhesive layer is preferably composed of an acrylic pressure-sensitive adhesive containing an acrylic polymer, a rubber-based pressure-sensitive adhesive containing a rubber-based polymer, a silicone-based pressure-sensitive adhesive containing a silicone-based polymer, and a urethane-based pressure-sensitive adhesive containing a urethane-based polymer. Includes at least one selected.
  • the pressure-sensitive adhesive layer preferably contains an acrylic pressure-sensitive adhesive in that the effects of the present invention can be further exhibited. That is, the pressure-sensitive adhesive layer contains an acrylic pressure-sensitive adhesive, and the acrylic pressure-sensitive adhesive contains an acrylic polymer as a base polymer in that the effects of the present invention can be further exhibited.
  • the acrylic pressure-sensitive adhesive will be described in detail as a typical example of the pressure-sensitive adhesive that can be contained in the pressure-sensitive adhesive layer.
  • the acrylic pressure-sensitive adhesive contains an acrylic polymer as a base polymer.
  • the acrylic pressure-sensitive adhesive may contain an oligomer.
  • the acrylic pressure-sensitive adhesive may contain a tack-imparting resin.
  • the acrylic pressure-sensitive adhesive may contain a cross-linking agent.
  • the acrylic pressure-sensitive adhesive contains an acrylic polymer, a tackifier resin, and a cross-linking agent
  • the content ratio of the total amount of the acrylic polymer, the pressure-imparting resin, and the cross-linking agent to the total amount of the acrylic pressure-sensitive adhesive is determined by the present invention. In terms of being able to further exhibit the effect, it is preferably 95% by weight or more, more preferably 97% by weight or more, and further preferably 99% by weight or more.
  • acrylic polymer for example, a polymer having a monomer component (M) containing an alkyl (meth) acrylate as a main monomer and further containing a submonomer having copolymerizability with the main monomer is preferable.
  • the main monomer means a component that occupies more than 50% by weight of the entire monomer component (M).
  • the acrylic polymer can be defined as being obtained by polymerizing the monomer component (M) in this way. This is because the acrylic polymer becomes an acrylic polymer by the polymerization reaction of the monomer component (M), and it is impossible to directly specify the acrylic polymer by its structure, and it is almost impractical. Since there are (“impossible / impractical circumstances”), the acrylic polymer can be appropriately specified as a “product” by the provision of “a product obtained by polymerizing the monomer component (M)”.
  • alkyl (meth) acrylate for example, a compound represented by the following formula (1) can be preferably used.
  • CH 2 C (R 1 ) COOR 2 (1)
  • R 1 in the above formula (1) is a hydrogen atom or a methyl group
  • R 2 is a chain alkyl group having 1 to 20 carbon atoms (hereinafter, such a range of carbon atoms is defined as “C1-”. It may be expressed as “20").
  • R 2 is preferably a chain alkyl group of C1-14, more preferably a chain alkyl group having C2-13, more preferably of C4-12 It is a chain alkyl group.
  • the chain shape means to include a linear shape and a branched shape.
  • the alkyl (meth) acrylate is a linear alkyl group
  • R 2 is C1-20, e.g., methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n- butyl (Meta) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Octyl (meth) acrylate, Isooctyl (meth) acrylate, Nonyl (meth) acrylate, Isononyl (meth) acrylate, Decyl (meth) acrylate, I
  • alkyl (meth) acrylate examples include n-butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), and lauryl (meth) acrylate in that the effects of the present invention can be further exhibited.
  • the homopolymer of the alkyl (meth) acrylate having a long-chain alkyl group of C10 or more has a temperature region (plateau region) in which the temperature dependence of viscoelasticity is small at a temperature higher than Tg.
  • the temperature dependence of tan ⁇ tends to be small.
  • the alkyl (meth) acrylate it is preferable to indispensably use an alkyl (meth) acrylate having a long-chain alkyl group of C10-16, and C10-13.
  • an alkyl (meth) acrylate having a long-chain alkyl group is more preferable, and it is particularly preferable to use a lauryl (meth) acrylate which is an alkyl (meth) acrylate having a long-chain alkyl group of C12 as essential.
  • the content of the alkyl (meth) acrylate in the total monomer component (M) used in the synthesis of the acrylic polymer is preferably 70% by weight or more, more preferably 70% by weight or more, in that the effect of the present invention can be further exhibited. It is 85% by weight or more, more preferably 90% by weight or more.
  • the upper limit of the content ratio of the alkyl (meth) acrylate is preferably 99.5% by weight or less, and more preferably 99% by weight or less.
  • the acrylic polymer may be obtained by polymerizing substantially only an alkyl (meth) acrylate.
  • the alkyl (meth) acrylate represented by the formula (1) R 1 is a hydrogen atom or a methyl group, and R 2 is C10-.
  • the content of the alkyl (meth) acrylate (m1), which is the chain alkyl group of 20, is preferably 5% by weight to 65% by weight, more preferably 6% by weight to 65% by weight, still more preferably 7. It is from% by weight to 65% by weight.
  • the content ratio of the alkyl (meth) acrylate (m1) in the monomer component (M) is within the above range, the effect of the present invention can be further exhibited.
  • the resulting protective film can exhibit excellent bending durability.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a chain alkyl group of C10-20
  • the alkyl (meth) acrylate (m1). in that it can more exhibit the effect of the present invention, R 2 is preferably a chain alkyl group of C10-14, more preferably a chain alkyl group having C10-13, more preferably C10-13 It is a chain alkyl group of C12, particularly preferably a chain alkyl group of C12, and most preferably a lauryl acrylate.
  • the content of 2-ethylhexyl acrylate in the monomer component (M) is preferably 15% by weight to 85% by weight, more preferably 17% by weight to 83% by weight. It is more preferably 20% by weight to 80% by weight, and particularly preferably 20% by weight to 75% by weight.
  • the content ratio of 2-ethylhexyl acrylate in the monomer component (M) is within the above range, the effect of the present invention can be further exhibited.
  • the resulting protective film can exhibit excellent bending durability.
  • the content ratio of 2-ethylhexyl acrylate in the monomer component (M) may be more than 85% by weight and 98% by weight or less.
  • the content ratio of the alkyl (meth) acrylate (m1) in the monomer component (M) is preferably less than 5% by weight, more preferably less than 3% by weight, still more preferably. It is less than 1% by weight, particularly preferably less than 0.1% by weight, and most preferably substantially 0% by weight.
  • the total content ratio of the alkyl (meth) acrylate (m1) and the 2-ethylhexyl acrylate in the monomer component (M) is preferably 65% by weight to 98% by weight, and more. It is preferably 70% by weight to 95% by weight, more preferably 72% by weight to 93% by weight, and particularly preferably 75% by weight to 90% by weight.
  • the total content ratio of the alkyl (meth) acrylate (m1) and the 2-ethylhexyl acrylate in the monomer component (M) is within the above range, the effect of the present invention can be further exhibited. In particular, the resulting protective film can exhibit excellent bending durability.
  • the acrylic polymer when the monomer component (M) contains an alkyl (meth) acrylate (m1) and a 2-ethylhexyl acrylate, the 2-ethylhexyl acrylate with respect to 100 parts by weight of the alkyl (meth) acrylate (m1)
  • the weight ratio is preferably 10 parts by weight to 1000 parts by weight, more preferably 20 parts by weight to 950 parts by weight, particularly preferably 30 parts by weight to 900 parts by weight, and most preferably 30 parts by weight to 880 parts by weight. It is a weight part.
  • the effect of the present invention can be further exhibited.
  • the resulting protective film can exhibit excellent bending durability.
  • the monomer component (M) is an alkyl (meth) acrylate represented by the formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is C4-. It may contain an alkyl (meth) acrylate (m2) which is a chain alkyl group of 7.
  • the content ratio of the alkyl (meth) acrylate (m2) in the monomer component (M) may be 50% by weight or more, but preferably less than 50% by weight, more preferably. It is 40% by weight or less, more preferably 35% by weight or less, particularly preferably 30% by weight or less, and most preferably 25% by weight or less. When the content ratio of the alkyl (meth) acrylate (m2) in the monomer component (M) is within the above range, the effect of the present invention can be further exhibited.
  • alkyl (meth) acrylate represented by the formula (1), where R 1 is a hydrogen atom or a methyl group and R 2 is a chain alkyl group of C4-7 as an alkyl (meth) acrylate (m2).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a chain alkyl group of C4-7 as an alkyl (meth) acrylate (m2).
  • the acrylic polymer is an acrylic polymer in which less than 50% by weight of the total monomer component (M) is n-butyl acrylate (BA).
  • the content ratio of n-butyl acrylate (BA) in the total monomer component (M) is preferably more than 0% by weight and 48% by weight or less in that the effect of the present invention can be more exhibited, and more. It is preferably 5% by weight to 45% by weight, more preferably 10% by weight to 43% by weight, particularly preferably 15% by weight to 40% by weight, and most preferably 20% by weight to 35% by weight. ..
  • the total monomer component (M) may further contain 2-ethylhexyl acrylate (2EHA) in a larger proportion than n-butyl acrylate (BA).
  • the acrylic polymer is an acrylic polymer in which 50% by weight or more of the total monomer component (M) is n-butyl acrylate (BA).
  • the content ratio of n-butyl acrylate (BA) in the total monomer component (M) is preferably more than 50% by weight and 100% by weight or less in that the effect of the present invention can be more exhibited, and more. It is preferably 55% by weight to 95% by weight, more preferably 60% by weight to 90% by weight, particularly preferably 63% by weight to 85% by weight, and most preferably 65% by weight to 80% by weight. ..
  • the total monomer component (M) may further contain 2-ethylhexyl acrylate (2EHA) in a smaller proportion than n-butyl acrylate (BA).
  • the acrylic polymer is an acrylic polymer in which less than 50% by weight of the total monomer component (M) is 2-ethylhexyl acrylate (2EHA).
  • the content ratio of 2-ethylhexyl acrylate (2EHA) in the total monomer component (M) is preferably more than 0% by weight and 48% by weight or less in that the effect of the present invention can be more exhibited, and more. It is preferably 5% by weight to 45% by weight, more preferably 10% by weight to 43% by weight, particularly preferably 15% by weight to 40% by weight, and most preferably 20% by weight to 35% by weight. ..
  • the total monomer component (M) may further contain n-butyl acrylate (BA) in a larger proportion than 2-ethylhexyl acrylate (2EHA).
  • the acrylic polymer is an acrylic polymer in which 50% by weight or more of the total monomer component (M) is 2-ethylhexyl acrylate (2EHA).
  • the content ratio of 2-ethylhexyl acrylate (2EHA) in the total monomer component (M) is preferably more than 50% by weight and 100% by weight or less in that the effect of the present invention can be more exhibited, and more. It is preferably 55% by weight to 98% by weight, more preferably 60% by weight to 90% by weight, particularly preferably 63% by weight to 85% by weight, and most preferably 65% by weight to 80% by weight. ..
  • the total monomer component (M) may further contain n-butyl acrylate (BA) in a smaller proportion than 2-ethylhexyl acrylate (2EHA).
  • the acrylic polymer may be copolymerized with other monomers as long as the effects of the present invention are not impaired.
  • Other monomers can be used, for example, for the purpose of introducing a functional group that can be a cross-linking base point to an acrylic polymer, improving adhesive strength, adjusting the glass transition temperature (Tg) of an acrylic polymer, adjusting the adhesive performance, and the like. can.
  • Suitable monomers that can contribute to the improvement of adhesive strength by introducing a functional group that can serve as a cross-linking base into an acrylic polymer include, for example, a hydroxyl group (OH group) -containing monomer, a carboxy group-containing monomer, an acid anhydride group-containing monomer, and nitrogen. Examples thereof include an amide group-containing monomer, an amino group-containing monomer, an imide group-containing monomer, an epoxy group-containing monomer, (meth) acryloylmorpholin, vinyl ethers and the like.
  • Examples of other monomers that can improve the cohesiveness and heat resistance of the pressure-sensitive adhesive include sulfonic acid group-containing monomers, phosphate group-containing monomers, cyano group-containing monomers, vinyl esters, aromatic vinyl compounds, and the like, and vinyl esters.
  • sulfonic acid group-containing monomers include phosphate group-containing monomers, cyano group-containing monomers, vinyl esters, aromatic vinyl compounds, and the like, and vinyl esters.
  • vinyl esters include vinyl acetate (VAc), vinyl propionate, vinyl laurate, and the like, with vinyl acetate (VAc) being preferred.
  • the other monomer is preferably at least one selected from the group consisting of a hydroxyl group-containing monomer, a carboxy group-containing monomer, and a nitrogen-containing monomer in that the effects of the present invention can be further exhibited.
  • the "other monomer” may be only one kind or two or more kinds.
  • the content ratio of the other monomer in the total monomer component (M) is preferably 0.001% by weight to 40% by weight, more preferably 0.01% by weight to 40% by weight, still more preferably 0.1. It is from% by weight to 10% by weight, particularly preferably 0.5% by weight to 5% by weight, and most preferably 1% by weight to 3% by weight.
  • the acrylic polymer is an acrylic polymer copolymerized with a carboxy group-containing monomer as another monomer.
  • the carboxy group-containing monomer include acrylic acid (AA), methacrylic acid (MAA), carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • acrylic acid (AA) and methacrylic acid (MAA) are preferably mentioned as the carboxy group-containing monomer, and acrylic acid (AA) is more preferable, because the effect of the present invention can be further exhibited. be.
  • the content ratio of the carboxy group-containing monomer in the total monomer component (M) is preferably 0.1% by weight to 10% by weight in that the effect of the present invention can be further exhibited. It is% by weight, more preferably 0.2% by weight to 8% by weight, still more preferably 0.5% by weight to 5% by weight, and particularly preferably 0.7% by weight to 4% by weight. Most preferably, it is 1% by weight to 3% by weight.
  • the acrylic polymer is an acrylic polymer copolymerized with a hydroxyl group-containing monomer as another monomer.
  • the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth).
  • Hydroxyalkyl (meth) acrylates such as acrylates; polypropylene glycol mono (meth) acrylates; N-hydroxyethyl (meth) acrylamides; and the like.
  • hydroxyalkyl (meth) acrylate in which the alkyl group is linear with 2 to 4 carbon atoms is preferable because the effect of the present invention can be further exhibited.
  • examples thereof include 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA), and more preferably 4-hydroxybutyl acrylate (4HBA).
  • the content ratio of the hydroxyl group-containing monomer in the total monomer component (M) is preferably 0.001% by weight to 10% by weight in that the effect of the present invention can be more exhibited. It is more preferably 0.01% by weight to 5% by weight, further preferably 0.02% by weight to 2% by weight, and particularly preferably 0.03% by weight to 1% by weight, most preferably. Is 0.05% by weight to 0.5% by weight.
  • the acrylic polymer is an acrylic polymer copolymerized with a nitrogen-containing monomer as another monomer.
  • the nitrogen-containing monomer include N-vinyl-2-pyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazin, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholin, and (meth) acryloyl.
  • nitrogen-containing vinyl-based monomers such as morpholin, N-vinylcarboxylic acid amides, and N-vinylcaprolactam
  • cyano group-containing acrylic monomers such as acrylonitrile and methacrylonitrile.
  • N-vinyl-2-pyrrolidone is preferable because the effect of the present invention can be more exhibited.
  • the content ratio of the nitrogen-containing monomer in the total monomer component (M) is preferably 0.1% by weight to 50% by weight in that the effect of the present invention can be more exhibited. It is more preferably 0.2% by weight to 30% by weight, further preferably 0.3% by weight to 20% by weight, and particularly preferably 0.4% by weight to 15% by weight, most preferably. Is 0.5% by weight to 15% by weight.
  • the Tg of the base polymer can be, for example, ⁇ 80 ° C. or higher in that the effect of the present invention can be more exhibited, and in particular, the obtained protective film can exhibit excellent bending durability.
  • the base polymer preferably an acrylic polymer
  • the base polymer is preferably Tg from the viewpoint of enhancing the deformability of the pressure-sensitive adhesive layer in the shearing direction, and particularly from the viewpoint that the obtained protective film can exhibit excellent bending durability. It is designed to be below -15 ° C.
  • the Tg of the base polymer is, for example, preferably ⁇ 10 ° C. or lower, more preferably ⁇ 15 ° C. or lower, still more preferably ⁇ 20 ° C. or lower, still more preferably ⁇ 25 ° C. or lower.
  • Tg is preferably ⁇ 70 ° C. or higher (more preferably) from the viewpoint of enhancing cohesiveness and shape restoration, and particularly from the viewpoint that the obtained protective film can exhibit excellent bending durability. Is designed to be ⁇ 65 ° C. or higher, more preferably ⁇ 60 ° C. or higher).
  • the Tg of the base polymer is derived from the Fox formula based on the Tg of the homopolymer of each monomer constituting the base polymer and the weight fraction (copolymerization ratio based on the weight) of the monomer.
  • Tg is the glass transition temperature (unit: K) of the copolymer
  • Wi is the weight fraction of the monomer i in the copolymer (copolymerization ratio based on the weight)
  • Tgi is the homopolymer of the monomer i. Represents the glass transition temperature (unit: K) of.
  • Tg of the homopolymer the value described in the publicly known material shall be adopted.
  • Tg of the homopolymer for example, the following values can be specifically used.
  • the acrylic polymer for example, various polymerization methods known as synthetic methods for the acrylic polymer, such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a suspension polymerization method, are appropriately adopted. Can be done. Among these polymerization methods, the solution polymerization method can be preferably used. As a monomer supply method for solution polymerization, a batch charging method, a continuous supply (dropping) method, a divided supply (dropping) method, or the like in which the entire amount of the monomer components is supplied at one time can be appropriately adopted.
  • a monomer supply method for solution polymerization a batch charging method, a continuous supply (dropping) method, a divided supply (dropping) method, or the like in which the entire amount of the monomer components is supplied at one time can be appropriately adopted.
  • the polymerization temperature can be appropriately selected depending on the type of the monomer and solvent used, the type of the polymerization initiator and the like, and is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, still more preferably 40 ° C.
  • the above is preferably 170 ° C. or lower, more preferably 160 ° C. or lower, and further preferably 140 ° C. or lower.
  • photopolymerization performed by irradiating with light such as UV (typically performed in the presence of a photopolymerization initiator) or irradiation with radiation such as ⁇ -rays and ⁇ -rays is performed. Active energy beam irradiation polymerization such as radiation polymerization may be adopted.
  • the solvent (polymerization solvent) used for solution polymerization can be appropriately selected from any suitable organic solvent.
  • suitable organic solvent examples thereof include aromatic compounds such as toluene (typically aromatic hydrocarbons), acetate esters such as ethyl acetate, and aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane.
  • the initiator (polymerization initiator) used for the polymerization can be appropriately selected from any suitable polymerization initiator according to the type of the polymerization method.
  • the polymerization initiator may be only one kind or two or more kinds.
  • examples of such a polymerization initiator include an azo-based polymerization initiator such as 2,2'-azobisisobutyronitrile (AIBN); a persulfate such as potassium persulfate; a benzoyl peroxide, hydrogen peroxide and the like.
  • Another example of the polymerization initiator is a redox-based initiator in which a peroxide and a reducing agent are combined.
  • the amount of the polymerization initiator used is preferably 0.005 part by weight to 1 part by weight, more preferably 0.01 part by weight to 1 part by weight, based on 100 parts by weight of all the monomer components.
  • the Mw of the acrylic polymer is preferably 10 ⁇ 10 4 to 500 ⁇ 10 4 , more preferably 10 ⁇ 10 4 to 150 ⁇ 10 4 , and further preferably 20 ⁇ 10 4 to 75 ⁇ 10 4 . Particularly preferably, it is 35 ⁇ 10 4 to 65 ⁇ 10 4 .
  • Mw means a value in terms of standard polystyrene obtained by GPC (gel permeation chromatography).
  • GPC apparatus for example, a model name “HLC-8320GPC” (column: TSKgel GMH-H (S), manufactured by Tosoh Corporation) can be used.
  • the acrylic pressure-sensitive adhesive may contain an oligomer.
  • the oligomer may be only one kind or two or more kinds.
  • the acrylic pressure-sensitive adhesive contains an oligomer, the effect of the present invention can be more exhibited.
  • the resulting protective film can exhibit excellent bending durability.
  • the weight average molecular weight Mw of the oligomer is preferably 1000 to 30,000, more preferably 1500 to 10000, still more preferably 2000 to 8000, and particularly preferably 2000 to 5000.
  • the adhesiveness and elasticity of the acrylic pressure-sensitive adhesive sheet can be improved.
  • an acrylic oligomer is preferable because it is easily compatible with an acrylic polymer.
  • the glass transition temperature Tg of the acrylic oligomer is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, further preferably 60 ° C. or higher, particularly preferably 80 ° C. or higher, and most preferably 100 ° C. or higher. That is all.
  • the upper limit of the glass transition temperature Tg of the acrylic oligomer is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 160 ° C. or lower.
  • the glass transition temperature Tg of the acrylic oligomer is determined from the Fox formula based on the Tg of the homopolymer of each constituent monomer and the weight fraction (copolymerization ratio based on the weight) of the monomer. The required value.
  • Tg is the glass transition temperature (unit: K) of the copolymer
  • Wi is the weight fraction of the monomer i in the copolymer (copolymerization ratio based on the weight)
  • Tgi is the homopolymer of the monomer i.
  • Tg of the homopolymer the values described in publicly known materials can be adopted, and for example, the values described in "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) can be used. .. When a plurality of numerical values are described in the above "Polymer Handbook", the value of conventional is adopted.
  • the acrylic oligomer contains an alicyclic alkyl (meth) acrylate as a main constituent monomer component.
  • the alicyclic alkyl (meth) acrylate may be only one kind or two or more kinds.
  • alicyclic alkyl (meth) acrylate examples include cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, and cyclooctyl (meth) acrylate; isobornyl (meth).
  • cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, and cyclooctyl (meth) acrylate; isobornyl (meth).
  • alicyclic alkyl (meth) acrylate dicyclopentanyl acrylate, dicyclopentanyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate are preferable in that the effects of the present invention can be further exhibited.
  • the content ratio of the alicyclic alkyl (meth) acrylate with respect to the total amount of the constituent monomer components of the acrylic oligomer is preferably 10% by weight to 99% by weight, more preferably 30 in that the effect of the present invention can be further exhibited. It is from% by weight to 98% by weight, more preferably 40% by weight to 97% by weight, and particularly preferably 50% by weight to 96% by weight.
  • the acrylic oligomer may contain a chain alkyl (meth) acrylate having a chain alkyl group as a constituent monomer component, and there is only one kind of chain alkyl (meth) acrylate having a chain alkyl group. It may be two or more kinds.
  • the chain shape means to include a linear shape and a branched shape.
  • the chain alkyl (meth) acrylate is preferably a chain alkyl (meth) acrylate having a chain alkyl group having 1 to 20 carbon atoms, and is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, or propyl.
  • methyl methacrylate is preferable in that the effect of the present invention can be more exhibited.
  • the content ratio of the chain alkyl (meth) acrylate with respect to the total amount of the constituent monomer components of the acrylic oligomer is preferably 10% by weight to 90% by weight, more preferably 20% by weight, in that the effect of the present invention can be more exhibited.
  • the acrylic oligomer may contain (meth) acrylic acid as a constituent monomer component, and the (meth) acrylic acid may be only one kind or two or more kinds.
  • acrylic acid is preferable in that the effects of the present invention can be more exhibited.
  • the content ratio of (meth) acrylic acid with respect to the total amount of the constituent monomer components of the acrylic oligomer is preferably 0.1% by weight to 20% by weight, more preferably 1 in that the effect of the present invention can be more exhibited. It is from% by weight to 10% by weight, more preferably 3% by weight to 7% by weight.
  • Oligomers are obtained by polymerizing the constituent monomer components by various polymerization methods.
  • any suitable additive may be used as long as the effect of the present invention is not impaired.
  • additives include polymerization initiators and chain transfer agents.
  • the content ratio of the oligomer in the acrylic pressure-sensitive adhesive is preferably 0.1 part by weight to 10 parts by weight, more preferably 10 parts by weight, based on 100 parts by weight of the acrylic polymer, in that the effect of the present invention can be more exhibited. It is 0.5 parts by weight to 8.0 parts by weight, more preferably 1.0 part by weight to 7.0 parts by weight, and particularly preferably 1.5 parts by weight to 6.0 parts by weight.
  • the acrylic pressure-sensitive adhesive may contain a tack-imparting resin in that the effects of the present invention can be more exhibited.
  • the tackifier resin include a rosin-based tackifier resin, a terpene-based tackifier resin, a hydrocarbon-based tackifier resin, an epoxy-based tackifier resin, a polyamide-based tackifier resin, an elastomer-based tackifier resin, and a phenol-based tackifier resin. , Ketone-based adhesive-imparting resin and the like.
  • the tackifier resin may be of only one type or of two or more types.
  • the amount of the tackifier resin used is preferably 5 parts by weight to 70 parts by weight, more preferably 10 parts by weight to 60 parts by weight, based on 100 parts by weight of the base polymer, in that the effect of the present invention can be more exhibited.
  • Parts more preferably 15 parts by weight to 50 parts by weight, further preferably 20 parts by weight to 45 parts by weight, particularly preferably 25 parts by weight to 40 parts by weight, and most preferably 25 parts by weight to parts. It is 35 parts by weight.
  • the tackifier resin preferably contains a tackifier resin TL having a softening point of less than 105 ° C. in that the effects of the present invention can be more exhibited.
  • the tackifier resin TL can effectively contribute to the improvement of the deformability of the pressure-sensitive adhesive layer in the surface direction (shearing direction).
  • the softening point of the tackifier resin used as the tackifier resin TL is preferably 50 ° C. to 103 ° C., more preferably 60 ° C. to 100 ° C., and further preferably.
  • the temperature is 65 ° C to 95 ° C, particularly preferably 70 ° C to 90 ° C, and most preferably 75 ° C to 85 ° C.
  • the softening point of the tackifier resin is defined as a value measured based on the softening point test method (ring ball method) specified in JIS K5902 and JIS K2207. Specifically, the sample is melted as quickly as possible at the lowest possible temperature, and the ring placed on a flat metal plate is carefully filled to prevent bubbles. After cooling, use a slightly heated sword to cut off the raised part from the plane including the upper end of the ring. Next, a support (ring stand) is placed in a glass container (heating bath) having a diameter of 85 mm or more and a height of 127 mm or more, and glycerin is poured until the depth becomes 90 mm or more.
  • a glass container heating bath
  • the steel ball (diameter 9.5 mm, weight 3.5 g) and the ring filled with the sample are immersed in glycerin so as not to contact each other, and the temperature of the glycerin is kept at 20 ° C plus or minus 5 ° C for 15 minutes. ..
  • a steel ball is placed in the center of the surface of the sample in the ring and placed in place on the support.
  • the distance from the upper end of the ring to the glycerin surface is kept at 50 mm, a thermometer is placed, the position of the center of the mercury bulb of the thermometer is set to the same height as the center of the ring, and the container is heated.
  • the flame of the Bunsen burner used for heating should be in the middle between the center and the edge of the bottom of the container to equalize the heating.
  • the rate at which the bath temperature rises after reaching 40 ° C. after the start of heating must be 5.0 plus or minus 0.5 ° C. per minute.
  • the temperature at which the sample gradually softens and flows down from the ring and finally comes into contact with the bottom plate is read, and this is used as the softening point. Two or more softening points are measured at the same time, and the average value is adopted.
  • the amount of the tackifier resin TL used is preferably 5 parts by weight to 50 parts by weight, more preferably 10 parts by weight or more, based on 100 parts by weight of the base polymer, in that the effect of the present invention can be further exhibited. It is 45 parts by weight, more preferably 15 parts by weight to 40 parts by weight, particularly preferably 20 parts by weight to 35 parts by weight, and most preferably 25 parts by weight to 32 parts by weight.
  • the tackifier resin TL one or more of the tackifier resins exemplified above, which are appropriately selected from those having a softening point of less than 105 ° C., can be adopted.
  • the tackifier resin TL preferably contains a rosin-based resin.
  • modified rosin ester examples include hydrogenated rosin ester.
  • the tackifier resin TL preferably contains a hydrogenated rosin ester in that the effects of the present invention can be more exhibited.
  • the softening point is preferably less than 105 ° C., more preferably 50 ° C. to 100 ° C., still more preferably 60 ° C. to 90 ° C. in that the effect of the present invention can be more exhibited. It is particularly preferably 70 ° C. to 85 ° C., and most preferably 75 ° C. to 85 ° C.
  • the tackifier resin TL may contain a non-hydrogenated rosin ester.
  • the non-hydrogenated rosin ester is a concept that comprehensively refers to the above-mentioned rosin esters other than the hydrogenated rosin ester.
  • Examples of the non-hydrogenated rosin ester include unmodified rosin ester, disproportionated rosin ester, and polymerized rosin ester.
  • the softening point is preferably less than 105 ° C., more preferably 50 ° C. to 100 ° C., still more preferably 60 ° C. to 90 ° C. in that the effect of the present invention can be more exhibited.
  • ° C. particularly preferably 70 ° C. to 85 ° C., and most preferably 75 ° C. to 85 ° C.
  • the tackifier resin TL may contain other tackifier resins in addition to the rosin-based resin.
  • the other tackifier resin one or more of the tackifier resins exemplified above, which are appropriately selected from those having a softening point of less than 105 ° C., may be adopted.
  • the tackifier resin TL may contain, for example, a rosin-based resin and a terpene resin.
  • the content ratio of the rosin-based resin in the entire tackifier resin TL is preferably more than 50% by weight, more preferably 55% by weight to 100% by weight, still more preferably, in that the effect of the present invention can be more exhibited. Is 60% by weight to 99% by weight, particularly preferably 65% by weight to 97% by weight, and most preferably 75% by weight to 97% by weight.
  • the tack-imparting resin may contain a combination of the tack-imparting resin TL and the tack-imparting resin TH having a softening point of 105 ° C. or higher (preferably 105 ° C. to 170 ° C.) in that the effect of the present invention can be further exhibited. good.
  • the tackifier resin TH may contain at least one selected from rosin-based tackifier resins (eg, rosin esters) and terpene-based tackifier resins (eg, terpene phenolic resins).
  • rosin-based tackifier resins eg, rosin esters
  • terpene-based tackifier resins eg, terpene phenolic resins
  • the acrylic pressure-sensitive adhesive may contain a cross-linking agent.
  • the cross-linking agent may be only one kind or two or more kinds. By using a cross-linking agent, an appropriate cohesive force can be imparted to the acrylic pressure-sensitive adhesive. Crosslinkers can also help control shift and return distances in retention tests.
  • the acrylic pressure-sensitive adhesive containing a cross-linking agent can be obtained, for example, by forming a pressure-sensitive adhesive layer using a pressure-sensitive adhesive composition containing the cross-linking agent.
  • the cross-linking agent may be contained in the acrylic pressure-sensitive adhesive in a form after the cross-linking reaction, a form before the cross-linking reaction, a form partially cross-linked, an intermediate or a composite form thereof, and the like.
  • the cross-linking agent is typically contained exclusively in the acrylic pressure-sensitive adhesive in the form after the cross-linking reaction.
  • the amount of the cross-linking agent used is preferably 0.005 parts by weight to 10 parts by weight, more preferably 0.008 parts by weight, based on 100 parts by weight of the base polymer, in that the effect of the present invention can be more exhibited. It is ⁇ 8 parts by weight, more preferably 0.01 part by weight to 7 parts by weight, further preferably 0.01 part by weight to 5 parts by weight, still more preferably 0.01 part by weight to 4 parts by weight. It is particularly preferably 0.01 parts by weight to 3 parts by weight, and most preferably 0.01 parts by weight to 2 parts by weight.
  • cross-linking agent examples include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, silicone-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, silane-based cross-linking agents, alkyl etherified melamine-based cross-linking agents, and metal chelate-based cross-linking agents.
  • Crosslinking agents such as peroxides and polyfunctional monomers, etc. are preferable, and isocyanate-based crosslinking agents, epoxy-based crosslinking agents, peroxides, and polyfunctionality are preferable in that the effects of the present invention can be further exhibited. It is a monomer, more preferably an isocyanate-based cross-linking agent, a peroxide, or a polyfunctional monomer.
  • the isocyanate-based cross-linking agent a compound having two or more isocyanate groups (including an isocyanate regenerated functional group in which the isocyanate group is temporarily protected by a blocking agent or quantification) can be used.
  • the isocyanate-based cross-linking agent include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and aliphatic isocyanates such as hexamethylene diisocyanate.
  • the isocyanate-based cross-linking agent includes lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; 2 , 4-Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylenepolyphenyl isocyanate and other aromatic diisocyanates; Trimethylol propane / tolylene diisocyanate trimer adduct (eg, manufactured by Toso Co., Ltd., Trade name Coronate L), Trimethylol propane / hexamethylene diisocyanate trimeric adduct (for example, manufactured by Toso Co., Ltd., trade name: Coronate HL), isocyanurate form of hex
  • Isocyanate adduct such as HX
  • Trimethylol propane adduct of xylylene diisocyanate for example, manufactured by Mitsui Kagaku Co., Ltd., trade name: Takenate D110N
  • Trimethylol propane adduct of xylylene diisocyanate for example, manufactured by Mitsui Kagaku Co., Ltd., product.
  • the amount of the isocyanate-based cross-linking agent used is preferably 0.005 parts by weight to 10 parts by weight, more preferably 0.008 parts by weight, based on 100 parts by weight of the base polymer, in that the effect of the present invention can be further exhibited. It is 8 parts by weight to 8 parts by weight, more preferably 0.01 part by weight to 7 parts by weight, further preferably 0.01 part by weight to 5 parts by weight, still more preferably 0.01 part by weight to 4 parts by weight. Parts, particularly preferably 0.01 parts by weight to 3 parts by weight, and most preferably 0.01 parts by weight to 2 parts by weight.
  • the weight ratio of the isocyanate-based cross-linking agent / hydroxyl group-containing monomer is preferably more than 20 and less than 50 in that the effect of the present invention can be more exhibited. It is more preferably 22 to 45, still more preferably 25 to 40, particularly preferably 27 to 40, and most preferably 30 to 35.
  • the weight ratio of the pressure-sensitive adhesive resin TL / isocyanate-based cross-linking agent preferably exceeds 2 in that the effect of the present invention can be more exhibited. It is less than 15, more preferably 5 to 13, still more preferably 7 to 12, and particularly preferably 7 to 11.
  • epoxy-based cross-linking agent a polyfunctional epoxy compound having two or more epoxy groups in one molecule can be used.
  • the epoxy-based cross-linking agent include N, N, N', N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 6-Hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, penta Elythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan
  • the amount of the epoxy-based cross-linking agent used is preferably 0.005 parts by weight to 10 parts by weight, preferably 0.005 parts by weight, based on 100 parts by weight of the base polymer, in that the effect of the present invention can be further exhibited. It is 10 parts by weight, more preferably 0.008 parts by weight to 8 parts by weight, further preferably 0.01 parts by weight to 7 parts by weight, still more preferably 0.01 parts by weight to 5 parts by weight. It is more preferably 0.01 part by weight to 4 parts by weight, particularly preferably 0.01 part by weight to 3 parts by weight, and most preferably 0.01 part by weight to 2 parts by weight.
  • polyfunctional monomer examples include 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polyethylene.
  • Glycoldi (meth) acrylate polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, etc., 2 Functional Monomer; Polyfunctional Monomer with Trifunctional or higher Functionality such as Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Tetramethylol Methantri (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate, etc.
  • the polyfunctional monomer preferably includes 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
  • the amount of the polyfunctional monomer used is preferably 0.005 parts by weight to 10 parts by weight, more preferably 0.008 parts by weight, based on 100 parts by weight of the base polymer, in that the effect of the present invention can be more exhibited. It is 8 parts by weight to 8 parts by weight, more preferably 0.01 part by weight to 7 parts by weight, further preferably 0.01 part by weight to 5 parts by weight, still more preferably 0.01 part by weight to 4 parts by weight. Parts, particularly preferably 0.01 parts by weight to 3 parts by weight, and most preferably 0.01 parts by weight to 2 parts by weight.
  • the polyfunctional monomer may be added as a base polymer to a so-called prepolymer having a low polymerization rate, and in this case, the prepolymer becomes the base polymer.
  • Acrylic adhesives include leveling agents, cross-linking aids, plasticizers, softeners, fillers, antistatic agents, antioxidants, UV absorbers, antioxidants, light stabilizers, etc., as required. It may contain various additives that are common in the field of agents. As for such various additives, conventionally known additives can be used by a conventional method.
  • the protective film according to the embodiment of the present invention may have an antistatic layer on the surface opposite to the surface of the base material layer having the pressure-sensitive adhesive layer.
  • the protective film according to the embodiment of the present invention can suppress the charge of the protective film itself, and it is difficult for dust to be adsorbed. This is a preferred embodiment.
  • the antistatic layer examples include a method of applying an antistatic resin composed of an antistatic agent and a resin component, a conductive polymer, and a conductive resin containing a conductive substance, and a method of vapor-depositing or plating a conductive substance. Can be mentioned.
  • antistatic agent contained in the antistatic resin examples include a cationic antistatic agent having a cationic functional group such as a quaternary ammonium salt, a pyridinium salt, and a first, second, and third amino groups; Anionic antistatic agents with anionic functional groups such as sulfonates, sulfates, phosphonates, phosphates; amphoteric antistatics such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives.
  • a cationic antistatic agent having a cationic functional group such as a quaternary ammonium salt, a pyridinium salt, and a first, second, and third amino groups
  • Anionic antistatic agents with anionic functional groups such as sulfonates, sulfates, phosphonates, phosphates
  • amphoteric antistatics such as alkylbetaine and its derivatives, imidazoline and its derivatives, a
  • Nonionic antistatic agent such as aminoalcohol and its derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives; The ion conductive polymer thus obtained; and the like can be mentioned.
  • These antistatic agents may be only one kind or two or more kinds.
  • the cationic antistatic agent has a quaternary ammonium group such as an alkyltrimethylammonium salt, an acyloylamide propyltrimethylammonium metosulfate, an alkylbenzylmethylammonium salt, choline acylchloride, and polydimethylaminoethylmethacrylate (meth).
  • These antistatic agents may be only one kind or two or more kinds.
  • anion-type antistatic agent examples include alkyl sulfonates, alkylbenzene sulfonates, alkyl sulfates, alkyl ethoxysulfates, alkyl phosphates, sulfonic acid group-containing styrene copolymers and the like. .. These antistatic agents may be only one kind or two or more kinds.
  • Examples of the zwitterionic antistatic agent include alkyl betaine, alkyl imidazolium betaine, and carbobetaine graft copolymerization. These antistatic agents may be only one kind or two or more kinds.
  • nonionic antistatic agent examples include fatty acid alkylolamide, di (2-hydroxyethyl) alkylamine, polyoxyethylene alkylamine, fatty acid glycerin ester, polyoxyethylene glycol fatty acid ester, sorbitan fatty acid ester, and polyoxysorbitan.
  • examples thereof include fatty acid esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl ethers, polyethylene glycols, polyoxyethylene diamines, copolymers composed of polyethers, polyesters and polyamides, and methoxypolyethylene glycol (meth) acrylates.
  • These antistatic agents may be only one kind or two or more kinds.
  • Examples of the conductive polymer include polyaniline, polypyrrole, polythiophene and the like. These conductive polymers may be only one kind or two or more kinds.
  • Examples of the conductive substance include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron and cobalt.
  • Examples include copper iodide and alloys or mixtures thereof. These conductive substances may be only one kind or two or more kinds.
  • the resin component used for the antistatic resin and the conductive resin for example, general-purpose resins such as polyester resin, acrylic resin, polyvinyl resin, urethane resin, melamine resin, and epoxy resin are used.
  • a polymer type antistatic agent it is not necessary to contain a resin component.
  • a cross-linking agent it is also possible to contain a methylolized or alkylolized melamine compound, a urea compound, a glioxal compound, an acrylamide compound; an epoxy compound; an isocyanate compound; or the like.
  • the antistatic layer for example, the above-mentioned antistatic resin, conductive polymer, conductive resin and the like are diluted with a solvent such as an organic solvent or water, and this coating liquid is applied to a substrate or the like and dried. It is formed by doing.
  • a solvent such as an organic solvent or water
  • Examples of the diluting solution used for forming the antistatic layer include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, methanol, ethanol, n-propanol, isopropanol, water and the like. .. These solvents may be only one kind or two or more kinds.
  • any appropriate coating method is appropriately used.
  • a coating method include roll coat, gravure coat, reverse coat, roll brush, spray coat, air knife coat, impregnation, curtain coat and the like.
  • Any appropriate method is appropriately used as the method of vapor deposition or plating of the conductive substance. Examples of such a method include vacuum vapor deposition, sputtering, ion plating, chemical vapor deposition, spray pyrolysis, chemical plating, electroplating and the like.
  • the thickness of the antistatic layer any appropriate thickness can be adopted as long as the effect of the present invention is not impaired.
  • the thickness of the antistatic layer is preferably 0.001 ⁇ m to 5 ⁇ m, and more preferably 0.005 ⁇ m to 1 ⁇ m in that the effect of the present invention can be more exhibited.
  • the protective film according to the embodiment of the present invention may have a top coat layer on the surface opposite to the surface of the base material layer having the pressure-sensitive adhesive layer.
  • the topcoat layer preferably contains a binder, more preferably a binder and a slip agent.
  • the binder may employ any suitable resin as long as the effects of the present invention are not impaired.
  • a resin is preferably at least one selected from the group consisting of polyester resins and urethane-based resins in that the effects of the present invention can be further exhibited.
  • polyester resin When the binder contains a polyester resin, the polyester resin may be of only one type or may be of two or more types.
  • the polyester resin is preferably a resin containing polyester as a main component.
  • the content ratio of polyester in the polyester resin is preferably more than 50% by weight, more preferably 75% by weight or more, and further preferably 90% by weight or more.
  • the polyester is preferably selected from polyvalent carboxylic acids (preferably dicarboxylic acids) having two or more carboxyl groups in one molecule and derivatives thereof (anhydrous polyvalent carboxylic acid anhydrides, esterified products, halides, etc.).
  • At least one compound (polyvalent carboxylic acid component) selected from at least one compound (polyvalent carboxylic acid component) and polyhydric alcohols (preferably diols) having two or more hydroxyl groups in one molecule. It has a structure condensed with an alcohol component).
  • Examples of the compound that can be adopted as the polyvalent carboxylic acid component include oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, ( ⁇ ) -apple acid, and meso-.
  • Product; D of any of the above-mentioned polyvalent carboxylic acids examples include steals (eg, alkyl esters, monoesters, diesters, etc.); acid halides corresponding to any of the polyvalent carboxylic acids described above (eg, dicarboxylic acid chlorides, etc.); and the like.
  • aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid and their acid anhydrides
  • adipic acid sebacic acid, azelaic acid, succinic acid, and fumal.
  • Aliphatic dicarboxylic acids such as acids, maleic acids, hymic acids, 1,4-cyclohexanedicarboxylic acids and their acid anhydrides; lower alkyl esters of the above dicarboxylic acids (eg, esters with monoalcohols having 1 to 3 carbon atoms). ; And so on.
  • Examples of the compound that can be adopted as the polyhydric alcohol component include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and neopentyl.
  • Glycol 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-1,3
  • diols such as -propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, xylylene glycol, hydrogenated bisphenol A, and bisphenol A. ..
  • Other examples include alkylene oxide adducts of these compounds (eg, ethylene oxide adducts, propylene oxide adducts, etc.).
  • the polyester resin preferably contains a water-dispersible polyester, and more preferably contains a water-dispersible polyester as a main component.
  • a hydrophilic functional group for example, at least one selected from hydrophilic functional groups such as a metal sulfonate group, a carboxyl group, an ether group, and a phosphoric acid group
  • it can be a polyester having improved water dispersibility.
  • a method for introducing a hydrophilic functional group into a polymer for example, a method for copolymerizing a compound having a hydrophilic functional group, polyester or a precursor thereof (for example, a polyhydric carboxylic acid component, a polyhydric alcohol). Any suitable method can be appropriately adopted, such as a method of modifying a component (components, oligomers thereof, etc.) to generate a hydrophilic functional group.
  • Preferred water-dispersible polyesters include polyesters (copolymerized polyesters) in which a compound having a hydrophilic functional group is copolymerized.
  • the polyester resin used as the binder may be mainly composed of saturated polyester or unsaturated polyester as the main component.
  • the polyester resin is preferably a saturated polyester having a main component thereof, and more preferably a saturated polyester having water dispersibility (for example, a saturated copolymerized polyester).
  • a polyester resin a polyester resin that may be prepared in the form of an aqueous dispersion
  • the molecular weight of the polyester resin is preferably 0.5 ⁇ 10 4 to 15 ⁇ 10 4 , and more preferably 1 as a standard polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC). It is ⁇ 10 4 to 6 ⁇ 10 4 .
  • the glass transition temperature (Tg) of the polyester resin is preferably 0 ° C to 100 ° C, more preferably 10 ° C to 80 ° C.
  • the urethane-based resin may be of only one type or of two or more types.
  • the urethane-based resin is preferably a urethane-based resin obtained by curing a composition containing the polyol (A) and the polyfunctional isocyanate compound (B).
  • polyol (A) only one type may be used, or two or more types may be used.
  • any suitable polyol can be adopted as long as it is a polyol having two or more OH groups.
  • a polyol (A) include a polyol (diol) having two OH groups, a polyol having three OH groups (triol), a polyol having four OH groups (tetraol), and five OH groups.
  • examples thereof include a polyol having 6 OH groups (pentaol) and a polyol having 6 OH groups (hexaol).
  • the polyol (A) preferably, a glycol such as ethylene glycol or propylene glycol having two or more OH groups is adopted as an essential component.
  • glycol is used as an essential component in this way, for example, it is possible to provide a urethane-based cured resin having excellent strength of the coating film after curing, excellent adhesion to a substrate, and excellent retention of additive substances.
  • the content of glycol in the polyol (A) is preferably 30% by weight to 100% by weight, more preferably 50% by weight to 100% by weight, still more preferably 70% by weight to 100% by weight. It is more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight, and most preferably substantially 100% by weight.
  • polyol (A) examples include ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 2-butyl-.
  • the polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.
  • the acid component examples include succinic acid, methylsuccinic acid, adipic acid, piceric acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-Cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphereldicarboxylic acid , These acid anhydrides and the like.
  • polyether polyol examples include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzene (catechol, resorcin, hydroquinone, etc.), etc.
  • examples thereof include a polyether polyol obtained by addition-polymerizing an alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide.
  • Specific examples thereof include polyethylene glycol, polypropylene glycol and polytetramethylene glycol.
  • polycaprolactone polyol examples include a caprolactone-based polyester diol obtained by ring-opening polymerization of a cyclic ester monomer such as ⁇ -caprolactone and ⁇ -valerolactone.
  • polycarbonate polyol examples include a polycarbonate polyol obtained by subjecting the above-mentioned polyol component and phosgen to a polycondensation reaction; the above-mentioned polyol component and dimethyl carbonate, diethyl carbonate, diprovyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, Polycarbonate polyol obtained by ester exchange condensation with carbonic acid diesters such as propylene carbonate, diphenyl carbonate, dibenzyl carbonate; copolymerized polycarbonate polyol obtained by using two or more of the above polyol components in combination; containing various polycarbonate polyols and a carboxyl group.
  • a polycarbonate polyol obtained by subjecting the above-mentioned polyol component and phosgen to a polycondensation reaction
  • Polycarbonate polyol obtained by esterifying a compound Polycarbonate polyol obtained by etherifying a various polycarbonate polyols and a hydroxyl group-containing compound; Obtaining by an ester exchange reaction between various polycarbonate polyols and an ester compound.
  • Polycarbonate-based polycarbonate polyol obtained by a polycondensation reaction between the various polycarbonate polyols and a dicarboxylic acid compound Examples thereof include a copolymerized polyether polycarbonate polyol obtained by copolymerizing and alkylene oxide.
  • castor oil-based polyol examples include castor oil-based polyol obtained by reacting a castor oil fatty acid with the above-mentioned polyol component. Specific examples thereof include castor oil-based polyols obtained by reacting castor oil fatty acid with polypropylene glycol.
  • the polyfunctional isocyanate compound (B) may be only one kind or two or more kinds.
  • polyfunctional isocyanate compound (B) any suitable polyfunctional isocyanate compound that can be used in the urethanization reaction can be adopted.
  • examples of such a polyfunctional isocyanate compound (B) include a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, and a polyfunctional aromatic isocyanate compound.
  • polyfunctional aliphatic isocyanate compound examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylenediocyanate, dodecamethylene diisocyanate, 2,4.
  • polyfunctional aliphatic isocyanate compound examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylenediocyanate, dodecamethylene diisocyanate, 2,4.
  • Examples thereof include 4-trimethylhexamethylene diisocyanate.
  • polyfunctional alicyclic isocyanate compound examples include 1,3-cyclopentene diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate.
  • examples thereof include hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate.
  • polyfunctional aromatic diisocyanate compound examples include phenylenediocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate, 4 , 4'-toluene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenediocyanate, xylylene diisocyanate and the like.
  • polyfunctional isocyanate compound (B) examples include a trimethylolpropane adduct compound of various polyfunctional isocyanate compounds as described above, a biuret compound reacted with water, and a trimer having an isocyanurate ring. Moreover, you may use these together.
  • the polyfunctional isocyanate compound (B) is preferably 5% by weight to 60% by weight, more preferably 8% by weight to 60% by weight, based on the polyol (A). %, More preferably 10% by weight to 60% by weight.
  • the urethane resin is typically obtained by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).
  • a composition may contain any suitable other components other than the polyol (A) and the polyfunctional isocyanate compound (B), as long as the effects of the present invention are not impaired.
  • other components include catalysts, resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, and the like.
  • examples thereof include antiaging agents, conductive agents, antioxidants, ultraviolet absorbers, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents and the like.
  • the effect of the present invention such as a urethanization reaction method using bulk polymerization or solution polymerization can be used. Any suitable method can be adopted as long as it does not impair.
  • the top coat layer can be a binder other than polyester resin and urethane resin (for example, acrylic resin, acrylic-styrene resin, acrylic-silicone resin, silicone resin, polysilazane) as a binder as long as the performance of the protective film is not significantly impaired. At least one resin selected from a resin, a fluororesin, and a polyolefin resin) may be further contained.
  • the binder of the topcoat layer is composed of at least one selected from the group consisting substantially of polyester resin and urethane resin, and is composed of polyester resin and urethane resin occupying the binder.
  • the proportion of at least one selected from the group is preferably 98% by weight to 100% by weight, more preferably 99% by weight to 100% by weight, still more preferably 99.5% by weight to 100% by weight. be.
  • the proportion of the binder in the entire top coat layer is preferably 15% by weight to 95% by weight, more preferably 25% by weight to 80% by weight.
  • the slip agent preferably contains an ester of a higher fatty acid and a higher alcohol (hereinafter, may be referred to as "wax ester").
  • the "higher fatty acid” is preferably a carboxylic acid having 8 or more carbon atoms, and the carbon atom number is more preferably 10 or more, still more preferably 10 to 40.
  • the carboxylic acid is preferably a monovalent carboxylic acid.
  • the "higher alcohol” is preferably an alcohol having 6 or more carbon atoms, and the carbon atom number is more preferably 10 or more, still more preferably 10 to 40.
  • the alcohol is preferably a monohydric or divalent alcohol, and more preferably a monohydric alcohol.
  • the topcoat layer having a composition containing such a wax ester in combination with the above-mentioned binder is difficult to whiten even if it is maintained under high temperature and high humidity conditions. Therefore, a protective film provided with a base material having such a top coat layer can have a higher appearance quality.
  • the top coat layer having the above composition realizes excellent whitening resistance (for example, the property of being difficult to whiten even when kept under high temperature and high humidity conditions). That is, it is presumed that the conventionally used silicone-based lubricant exerts a function of imparting slipperiness to the surface of the topcoat layer by bleeding.
  • the degree of bleeding of these silicone-based lubricants tends to vary depending on the storage conditions (temperature, humidity, aging, etc.). Therefore, for example, when the protective film is kept under normal storage conditions (for example, 25 ° C., 50% RH), it has an appropriate slipperiness for a relatively long period (for example, about 3 months) immediately after the protective film is manufactured.
  • the amount of silicone-based lubricant used is set so that It ends up. Such an excessively bleeding silicone-based lubricant may cause the top coat layer (and thus the protective film) to whiten.
  • top coat layer a specific combination of wax ester as a slip agent and polyester resin as a binder is adopted. According to such a combination of the slip agent and the binder, the degree of bleeding from the top coat layer of the wax ester is not easily affected by the storage conditions. This can improve the whitening resistance of the protective film.
  • one or more of the compounds represented by the general formula (W) can be preferably adopted.
  • Each of X and Y in the formula (W) is independently and preferably a hydrocarbon group having 10 to 40 carbon atoms, and the carbon atom number thereof is more preferably 10 to 35, still more preferably 14. It is ⁇ 35, and particularly preferably 20 to 32. If the number of carbon atoms is too small, the effect of imparting slipperiness to the topcoat layer may be insufficient.
  • the above hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • the above hydrocarbon group is preferably a saturated hydrocarbon group.
  • the above-mentioned hydrocarbon group may have a structure containing an aromatic ring, a structure not containing an aromatic ring (aliphatic hydrocarbon group), or a structure containing an aliphatic ring. It may be a hydrocarbon group (aliphatic hydrocarbon group) or a chain (including linear and branched) hydrocarbon groups.
  • X and Y in the formula (W) are independent compounds, preferably a chain alkyl group having 10 to 40 carbon atoms, and more preferably 10 to 40 carbon atoms. It is a compound that is a linear alkyl group. Specific examples of such compounds include, for example, myricyl cerotic acid (CH 3 (CH 2 ) 24 COO (CH 2 ) 29 CH 3 ), myricyl palmitate (CH 3 (CH 2 ) 14 COO (CH 2 ) 29 ).
  • cetyl palmitate (CH 3 (CH 2 ) 14 COO (CH 2 ) 15 CH 3 ), stearyl stearyl acid (CH 3 (CH 2 ) 16 COO (CH 2 ) 17 CH 3 ) and the like.
  • the wax ester has a melting point of preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, and particularly preferably 75 ° C. or higher. According to such a wax ester, higher whitening resistance can be realized.
  • the wax ester preferably has a melting point of 100 ° C. or lower. Since such a wax ester has a high effect of imparting slipperiness, it is possible to form a topcoat layer having higher scratch resistance. It is preferable that the melting point of the wax ester is 100 ° C. or lower from the viewpoint that it is easy to prepare an aqueous dispersion of the wax ester. As such a wax ester, for example, myricyl cerotic acid can be preferably adopted.
  • Natural wax containing such wax ester can be used as a raw material for the top coat layer.
  • the content ratio of the above wax esters is preferably more than 50% by weight based on the non-volatile content (NV). More, more preferably 65% by weight or more, still more preferably 75% by weight or more.
  • Examples of such natural wax include carnauba wax (generally, beeswax cerotic acid is contained in a proportion of preferably 60% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more), palm.
  • Vegetable waxes such as wax; animal waxes such as beeswax and whale wax; and the like can be mentioned.
  • the melting point of such a natural wax is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, and particularly preferably 75 ° C. or higher.
  • a chemically synthesized wax ester may be used, or a wax ester obtained by purifying natural wax may be used. These raw materials may be only one kind or two or more kinds.
  • the proportion of the slip agent in the entire top coat layer is preferably 5% by weight to 50% by weight, more preferably 10% by weight to 40% by weight. If the content of the slip agent is too small, the scratch resistance may be easily lowered. If the content ratio of the slip agent is too large, the effect of improving the whitening resistance may be insufficient.
  • the top coat layer may contain other slip agents in addition to the wax ester.
  • slip agents include wax esters such as petroleum wax (paraffin wax, etc.), mineral wax (montan wax, etc.), higher fatty acid (serotinic acid, etc.), and triglyceride (palmitic acid triglyceride, etc.).
  • wax esters such as petroleum wax (paraffin wax, etc.), mineral wax (montan wax, etc.), higher fatty acid (serotinic acid, etc.), and triglyceride (palmitic acid triglyceride, etc.).
  • a silicone-based lubricant, a fluorine-based lubricant, or the like may be contained.
  • a preferred embodiment of the topcoat layer is a form in which the silicone-based lubricant and the fluorine-based lubricant are substantially not contained.
  • the total content of the silicone-based lubricant and the fluorine-based lubricant is 0, preferably 0 in the entire top
  • the top coat layer may be an antistatic component, a cross-linking agent, an antioxidant, a coloring agent (pigment, dye, etc.), a fluidity adjusting agent (thixotropic agent, thickening agent, etc.), a film-forming auxiliary, and a surfactant, if necessary. It may contain additives such as activators (antifoaming agents, dispersants, etc.), preservatives and the like.
  • a preferred embodiment of the topcoat layer contains an antistatic component.
  • the antistatic component is a component that can exert an action of preventing or suppressing the charge of the protective film.
  • an antistatic component for example, an organic or inorganic conductive substance, various antistatic agents, or the like can be used as the antistatic component. It is also possible to use an antistatic agent that can be used in the antistatic layer described above.
  • organic conductive substance examples include a cationic antistatic agent having a cationic functional group such as a quaternary ammonium salt, a pyridinium salt, a primary amino group, a secondary amino group, and a tertiary amino group; a sulfonate or a sulfate ester salt.
  • a cationic antistatic agent having a cationic functional group such as a quaternary ammonium salt, a pyridinium salt, a primary amino group, a secondary amino group, and a tertiary amino group
  • a sulfonate or a sulfate ester salt examples include a cationic antistatic agent having a cationic functional group such as a quaternary ammonium salt, a pyridinium salt, a primary amino group, a secondary amino group, and a tertiary amino group.
  • anionic antistatic agents having anionic functional groups such as phosphate salts
  • amphoteric ionic antistatic agents such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives
  • aminoalcohol and Nonionic antistatic agents such as its derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives; polymerized or polymerized with the above cationic, anionic and amphoteric ionic ionic conductive groups (eg, quaternary ammonium bases).
  • Examples thereof include ionic conductive polymers obtained by copolymerization; conductive polymers such as polythiophene, polyaniline, polypyrrole, polyethyleneimine, and allylamine-based polymers.
  • conductive polymers such as polythiophene, polyaniline, polypyrrole, polyethyleneimine, and allylamine-based polymers.
  • Such an antistatic agent may be only one kind or two or more kinds.
  • the inorganic conductive substance examples include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron and cobalt. , Copper iodide, ITO (indium oxide / tin oxide), ATO (antimony oxide / tin oxide) and the like.
  • Such an inorganic conductive substance may be only one kind or two or more kinds.
  • the antistatic agent examples include a cationic antistatic agent, an anionic antistatic agent, a zwitterionic antistatic agent, a nonionic antistatic agent, and the above-mentioned cationic, anionic, and zwitterionic ionic conductive groups.
  • examples thereof include an ion conductive polymer obtained by polymerizing or copolymerizing a monomer.
  • the antistatic component preferably contains an organic conductive substance.
  • the organic conductive substance various conductive polymers can be preferably used. According to such a configuration, both good antistatic property and high scratch resistance can be achieved at the same time.
  • the conductive polymer examples include polythiophene, polyaniline, polypyrrole, polyethyleneimine, and allylamine-based polymers. Such a conductive polymer may be only one kind or two or more kinds. Further, it may be used in combination with other antistatic components (inorganic conductive substance, antistatic agent, etc.).
  • the amount of the conductive polymer used is preferably 1 part by weight to 100 parts by weight, more preferably 2 parts by weight to 70 parts by weight, still more preferably, with respect to 100 parts by weight of the binder contained in the top coat layer. It is 3 parts by weight to 50 parts by weight. If the amount of the conductive polymer used is too small, the antistatic effect may be reduced. If the amount of the conductive polymer used is too large, the compatibility of the conductive polymer in the topcoat layer may be insufficient, and the appearance quality of the topcoat layer may be deteriorated or the solvent resistance may be deteriorated. ..
  • the conductive polymer include polythiophene and polyaniline.
  • the polythiophene the polystyrene-equivalent weight average molecular weight Mw is preferably 40 ⁇ 10 4 or less, and more preferably 30 ⁇ 10 4 or less.
  • the polyaniline the polystyrene-equivalent weight average molecular weight Mw is preferably 50 ⁇ 10 4 or less, and more preferably 30 ⁇ 10 4 or less.
  • the weight average molecular weight Mw in terms of polystyrene of the conductive polymer is preferably at 0.1 ⁇ 10 4 or more, more preferably 0.5 ⁇ 10 4 or more.
  • polythiophene means a polymer of unsubstituted or substituted thiophene.
  • substituted thiophene polymer include poly (3,4-ethylenedioxythiophene) and the like.
  • the conductive polymer used for preparing the coating material is the said.
  • a form in which the conductive polymer is dissolved or dispersed in water aqueous polymer aqueous solution
  • a conductive polymer aqueous solution dissolves, for example, a conductive polymer having a hydrophilic functional group (a conductive polymer that can be synthesized by a method such as copolymerizing a monomer having a hydrophilic functional group in the molecule) in water.
  • a conductive polymer having a hydrophilic functional group a conductive polymer that can be synthesized by a method such as copolymerizing a monomer having a hydrophilic functional group in the molecule
  • it can be prepared by dispersing.
  • hydrophilic functional group examples include an acid ester group (for example, —O—PO (OH) 2).
  • Such hydrophilic functional groups may form salts.
  • commercially available products of the aqueous polythiophene solution include the trade name "Denatron” series manufactured by Nagase Chemtech.
  • Examples of commercially available products of the polyaniline sulfonic acid aqueous solution include the trade name “aqua-PASS” manufactured by Mitsubishi Rayon Co., Ltd.
  • an aqueous polythiophene solution is preferably used.
  • a polythiophene aqueous solution containing polystyrene sulfonate (PSS) (for example, a form in which PSS is added as a dopant to polythiophene) is preferable.
  • PSS polystyrene sulfonate
  • Such an aqueous solution of polythiophene may contain polythiophene: PSS in a mass ratio of preferably 1: 1 to 1:10.
  • the total content of polythiophene and PSS in such an aqueous solution of polythiophene is preferably 1% by mass to 5% by weight.
  • the total amount of polythiophene and PSS is preferably 5 parts by weight to 200 parts by weight, more preferably 10 parts by weight, based on 100 parts by weight of the binder. It is from 100 parts by weight to 100 parts by weight, more preferably 25 parts by weight to 70 parts by weight.
  • the topcoat layer contains, if necessary, a conductive polymer and one or more other antistatic components (organic conductive substances other than the conductive polymer, inorganic conductive substances, antistatic agents, etc.). You may.
  • the topcoat layer is substantially free of antistatic components other than the conductive polymer. That is, it is preferable that the antistatic component contained in the top coat layer is substantially composed of only the conductive polymer.
  • the topcoat layer preferably contains a cross-linking agent.
  • a cross-linking agent such as a melamine-based cross-linking agent, an isocyanate-based cross-linking agent, or an epoxy-based cross-linking agent used for cross-linking a general resin can be appropriately selected and used.
  • the cross-linking agent comprises a melamine-based cross-linking agent.
  • the cross-linking agent may be a top coat layer consisting substantially only of a melamine-based cross-linking agent (melamine-based resin) (that is, substantially free of a cross-linking agent other than the melamine-based cross-linking agent).
  • melamine-based resin melamine-based resin
  • One preferred embodiment of the topcoat layer is when the material of the substrate layer is at least one selected from polyimide and polyetheretherketone, the topcoat layer contains a binder containing a urethane resin and an antistatic component. It is an aspect. As described above, by adopting a binder containing a urethane resin as the binder of the antistatic component of the top coat layer, the top on the surface of the base material layer made of at least one selected from polyimide and polyetheretherketone. The coating formability of the coat layer becomes excellent, the appearance can be improved, and excellent antistatic property can be exhibited.
  • a binder containing a polyester resin is often preferable, but for a specific base material layer in which the material of the base material layer is at least one selected from polyimide and polyetheretherketone. Therefore, the affinity of the binder containing the polyester resin may be low, and the appearance of the topcoat layer after coating may be deteriorated, or excellent antistatic properties may not be exhibited.
  • the top coat layer may contain a binder containing a urethane resin and an antistatic component. The coating formability of the top coat layer on the surface of the base material layer becomes excellent, the appearance can be improved, and excellent antistatic property can be exhibited.
  • the topcoat layer is formed by a method comprising applying a liquid composition (coating material for forming a topcoat layer) in which the above resin components and additives used as necessary are dispersed or dissolved in an appropriate solvent to a substrate.
  • a liquid composition coating material for forming a topcoat layer
  • a method of applying the coating material to the first surface of the base material, drying it, and performing a curing treatment (heat treatment, ultraviolet treatment, etc.) as necessary can be preferably adopted.
  • the NV (nonvolatile content) of the coating material is preferably 5% by weight or less, more preferably 0.05% by weight to 5% by weight, still more preferably 0.05% by weight to 1% by weight.
  • the NV of the coating material is preferably 0.05% by weight to 0.50% by weight, more preferably 0.10% by weight to 0.30% by weight. do. By using such a low NV coating material, a more uniform top coat layer can be formed.
  • a solvent capable of stably dissolving or dispersing the top coat layer forming component is preferable.
  • a solvent can be an organic solvent, water, or a mixed solvent thereof.
  • the organic solvent include esters such as ethyl acetate; ketones such as methyl ethyl ketone, acetone and cyclohexanone; cyclic ethers such as tetrahydrofuran (THF) and dioxane; aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane.
  • the solvent constituting the coating material for forming the top coat layer is water or a mixed solvent containing water as a main component (for example, a mixed solvent of water and ethanol).
  • the thickness of the top coat layer is preferably 3 nm to 500 nm, more preferably 3 nm to 100 nm, and even more preferably 3 nm to 60 nm. If the thickness of the top coat layer is too large, the transparency (light transmittance) of the protective film may easily decrease. If the thickness of the top coat layer is too small, it may be difficult to form the top coat layer uniformly. For example, the thickness of the top coat layer may vary greatly depending on the location. Therefore. , The appearance of the protective film may be uneven.
  • the thickness of the topcoat layer can be grasped by observing the cross section of the topcoat layer with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • a target sample a substrate on which a topcoat layer is formed, a protective film provided with a substrate, etc.
  • the result obtained by TEM observation of the sample cross section by the ultrathin section method can be preferably adopted as the thickness of the top coat layer.
  • a TEM model "H-7650" manufactured by Hitachi, Ltd. can be used.
  • the cross-sectional image obtained under the conditions of acceleration voltage: 100 kV and Magnification: 60,000 times is binarized, and then the cross-sectional area of the top coat is divided by the sample length in the field of view. By doing so, the thickness of the top coat layer (average thickness in the visual field) is actually measured. If the topcoat layer can be observed clearly enough without heavy metal dyeing, the heavy metal dyeing treatment may be omitted.
  • a calibration curve is obtained for the correlation between the thickness grasped by the TEM and the detection result by various thickness detection devices (for example, surface roughness meter, interference thickness meter, infrared spectrophotometer, various X-ray diffractometers, etc.). The thickness of the top coat layer may be obtained by creating and calculating.
  • the surface resistance value measured on the surface of the topcoat layer is preferably 10 12 ⁇ or less, more preferably 10 4 ⁇ to 10 12 ⁇ , still more preferably 10 4 ⁇ to 10 11 ⁇ , and particularly. It is preferably 5 ⁇ 10 4 ⁇ to 10 10 ⁇ , and most preferably 10 4 ⁇ to 10 9 ⁇ .
  • a protective film exhibiting such a surface resistance value can be suitably used as a protective film used in a process of processing or transporting an article that dislikes static electricity, such as a liquid crystal cell or a semiconductor device.
  • the value of the surface resistance value can be calculated from the value of the surface resistance measured in an atmosphere of 23 ° C. and 50% RH using a commercially available insulation resistance measuring device.
  • the coefficient of friction of the top coat layer is preferably 0.4 or less.
  • the lower limit of the friction coefficient is preferably 0.1 or more, more preferably 0.15 or more, in consideration of the balance with other characteristics (for example, appearance quality and printability).
  • the coefficient of friction for example, a value obtained by rubbing the surface of the top coat layer with a vertical load of 40 mN in a measurement environment of 23 ° C. and 50% RH can be adopted.
  • the amount of slipper used may be set so that a favorable coefficient of friction is achieved.
  • the surface of the top coat layer has a property of being easily printed with an oil-based ink (for example, using an oil-based marking pen).
  • the protective film having such a top coat layer has an identification number of the adherend to be protected in the process of processing or transporting the adherend (for example, an optical component) performed with the protective film attached. Etc. are suitable for being described and displayed on the protective film. Therefore, a top coat layer having excellent printability in addition to appearance quality is preferable.
  • a top coat layer having an alcohol-based solvent and having high printability for oil-based inks containing pigments is preferable.
  • a top coat layer in which the printed ink is difficult to remove due to rubbing or transfer (that is, excellent in print adhesion) is preferable.
  • the topcoat layer preferably has solvent resistance to such an extent that the print is not noticeably changed in appearance even if the print is wiped with alcohol (for example, ethyl alcohol) when the print is corrected or erased.
  • the topcoat layer preferably contains a wax ester as a slip agent
  • the surface of the topcoat layer is further stripped (eg, any suitable stripping treatment such as a silicone-based stripping agent or a long-chain alkyl-based stripping agent).
  • Sufficient slipperiness can be realized even in an embodiment in which the agent is not applied and dried.
  • Such an embodiment in which the surface of the top coat layer is not further peeled can prevent whitening caused by the peeling agent (for example, whitening due to storage under heating and humidifying conditions). It is preferable in that. It is also advantageous in terms of solvent resistance.
  • the protective film according to the embodiment of the present invention can also be implemented in an embodiment including a base material, an adhesive layer, and a top coat layer, as well as other layers.
  • Examples of such an arrangement of the "other layer” include between the first surface (back surface) of the base material and the top coat layer, between the second surface (front surface) of the base material and the pressure-sensitive adhesive layer, and the like.
  • the layer arranged between the back surface of the base material and the top coat layer may be, for example, a layer containing an antistatic component (antistatic layer).
  • the layer arranged between the front surface of the base material and the pressure-sensitive adhesive layer may be, for example, an undercoat layer (anchor layer), an antistatic layer, or the like that enhances the anchoring property of the pressure-sensitive adhesive layer with respect to the second surface.
  • the protective film may have a structure in which an antistatic layer is arranged on the front surface of the base material, an anchor layer is arranged on the antistatic layer, and an adhesive layer is arranged on the anchor layer.
  • the protective film according to the embodiment of the present invention has excellent flexibility and transparency, and therefore, for example, a bendable device (bendable device), a foldable device (foldable device), or a roller having a movable bending portion. It may be suitably provided for a bull device (a device that can be rolled).
  • the protective film according to the embodiment of the present invention is particularly excellent in flexibility and transparency, so that it has been more difficult to apply foldable devices (foldable devices) and rollable devices (rollable devices). ) Can be suitably provided.
  • the foldable device according to the embodiment of the present invention includes a protective film according to the embodiment of the present invention.
  • the foldable device of the present invention may include any suitable other member as long as it is provided with the protective film according to the embodiment of the present invention.
  • the rollable device according to the embodiment of the present invention includes a protective film according to the embodiment of the present invention.
  • the rollable device of the present invention may include any suitable other member as long as it is provided with the protective film according to the embodiment of the present invention.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of a foldable device according to an embodiment of the present invention as a representative example of one usage embodiment of the protective film of the present invention.
  • the foldable device 1000 according to the embodiment of the present invention includes a cover film 10, an adhesive layer 20, a polarizing plate 30, an adhesive layer 40, a touch sensor 50, an adhesive layer 60, an OLED 70, and an embodiment of the present invention.
  • the protective film 100 is provided.
  • the outermost layer of the OLED 70 on the side of the protective film 100 according to the embodiment of the present invention is typically a polyimide substrate.
  • a barrier layer is preferably provided on the opposite side of the protective film 100 according to the embodiment of the present invention of the polyimide substrate.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of a foldable device according to an embodiment of the present invention as a representative example of one usage embodiment of the protective film of the present invention.
  • the foldable device 1000 according to the embodiment of the present invention includes a
  • the protective film 100 is composed of the pressure-sensitive adhesive layer 80 and the base material layer 90.
  • the pressure-sensitive adhesive layer 20, the pressure-sensitive adhesive layer 40, and the pressure-sensitive adhesive layer 60 are. It may be a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive having the same composition as the pressure-sensitive adhesive layer 80 constituting the protective film 100 of the present invention, or it may be a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive having a different composition.
  • the protective film according to the embodiment of the present invention has excellent flexibility and transparency, and therefore, for example, a bendable device (bendable device), a foldable device (foldable device), or a roller having a movable bending portion. It may be suitably provided on the back surface (opposite surface of the display surface) of a bull device (a device that can be rolled).
  • FIG. 1 is a diagram provided on the back surface (opposite surface of the display surface) of a foldable device (foldable device).
  • the zoom lens is 1.00x and the objective lens is 2.5x / 0 with NewView7300 (manufactured by ZYGO).
  • the surface roughness was measured with .075 TI OFN22 WD 10.3 (manufactured by Nikon Corporation), and Ra was calculated using analysis software (Metaro Pro).
  • the protective film in a flat state is fixed at 90 ° C. with the adhesive layer surface facing outward and the protective film bent at 6 ⁇ , sandwiched between the silicone-treated surfaces of the silicone-treated separator. It was held for 48 hours. Then, the bending was released, and the film was allowed to stand at 23 ° C. and 50% RH for 24 hours, and then the angle of the bent film was measured. The case where the state was completely restored to the original state was set to 180 degrees, and the case where the bent state at the initial fixing was maintained as it was was set to 0 degrees.
  • haze (%) (Td / Tt) x 100 (Td: diffusion transmittance, Tt: Calculated by total light transmittance). The total light transmittance was measured according to JIS-K-7316.
  • ⁇ Young's modulus> A sample piece is cut into strips with a width of 10 mm, and the strip-shaped sample pieces are measured by pulling them in the longitudinal direction at a distance between chucks of 100 mm with a universal tensile compression tester (Tensilon) under a temperature environment of 25 ° C. The Young's modulus was determined from the obtained SS (Strine-Strength) curve. The measurement conditions were a tensile speed of 200 mm / min and a chuck spacing of 50 mm.
  • the method of obtaining Young's modulus from the SS curve was to create a graph of the SS curve, draw a tangent line (linear expression) on the graph in the range of displacement of 1 mm to 2 mm, and obtain it from the inclination of the tangent line.
  • the thickness was calculated using the thickness of the base material layer.
  • the protective film was cut into a width of 25 mm and a length of 150 mm to prepare a sample for evaluation.
  • the surface of the pressure-sensitive adhesive layer of the evaluation sample is attached to a glass plate (manufactured by Matsunami Glass Industry Co., Ltd., trade name: microslide glass S) by one reciprocating 2.0 kg roller. Attached.
  • peeling is performed at a peeling angle of 180 degrees and a tensile speed of 300 mm / min using a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB). Then, the adhesive strength was measured.
  • ⁇ Surface resistance value> Using a resistivity meter (Mitsubishi Chemical Analytical Co., Ltd., "High Resta UP MCP-HT450 type"), contact the URS probe with the surface of the protective film not attached to the adhesive layer, and apply the voltage at 100 V and the voltage application time for 10 seconds. The surface resistivity value was measured.
  • a resistivity meter Mitsubishi Chemical Analytical Co., Ltd., "High Resta UP MCP-HT450 type
  • the temperature is raised to 65 ° C. and the reaction is carried out for 10 hours, and then ethyl acetate is added to obtain a solution of the acrylic polymer (a) having a solid content concentration of 30% by weight. rice field.
  • an isocyanate-based cross-linking agent (trade name "Takenate D110N", manufactured by Mitsui Chemicals, Inc.) was added to the solution of the acrylic polymer (a) with respect to 100 parts by weight of the acrylic polymer (a) (solid content).
  • the pressure-sensitive adhesive composition A was prepared by adding 1 part by weight in terms of conversion. The compositions are summarized in Table 1.
  • oligomer (1) a solid acrylic oligomer (oligomer (1)).
  • the weight average molecular weight of the oligomer (1) was 5100, and the glass transition temperature (Tg) was 130 ° C.
  • Prepolymer composition B 100 parts by weight, 1,6-hexanediol diacrylate (HDDA): 0.07 parts by weight, oligomer (1): 3 parts by weight, and silane coupling agent (Shin-Etsu) as post-addition components.
  • Chemical "KBM403" After adding 0.3 parts by weight, these were uniformly mixed to prepare a pressure-sensitive adhesive composition B.
  • Table 1 The compositions are summarized in Table 1.
  • Prepolymer composition C 100 parts by weight, 1,6-hexanediol diacrylate (HDDA): 0.06 parts by weight, oligomer (1) prepared in Production Example 2: 3 parts by weight, and post-addition component.
  • Silane coupling agent (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.): After adding 0.3 parts by weight, these were uniformly mixed to prepare a pressure-sensitive adhesive composition C.
  • Table 1 The compositions are summarized in Table 1.
  • Adhesive Composition D Acrylic polymer D: 100 parts by weight, Coronate HX as a cross-linking agent (manufactured by Toso Co., Ltd., isocyanate-based cross-linking agent): 0.05 parts by weight, oligomer (1) prepared in Production Example 2: 2 parts by weight, antioxidant Irganox 1010 (manufactured by BASF): 0.3 parts by weight and Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.): 0.01 parts by weight are mixed and stirred sufficiently to reduce the total solid content.
  • the pressure-sensitive adhesive composition D was prepared by diluting with ethyl acetate and acetylacetone having a solvent content of 2% by weight so as to be 21% by weight. The compositions are summarized in Table 1.
  • Adhesive Composition E Acrylic polymer E: 100 parts by weight, Coronate HX (manufactured by Toso Co., Ltd., isocyanate-based cross-linking agent): 0.03 parts by weight, oligomer (1) prepared in Production Example 2: 5 parts by weight, antioxidant Irganox 1010 (manufactured by BASF): 0.3 parts by weight and Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.): 0.01 parts by weight are mixed and stirred sufficiently to reduce the total solid content.
  • the pressure-sensitive adhesive composition E was prepared by diluting with ethyl acetate to be 21% by weight and acetylacetone to be 2% by weight of the solvent content. The compositions are summarized in Table 1.
  • Adhesive Composition F (Preparation of Adhesive Composition F)
  • Acrylic polymer E prepared in Production Example 5 100 parts by weight, peroxide as a cross-linking agent (Niper BMT-40SV, manufactured by Nippon Yushi Co., Ltd.): 0.25 parts by weight, oligomer (1) prepared in Production Example 2.
  • 3 parts by weight, Irganox 1010 (manufactured by BASF) as an antioxidant: 0.3 parts by weight, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.): 0.01 parts by weight as a catalyst are mixed and sufficiently stirred.
  • the pressure-sensitive adhesive composition F was prepared by diluting with ethyl acetate and acetylacetone having a solvent content of 2% by weight so that the total solid content was 21% by weight.
  • Table 1 The compositions are summarized in Table 1.
  • Prepolymer composition G 100 parts by weight, 1,6-hexanediol diacrylate (HDDA): 0.30 parts by weight as a post-addition component, and a silane coupling agent ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd.): 0. After adding 3 parts by weight, these were uniformly mixed to prepare a pressure-sensitive adhesive composition G.
  • the compositions are summarized in Table 1.
  • Example 1 A commercially available release liner (Diafoil MRF-38), manufactured by Mitsubishi Plastics Co., Ltd. was prepared.
  • the pressure-sensitive adhesive composition A was applied to one surface (peeling surface) of the peeling liner so that the thickness after drying was 25 ⁇ m, and dried at 130 ° C. for 3 minutes. In this way, a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m composed of the acrylic pressure-sensitive adhesive A corresponding to the pressure-sensitive adhesive composition A was formed on the peeling surface of the peeling liner.
  • a base material layer a polyimide-based base material having a thickness of 25 ⁇ m (trade name “UPIREX-25S”, manufactured by Ube Industries, Ltd.) was prepared.
  • the pressure-sensitive adhesive layer formed on the release liner was bonded to one surface of the base material layer.
  • the release liner was left as it was on the pressure-sensitive adhesive layer and used to protect the surface of the pressure-sensitive adhesive layer (the surface of the pressure-sensitive adhesive layer).
  • the obtained structure was passed once through a laminator (0.3 MPa, speed 0.5 m / min) at 80 ° C. and then aged in an oven at 50 ° C. for 1 day. In this way, the protective film (1) was obtained.
  • the results are shown in Table 2.
  • Example 2 A protective film (2) was obtained in the same manner as in Example 1 except that a polyimide-based substrate having a thickness of 50 ⁇ m (trade name “UPIREX-50RN”, manufactured by Ube Industries, Ltd.) was used as the substrate layer. The results are shown in Table 2.
  • Example 3 A protective film (3) was obtained in the same manner as in Example 1 except that a 25 ⁇ m-thick polyetheretherketone (PEEK) -based substrate (trade name “Expeak”, manufactured by Kurabo Industries Ltd.) was used as the substrate layer. rice field. The results are shown in Table 2.
  • PEEK polyetheretherketone
  • Example 4 A protective film (4) was obtained in the same manner as in Example 1 except that a polyimide-based substrate having a thickness of 50 ⁇ m (trade name “Neoprim S100”, manufactured by Mitsubishi Gas Chemical Company Limited) was used as the substrate layer. The results are shown in Table 2.
  • Example 5 A protective film (5) was obtained in the same manner as in Example 1 except that a polyimide-based substrate having a thickness of 50 ⁇ m (trade name “UPIREX-50S”, manufactured by Ube Industries, Ltd.) was used as the substrate layer. The results are shown in Table 2.
  • Example 6 A protective film (6) was obtained in the same manner as in Example 1 except that a PEN-based base material having a thickness of 50 ⁇ m (trade name “PEN Q51”, manufactured by Teijin Limited) was used as the base material layer. The results are shown in Table 2.
  • Example 7 A polyethylene terephthalate (PET) film (Mitsubishi Chemical "Diafoil MRF75”) with a thickness of 75 ⁇ m provided with a silicone-based release layer on the surface is used as a base material (cum-heavy release film), and the pressure-sensitive adhesive composition B is placed on the base material.
  • a coating layer was formed by coating so as to have a thickness of 25 ⁇ m.
  • a PET film (“Diafoil MRE75” manufactured by Mitsubishi Chemical Corporation) having a thickness of 75 ⁇ m, one side of which was treated with silicone peeling, was bonded onto this coating layer as a cover sheet (also a light peeling film).
  • the laminated body is photo-cured by irradiating it with ultraviolet rays from the cover sheet side with a black light whose position is adjusted so that the irradiation intensity on the irradiation surface directly under the lamp is 5 mW / cm 2, and a pressure-sensitive adhesive sheet having a thickness of 25 ⁇ m is formed. Obtained.
  • a base material layer a polyimide-based base material having a thickness of 50 ⁇ m (trade name “UPIREX-50S”, manufactured by Ube Industries, Ltd.) was prepared. The light release film of the pressure-sensitive adhesive sheet was peeled off and the pressure-sensitive adhesive layer was attached to one surface of the base material layer.
  • the heavy release film was left as it was on the pressure-sensitive adhesive layer and used to protect the surface of the pressure-sensitive adhesive layer (the surface of the pressure-sensitive adhesive layer).
  • the obtained structure was passed once through a laminator (0.3 MPa, speed 0.5 m / min) at 80 ° C. and then aged in an oven at 50 ° C. for 1 day. In this way, the protective film (7) was obtained.
  • the results are shown in Table 2.
  • Example 8 A protective film (8) was obtained in the same manner as in Example 7 except that the pressure-sensitive adhesive composition C was used instead of the pressure-sensitive adhesive composition B. The results are shown in Table 2.
  • Example 9 A protective film (9) was obtained in the same manner as in Example 5 except that the pressure-sensitive adhesive composition D was used instead of the pressure-sensitive adhesive composition A. The results are shown in Table 2.
  • Example 10 A protective film (10) was obtained in the same manner as in Example 5 except that the pressure-sensitive adhesive composition E was used instead of the pressure-sensitive adhesive composition A. The results are shown in Table 2.
  • Example 11 A commercially available release liner (Diafoil MRF-38), manufactured by Mitsubishi Plastics Co., Ltd. was prepared.
  • the pressure-sensitive adhesive composition F was applied to one surface (peeling surface) of the peeling liner so that the thickness after drying was 25 ⁇ m, and dried at 155 ° C. for 3 minutes. In this way, a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m composed of the acrylic pressure-sensitive adhesive F corresponding to the pressure-sensitive adhesive composition F was formed on the peeling surface of the release liner.
  • a base material layer a polyimide-based base material having a thickness of 50 ⁇ m (trade name “UPIREX-50S”, manufactured by Ube Industries, Ltd.) was prepared.
  • the pressure-sensitive adhesive layer formed on the release liner was bonded to one surface of the base material layer.
  • the release liner was left as it was on the pressure-sensitive adhesive layer and used to protect the surface of the pressure-sensitive adhesive layer (the surface of the pressure-sensitive adhesive layer).
  • the obtained structure was passed once through a laminator (0.3 MPa, speed 0.5 m / min) at 80 ° C. and then aged in an oven at 50 ° C. for 1 day. In this way, the protective film (11) was obtained.
  • the results are shown in Table 2.
  • Example 12 A protective film (12) was obtained in the same manner as in Example 7 except that the pressure-sensitive adhesive composition G was used instead of the pressure-sensitive adhesive composition B. The results are shown in Table 2.
  • a protective film (C1) was obtained in the same manner as in Example 1 except that a polyester-based base material having a thickness of 25 ⁇ m (trade name “Lumilar S10”, manufactured by Toray Industries, Inc.) was used as the base material layer. The results are shown in Table 2.
  • a protective film (C2) was obtained in the same manner as in Example 1 except that a polyester-based base material having a thickness of 50 ⁇ m (trade name “Lumilar S10”, manufactured by Toray Industries, Inc.) was used as the base material layer. The results are shown in Table 2.
  • a protective film (C3) was obtained in the same manner as in Example 1 except that a polyimide-based base material having a thickness of 50 ⁇ m (trade name “Kapton 200H”, manufactured by Toray DuPont Co., Ltd.) was used as the base material layer. The results are shown in Table 2.
  • a protective film (C4) was obtained in the same manner as in Example 1 except that a polyimide-based substrate having a thickness of 50 ⁇ m (trade name “Pixio BP”, manufactured by Kaneka Corporation) was used as the substrate layer. The results are shown in Table 2.
  • the protective film of the present invention has excellent bending recovery property, does not destroy the barrier layer even when attached to the back side of a polyimide substrate provided with a barrier layer, has excellent transparency, and has excellent foreign matter inspection property. Therefore, for example, it is movable. It may be suitably provided for a bendable device (a device that can be bent), a foldable device (a device that can be folded), and a rollable device (a device that can be rolled) having a bent portion.

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022224643A1 (ja) * 2021-04-19 2022-10-27 日東電工株式会社 アクリル系粘着剤組成物、アクリル系粘着剤、粘着フィルム、および、フレキシブルデバイス
WO2024024686A1 (ja) * 2022-07-26 2024-02-01 東洋インキＳｃホールディングス株式会社 フレキシブルディスプレイ用積層体、ならびにフレキシブルディスプレイ

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI855480B (zh) * 2022-12-26 2024-09-11 日商愛天思股份有限公司 黏著劑層、使用其的黏著片、積層體及撓性圖像顯示裝置

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008045057A (ja) * 2006-08-18 2008-02-28 Toyo Ink Mfg Co Ltd アクリル粘着剤の製造方法
JP2012015441A (ja) * 2010-07-05 2012-01-19 Teijin Dupont Films Japan Ltd フレキシブルプリント回路基板補強用フィルム、それからなるフレキシブルプリント回路補強板、およびそれらからなるフレキシブルプリント回路基板積層体
JP2013227533A (ja) * 2012-03-26 2013-11-07 Nitto Denko Corp 表面保護フィルム
JP2019056115A (ja) * 2014-04-16 2019-04-11 日東電工株式会社 粘着シート、及び、光学部材
JP2019173005A (ja) * 2018-03-29 2019-10-10 三菱ケミカル株式会社 粘着シート、積層シート及びそれを用いた画像表示装置
WO2020066842A1 (ja) * 2018-09-27 2020-04-02 日東電工株式会社 補強フィルム
JP2020204010A (ja) * 2018-11-28 2020-12-24 日東電工株式会社 粘着フィルム、フォルダブルデバイス、および、ローラブルデバイス

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53113085A (en) 1977-03-15 1978-10-03 Bio Research Center Co Production of lactic acid from cellulosic substance
KR100508822B1 (ko) * 2002-03-20 2005-08-17 가부시키가이샤 구라레 폴리비닐 알콜계 필름
JP2004188598A (ja) 2002-12-06 2004-07-08 Nippon Zeon Co Ltd 樹脂材料の製造法
JP2005002220A (ja) 2003-06-12 2005-01-06 Toyobo Co Ltd 一軸配向ポリエステルフィルム、並びにこれを用いた表面保護フィルム及び離型フィルム
KR100716145B1 (ko) 2005-12-06 2007-05-10 도레이새한 주식회사 편광판용 폴리에스테르 이형필름
JP2008101962A (ja) * 2006-10-18 2008-05-01 Toray Ind Inc アライメントマークの認識方法
JP5942222B2 (ja) 2010-12-15 2016-06-29 旭化成株式会社 光学部材用積層表面保護フィルム
US9955769B2 (en) * 2014-07-25 2018-05-01 The Procter & Gamble Company Applicator heads for handheld treatment apparatus for modifying keratinous surfaces
JP6419548B2 (ja) * 2014-11-27 2018-11-07 日東電工株式会社 表面保護フィルム、表面保護フィルムの製造方法、及び、光学部材
WO2017057411A1 (ja) * 2015-09-28 2017-04-06 リンテック株式会社 粘着シート、及び粘着シートの製造方法
JP2017212038A (ja) 2016-05-23 2017-11-30 株式会社ジャパンディスプレイ 表示装置
WO2018088543A1 (ja) * 2016-11-11 2018-05-17 宇部興産株式会社 ポリイミドフィルムとハードコート層とを含む積層体
KR102399713B1 (ko) * 2016-12-16 2022-05-19 도레이 필름 카코우 가부시키가이샤 이형 필름 및 보호 필름
JP6376271B1 (ja) 2017-12-08 2018-08-22 東洋インキＳｃホールディングス株式会社 フレキシブルデバイス用積層体の製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008045057A (ja) * 2006-08-18 2008-02-28 Toyo Ink Mfg Co Ltd アクリル粘着剤の製造方法
JP2012015441A (ja) * 2010-07-05 2012-01-19 Teijin Dupont Films Japan Ltd フレキシブルプリント回路基板補強用フィルム、それからなるフレキシブルプリント回路補強板、およびそれらからなるフレキシブルプリント回路基板積層体
JP2013227533A (ja) * 2012-03-26 2013-11-07 Nitto Denko Corp 表面保護フィルム
JP2019056115A (ja) * 2014-04-16 2019-04-11 日東電工株式会社 粘着シート、及び、光学部材
JP2019173005A (ja) * 2018-03-29 2019-10-10 三菱ケミカル株式会社 粘着シート、積層シート及びそれを用いた画像表示装置
WO2020066842A1 (ja) * 2018-09-27 2020-04-02 日東電工株式会社 補強フィルム
JP2020204010A (ja) * 2018-11-28 2020-12-24 日東電工株式会社 粘着フィルム、フォルダブルデバイス、および、ローラブルデバイス

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022224643A1 (ja) * 2021-04-19 2022-10-27 日東電工株式会社 アクリル系粘着剤組成物、アクリル系粘着剤、粘着フィルム、および、フレキシブルデバイス
WO2024024686A1 (ja) * 2022-07-26 2024-02-01 東洋インキＳｃホールディングス株式会社 フレキシブルディスプレイ用積層体、ならびにフレキシブルディスプレイ
JPWO2024024686A1 (enrdf_load_stackoverflow) * 2022-07-26 2024-02-01

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