WO2019155939A1 - Feuille adhésive, élément optique et dispositif d'affichage - Google Patents

Feuille adhésive, élément optique et dispositif d'affichage Download PDF

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Publication number
WO2019155939A1
WO2019155939A1 PCT/JP2019/002924 JP2019002924W WO2019155939A1 WO 2019155939 A1 WO2019155939 A1 WO 2019155939A1 JP 2019002924 W JP2019002924 W JP 2019002924W WO 2019155939 A1 WO2019155939 A1 WO 2019155939A1
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WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
meth
adhesive sheet
acrylate
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PCT/JP2019/002924
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English (en)
Japanese (ja)
Inventor
奈津子 沖田
数馬 三井
林　圭治
Original Assignee
日東電工株式会社
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Priority claimed from JP2018192646A external-priority patent/JP2019137831A/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020207022995A priority Critical patent/KR20200119802A/ko
Priority to CN201980012169.XA priority patent/CN111699232B/zh
Publication of WO2019155939A1 publication Critical patent/WO2019155939A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • 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
    • C09J7/20—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

Definitions

  • the present invention relates to an adhesive sheet, particularly a surface protective film.
  • the surface protective film is preferably used for applications such as attaching to the surface of an optical member or a display device to protect the surface.
  • the optical member include an ITO film, a polarizing plate, a diffusion plate, a brightness enhancement film, a cover glass, an organic EL panel formed by laminating them, and a liquid crystal panel.
  • the display device include a monitor, a television, and a smartphone.
  • the surface protective film has a configuration in which an adhesive layer is provided on a film-like base film (support).
  • a surface protective film is bonded to an optical member that is an adherend or a display device including the optical member via the pressure-sensitive adhesive layer, and is transported during manufacturing and processing of the optical member and the electronic member that constitutes the display device. It is used for the purpose of protecting the surface of an optical member from scratches and dirt at the time of inspection, shipping inspection, transportation, and the like. Thereafter, after the surface of the pressure-sensitive adhesive layer of the surface protective film is actually attached to an optical member or a display device, the surface protective film is peeled off and removed when it is no longer needed.
  • a surface protection film on the display apparatus which comprises an optical member and an optical member, and a display (screen) which comprises a display apparatus from a viewpoint of pasting a surface protection film on handling property at the time of manufacture and processing, a display, etc.
  • a thick substrate for example, polyethylene terephthalate
  • Patent Documents 1 and 2 when non-stretched polypropylene (CPP) or polyethylene (PE), which is weak, is used as the base material of the surface protective film, a defect in appearance characteristics called fish eye occurs, In some cases, defects such as inability to confirm defects during shipping inspection occurred.
  • CPP polypropylene
  • PE polyethylene
  • optical members and display devices having a curved portion or an uneven portion have increased, and displays constituting the display device have increased.
  • the curved portion and the uneven portion have been followed.
  • the present inventors as a result of earnest research, by combining a weak base material and a pressure-sensitive adhesive layer that easily follows a curved surface such as a curved portion or an uneven portion, Follows the adherend during manufacturing, processing, transport, shipping inspection, transportation, etc. of optical members and display devices that have curved or uneven portions that are adherends, displays that constitute the display device, etc.
  • the present invention has been completed by finding a pressure-sensitive adhesive sheet (surface protective film) that can sufficiently protect the surface.
  • the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition on one side or both sides of a base film, wherein the base film is a non-polyolefin film, Is cut into a width of 50 mm and a length of 100 mm, and the vertical droop distance L when fixed to a horizontal base so that it protrudes 50 mm in the length direction is 30 mm or more, and the adhesive layer surface is bonded to glass
  • the peeling force when pulled at a peeling speed of 1 mm / min in the 90-degree direction is 3.0 gf / 50 mm or more.
  • the pressure-sensitive adhesive layer is preferably formed from a pressure-sensitive adhesive composition containing at least one selected from an acrylic pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, and a silicone pressure-sensitive adhesive. .
  • the non-polyolefin film preferably has a tensile modulus of less than 1.5 ⁇ 10 9 Pa.
  • the non-polyolefin film is preferably a polyester film.
  • the optical member of the present invention is preferably protected by the pressure-sensitive adhesive sheet.
  • the display device of the present invention is preferably protected by the adhesive sheet.
  • the pressure-sensitive adhesive sheet of the present invention is a combination of a base film that is weak and can follow a curved surface such as a curved portion or a concavo-convex portion and a pressure-sensitive adhesive layer that has a good adhesive property to a curved surface such as a curved portion or a concavo-convex portion.
  • the adhesive sheet can follow the optical member and display device of the curved portion and the concavo-convex portion, at the time of production and processing of the display constituting the display device, at the time of transportation, at the time of shipping inspection, at the time of transportation,
  • a pressure-sensitive adhesive sheet (surface protective film) excellent in protective performance can be obtained and is useful.
  • the pressure-sensitive adhesive sheet (surface protective film) disclosed herein generally has a pressure-sensitive adhesive layer surface in a form called a pressure-sensitive adhesive tape, a pressure-sensitive adhesive label, a pressure-sensitive adhesive film, etc., an optical member, a display device (a display constituting the device), etc.
  • a surface protective film for protecting the surface of the display at the time of production / processing of a display having a curved portion or an uneven portion, at the time of transportation, at the time of shipping inspection, at the time of transportation.
  • the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet is typically formed continuously, but is not limited to such a form, for example, a pressure-sensitive adhesive formed in a regular or random pattern such as a spot or stripe. It may be an agent layer. Further, the pressure-sensitive adhesive sheet disclosed herein may be in the form of a roll or a single sheet.
  • the pressure-sensitive adhesive sheet of the present invention has a base film, and the base film is a non-polyolefin film.
  • the polyolefin film is weaker than the non-polyolefin film, but it is presumed that the reason why the polyolefin film is weak is that there are few unsaturated bonds and the rotation of the carbon chain is not restricted.
  • a polyolefin-based film is used as a base film constituting a surface protective film, defects in appearance characteristics called fish eyes may occur, and defects such as failure to be confirmed during shipping inspection may occur, which is preferable. Absent.
  • Fisheye means that transparent or semi-transparent fish-like particles remain in the base film in the base film forming process, which is caused by resin gel or unmelted material. It will be. If a polyolefin film is used as the base film, the melt viscosity of the resin is high and it cannot be passed through a high-accuracy filter during the film formation process, so unmelted material cannot be removed and there is a tendency to contain a lot of fish eyes. Yes, not preferred.
  • polyethylene when radicals are generated in the molecule when the resin is melted, the polyethylene molecules react with each other and easily gel, so that a lot of fish eyes are generated, making it difficult to apply to optical applications.
  • non-polyolefin film has a low melt viscosity, so it can be passed through a high-precision filter during film formation, and it can remove unmelted materials that cause fish eyes, etc. And can be applied to optical applications.
  • the base film is a non-polyolefin film, for example, a polyester polymer such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate; diacetyl cellulose, triacetyl cellulose Cellulose polymer such as: polycarbonate polymer; acrylic polymer such as polymethylmethacrylate; etc.
  • Main resin component main component of resin component, typically component accounting for 50% by weight or more
  • the constituted plastic film can be preferably used as the base film.
  • the non-polyolefin film is preferably a polyester film using a polyester polymer, among which optical properties (transparency, etc.), mechanical strength, thermal stability, moisture shielding properties, isotropic properties, It is preferable to use a material excellent in properties such as flexibility and dimensional stability.
  • a polyester film that is not too strong as a base film has flexibility, so that the pressure-sensitive adhesive composition can be applied by a roll coater or the like, and can be wound into a roll, which is useful. is there.
  • the film which has two or more types of ester bonds can also be used, and what combined polyethylene terephthalate and polybutylene terephthalate can be used preferably.
  • the resin material examples include styrene polymers such as polystyrene and acrylonitrile-styrene copolymers; vinyl chloride polymers; amide polymers such as nylon 6, nylon 6, 6, and aromatic polyamide; Examples of resin materials are listed. Still other examples of the resin material include imide polymers, sulfone polymers, polyether sulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers. , Arylate polymers, polyoxymethylene polymers, epoxy polymers and the like. A base film made of a blend of two or more of the above-described polymers may be used.
  • the non-polyolefin film preferably has a tensile modulus of less than 1.5 ⁇ 10 9 Pa, more preferably 1.3 ⁇ 10 9 Pa or less, and 1.0 ⁇ 10 7. To 1.3 ⁇ 10 9 Pa is more preferable, and 1.0 ⁇ 10 8 to 1.3 ⁇ 10 9 Pa is particularly preferable.
  • a base film that is somewhat stiff is used, so that it is easy to follow a curved portion or uneven portion of a display or the like. This is a preferred embodiment.
  • the stiffness of the base film becomes too strong, and it may not be possible to follow the curved portion or the uneven portion of a display or the like. Is not preferable.
  • various additives such as an antioxidant, an ultraviolet absorber, a plasticizer, and a colorant (pigment, dye, etc.) may be blended as necessary.
  • a known or conventional surface treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of a primer may be performed.
  • Such surface treatment can be, for example, a treatment for improving the adhesion between the base film and the pressure-sensitive adhesive layer (the anchoring property of the pressure-sensitive adhesive layer).
  • the base film It is also possible to use a polyester film subjected to antistatic treatment as the base film.
  • the antistatic treatment may be performed on either the surface of the base film that contacts the pressure-sensitive adhesive layer or the surface of the base film that does not contact the pressure-sensitive adhesive layer.
  • Use of the substrate film is preferable because charging of the pressure-sensitive adhesive sheet (surface protective film) itself when peeled is suppressed.
  • the base film is a polyester film, and the antistatic treatment is applied to the polyester film, thereby reducing the charge of the pressure-sensitive adhesive sheet (surface protective film) itself and having an excellent antistatic ability to the adherend. Is obtained.
  • antistatic resin which consists of an antistatic agent and a resin component, a conductive polymer, and a conductive substance.
  • examples thereof include a method of applying a conductive resin, a method of depositing or plating a conductive material, a method of kneading an antistatic agent, and the like.
  • the thickness of the base film is usually 5 to 200 ⁇ m, preferably about 8 to 150 ⁇ m, more preferably 10 to 100 ⁇ m, and still more preferably about 13 to 100 ⁇ m.
  • the thickness of the base film is within the above range, it is preferable because it is excellent in bonding workability to the adherend, peelability from the adherend and workability.
  • the pressure-sensitive adhesive sheet of the present invention is characterized by having a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition on one side or both sides of a base film.
  • the pressure-sensitive adhesive layer used in the present invention can be used without particular limitation as long as it is formed from a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive polymer.
  • Examples of the pressure-sensitive adhesive composition include acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, synthetic rubber-based pressure-sensitive adhesives, natural rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and polyester-based pressure-sensitive adhesives.
  • the (meth) acrylic polymer which is a pressure-sensitive polymer constituting the acrylic pressure-sensitive adhesive
  • the (meth) acrylic polymer is an alkyl having 1 to 14 carbon atoms as a raw material monomer constituting the pressure-sensitive adhesive layer.
  • a (meth) acrylic monomer having a group can be used as the main monomer.
  • As said (meth) acrylic-type monomer 1 type (s) or 2 or more types can be used.
  • a pressure-sensitive adhesive sheet (surface protective film) having excellent properties and removability can be obtained.
  • the (meth) acrylic polymer refers to an acrylic polymer and / or a methacrylic polymer
  • the (meth) acrylate refers to acrylate and / or methacrylate.
  • the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) ) Acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl ( (Meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (
  • Suitable examples include (meth) acrylic monomers having an alkyl group having 4 to 14 carbon atoms such as n-tetradecyl (meth) acrylate.
  • a hydroxyl group-containing (meth) acrylic monomer can be used as a raw material monomer.
  • hydroxyl group containing (meth) acrylic-type monomer 1 type (s) or 2 or more types can be used.
  • hydroxyl group-containing (meth) acrylic monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. , 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, etc. .
  • the hydroxyl group-containing (meth) acrylic monomer is preferably contained in an amount of 20% by weight or less with respect to 100% by weight of the total amount of monomer components constituting the (meth) acrylic polymer, more preferably 0.1 to It is 15% by weight or less, more preferably 1 to 10% by weight.
  • the balance between the wettability of the pressure-sensitive adhesive composition and the cohesive force of the resulting pressure-sensitive adhesive layer can be easily controlled, which is preferable.
  • the glass transition temperature and release of the (meth) acrylic polymer should be adjusted so that the Tg is 0 ° C. or lower (usually ⁇ 100 ° C. or higher) because the adhesive performance is easily balanced.
  • a polymerizable monomer or the like for adjusting the property can be used as long as the effects of the present invention are not impaired.
  • the (meth) acrylic polymer can use a carboxyl group-containing (meth) acrylic monomer as a raw material monomer.
  • the pressure-sensitive adhesive layer pressure-sensitive adhesive sheet, surface protective film
  • the cohesive force of the pressure-sensitive adhesive layer it is excellent in shearing force, which is preferable.
  • carboxyl group-containing (meth) acrylic monomer examples include (meth) acrylic acid, carboxylethyl (meth) acrylate, carboxylpentyl (meth) acrylate, and the like.
  • acrylic acid as a carboxyl group-containing (meth) acrylic monomer
  • the glass transition temperature (Tg) can be increased and the cohesive force can be increased.
  • curved surfaces such as irregular surfaces and curved portions When bonded together, the substrate is repelled due to the stiffness, but an adhesive with high cohesive strength is preferable because it is difficult to deform and has excellent resilience resistance.
  • the carboxyl group-containing (meth) acrylic monomer is preferably 20% by weight or less, and preferably 1 to 15% by weight with respect to 100% by weight of the total amount of monomer components constituting the (meth) acrylic polymer. More preferably, the content is 2 to 12% by weight. Within the above range, the balance between the wettability of the pressure-sensitive adhesive composition and the cohesive force of the resulting pressure-sensitive adhesive layer can be easily controlled, which is preferable.
  • the (meth) acrylic polymer can be used without any particular limitation as long as other polymerizable monomers other than the raw material monomer are within the range not impairing the characteristics of the present invention.
  • a cohesive force / heat resistance improving component such as a cyano group-containing monomer, vinyl ester monomer, aromatic vinyl monomer, amide group-containing monomer, imide group-containing monomer, amino group-containing monomer, epoxy
  • a component having a functional group that functions as a crosslinking base point can be used as appropriate, such as a group-containing monomer, N-acryloylmorpholine, vinyl ether monomer, and the like.
  • a cyano group-containing monomer an amide group-containing monomer, an imide group-containing monomer, an amino group-containing monomer, and a nitrogen-containing monomer such as N-acryloylmorpholine.
  • a nitrogen-containing monomer is useful because it can secure an appropriate peeling force (adhesive strength) that does not cause floating or peeling, and can provide a pressure-sensitive adhesive sheet (surface protective film) excellent in shearing force.
  • These polymerizable monomers can be used alone or in combination of two or more.
  • Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
  • Examples of the amide group-containing monomer include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, and N, N-diethyl.
  • Examples include methacrylamide, N, N′-methylenebisacrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, and diacetone acrylamide.
  • Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconimide.
  • amino group-containing monomer examples include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like.
  • Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, and vinyl laurate.
  • aromatic vinyl monomer examples include styrene, chlorostyrene, chloromethyl styrene, ⁇ -methyl styrene, and other substituted styrene.
  • epoxy group-containing monomer examples include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and allyl glycidyl ether.
  • vinyl ether monomer examples include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.
  • the other polymerizable monomer is preferably 0 to 30% by weight, and preferably 0 to 10% by weight, based on 100% by weight of the total amount of monomer components constituting the (meth) acrylic polymer. It is more preferable.
  • the other polymerizable monomers can be appropriately adjusted in order to obtain desired characteristics.
  • the (meth) acrylic polymer may further contain an alkylene oxide group-containing reactive monomer as a monomer component.
  • the average addition mole number of the oxyalkylene unit of the alkylene oxide group-containing reactive monomer is preferably 1 to 40, and preferably 3 to 40 from the viewpoint of compatibility with the oxyalkylene group-containing compound. Is more preferably 4 to 35, and particularly preferably 5 to 30.
  • the average added mole number is 1 or more, the effect of reducing the contamination of the adherend (protected body) tends to be obtained efficiently.
  • the said average added mole number is larger than 40, since interaction with an oxyalkylene group containing compound is large and there exists a tendency for the viscosity of an adhesive composition to rise and for coating to become difficult, it is unpreferable.
  • the terminal of the oxyalkylene chain may be a hydroxyl group or may be substituted with another functional group.
  • the alkylene oxide group-containing reactive monomer may be used alone or in combination of two or more, but the total content is the total amount of monomer components of the (meth) acrylic polymer. Among them, 0 to 20% by weight is preferable, and 0 to 10% by weight is more preferable. When the content of the alkylene oxide group-containing reactive monomer exceeds 20% by weight, the contamination on the adherend deteriorates, which is not preferable.
  • Examples of the oxyalkylene unit of the alkylene oxide group-containing reactive monomer include those having an alkylene group having 1 to 6 carbon atoms, such as an oxymethylene group, an oxyethylene group, an oxypropylene group, and an oxybutylene group. It is done.
  • the hydrocarbon group of the oxyalkylene chain may be linear or branched.
  • the alkylene oxide group-containing reactive monomer is a reactive monomer having an ethylene oxide group.
  • a reactive monomer-containing (meth) acrylic polymer having an ethylene oxide group as a base polymer, the compatibility between the base polymer and the oxyalkylene group-containing compound is improved, and bleeding to the adherend is suitably suppressed, A low-contamination pressure-sensitive adhesive composition is obtained.
  • alkylene oxide group-containing reactive monomer examples include (meth) acrylic acid alkylene oxide adducts and reactive surfactants having reactive substituents such as acryloyl group, methacryloyl group, and allyl group in the molecule. can give.
  • the (meth) acrylic acid alkylene oxide adduct include, for example, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) ) Acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, octoxy polyethylene glycol (meth) acrylate, lauroxy polyethylene Glycol (meth) acrylate, stearoxy polyethylene glycol Lumpur (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, octoxypolyethylene glycol - polyprop
  • the reactive surfactant include, for example, an anionic reactive surfactant having a (meth) acryloyl group or an allyl group, a nonionic reactive surfactant, and a cationic reactive surfactant. Is given.
  • the (meth) acrylic polymer preferably has a weight average molecular weight (Mw) of 100,000 to 2,000,000, more preferably 200,000 to 1,500,000, still more preferably 300,000 to 1,200,000, particularly preferably 300,000 to 1,000,000. Most preferably, it is 400,000 to 800,000.
  • Mw weight average molecular weight
  • the adhesive force tends to be generated due to the reduced cohesive force of the pressure-sensitive adhesive layer.
  • the weight average molecular weight exceeds 2 million, the fluidity of the polymer is lowered, the wetting to the adherend (for example, polarizing plate) becomes insufficient, and the adherend and the adhesive sheet (surface protective film) There is a tendency to cause blisters generated between the pressure-sensitive adhesive layer.
  • a weight average molecular weight means what was obtained by measuring by GPC (gel permeation chromatography).
  • the glass transition temperature (Tg) of the (meth) acrylic polymer is preferably ⁇ 60 to 0 ° C., more preferably ⁇ 50 to ⁇ 10 ° C.
  • the glass transition temperature is higher than 0 ° C.
  • the polymer hardly flows, for example, the wettability to the polarizing plate which is an optical member becomes insufficient, and between the polarizing plate and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (surface protective film). There is a tendency to cause blisters to occur.
  • the glass transition temperature (Tg) is lower than ⁇ 60 ° C., the cohesive force of the pressure-sensitive adhesive becomes low.
  • the pressure-sensitive adhesive when bonded to a curved surface such as a curved surface or an uneven surface, the pressure-sensitive adhesive loses the repulsive force of the substrate. There is a tendency to float.
  • Tg glass transition temperature
  • the glass transition temperature of a (meth) acrylic-type polymer can be adjusted in the said range by changing the monomer component and composition ratio to be used suitably.
  • the polymerization method of the (meth) acrylic polymer is not particularly limited, and can be polymerized by known methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, etc. From the viewpoint of characteristics such as low contamination to the adherend (protected body), solution polymerization is a more preferable embodiment. Further, the polymer obtained may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.
  • urethane-type adhesive When using a urethane-type adhesive for the said adhesive layer, arbitrary appropriate urethane-type adhesives can be employ
  • a urethane type adhesive Preferably, what consists of a urethane type polymer which is an adhesive polymer obtained by making a polyol and a polyisocyanate compound react is mentioned.
  • the polyol include polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol.
  • the polyisocyanate compound include diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and the like.
  • silicone type adhesive When using a silicone type adhesive for the said adhesive layer, arbitrary appropriate silicone type adhesives can be employ
  • a silicone-based pressure-sensitive adhesive one obtained by blending or agglomerating a silicone-based polymer that is a pressure-sensitive polymer can be preferably used.
  • silicone pressure-sensitive adhesive examples include addition reaction curable silicone pressure-sensitive adhesives and peroxide curable silicone pressure-sensitive adhesives.
  • peroxides benzoyl peroxide and the like
  • an addition reaction curable silicone pressure-sensitive adhesive is preferable.
  • the curing reaction of the addition reaction curable silicone pressure-sensitive adhesive for example, when obtaining a polyalkyl silicone pressure-sensitive adhesive, generally, a method of curing a polyalkylhydrogensiloxane composition with a platinum catalyst can be mentioned.
  • the pressure-sensitive adhesive composition used in the present invention can also contain an oxyalkylene group-containing compound.
  • an oxyalkylene group-containing compound By containing the oxyalkylene group-containing compound, it is possible to further develop light peelability.
  • the oxyalkylene group-containing compound include an organopolysiloxane having an oxyalkylene chain and an oxyalkylene group-containing compound not containing an organopolysiloxane.
  • organopolysiloxane having an oxyalkylene chain examples include specific examples of the organopolysiloxane having an oxyalkylene chain in the main chain, such as a commercial product, and trade names of X-22-4952, X-22. -4272, X-22-6266, KF-6004, KF-889 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-201, SF8427 (above, made by Toray Dow Corning), IM22 (made by Asahi Kasei Wacker), etc. Is given.
  • organosiloxane having an oxyalkylene chain in the side chain examples include, for example, trade names KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945.
  • oxyalkylene group-containing compound not containing the organopolysiloxane examples include, for example, polyoxyalkylene alkylamine, polyoxyalkylene diamine, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene alkyl phenyl ether.
  • Nonionic surfactants such as polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allyl ether, polyoxyalkylene alkyl phenyl allyl ether; polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene alkyl ether phosphate ester salt, Oxyalkylene alkylphenyl ether sulfate ester salt, polyoxyalkylene alkylphenyl ether phosphate Anionic surfactants such as salt of salts; other cationic surfactants having polyoxyalkylene chains (polyalkylene oxide chains), amphoteric surfactants, polyether compounds having polyoxyalkylene chains (and their Derivatives), acrylic compounds having a polyoxyalkylene chain (and derivatives thereof), and the like. Moreover, you may mix
  • Such polyoxyalkylene chain-containing compounds may
  • polyether compound (polyether component) having a polyoxyalkylene chain examples include a block copolymer of polypropylene glycol (PPG) -polyethylene glycol (PEG), a block copolymer of PPG-PEG-PPG, Examples thereof include a block copolymer of PEG-PPG-PEG.
  • the derivative of the polyether compound having a polyoxyalkylene chain include an oxypropylene group-containing compound (PPG monoalkyl ether, PEG-PPG monoalkyl ether, etc.) whose terminal is etherified, and oxypropylene whose terminal is acetylated Group-containing compounds (terminal acetylated PPG and the like), and the like.
  • the acrylic compound having a polyoxyalkylene chain include a (meth) acrylate polymer having an oxyalkylene group.
  • the oxyalkylene group has an addition mole number of oxyalkylene units of preferably 1 to 50, more preferably 2 to 30, and further preferably 2 to 20.
  • the terminal of the oxyalkylene chain may be a hydroxyl group, or may be substituted with an alkyl group, a phenyl group or the like.
  • the (meth) acrylate polymer having an oxyalkylene group is preferably a polymer containing (meth) acrylic acid alkylene oxide as a monomer component, and specific examples of the (meth) acrylic acid alkylene oxide include ethylene.
  • glycol group-containing (meth) acrylates include methoxy-polyethylene glycol (meth) acrylate types such as methoxy-diethylene glycol (meth) acrylate and methoxy-triethylene glycol (meth) acrylate, ethoxy-diethylene glycol (meth) acrylate, ethoxy -Ethoxy-polyethylene glycol (meth) acrylate type such as triethylene glycol (meth) acrylate, butoxy-diethylene glycol (meth) acrylate, buto Butoxy-polyethylene glycol (meth) acrylate type such as cy-triethylene glycol (meth) acrylate, phenoxy-polyethylene glycol (meth) acrylate type
  • the monomer component other monomer components other than the (meth) acrylic acid alkylene oxide can also be used.
  • specific examples of other monomer components include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • the pressure-sensitive adhesive composition preferably contains a crosslinking agent. Moreover, in this invention, it can be set as an adhesive layer using the said adhesive composition.
  • the pressure-sensitive adhesive composition is an acrylic pressure-sensitive adhesive containing the (meth) acrylic polymer
  • the constitutional unit, the structural ratio, the selection and addition ratio of the cross-linking agent, etc. are appropriately determined.
  • an isocyanate compound As the crosslinking agent used in the present invention, an isocyanate compound, an epoxy compound, a melamine resin, an aziridine derivative, a metal chelate compound, or the like may be used.
  • an epoxy compound is preferable because the cohesive force of the adhesive increases. It becomes an aspect.
  • these compounds may be used independently and may be used in mixture of 2 or more types.
  • isocyanate compound examples include aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), dimer diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI), 1, Alicyclic isocyanates such as 3-bis (isocyanatomethyl) cyclohexane, aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate (XDI), and the isocyanate compound Allophanate bond, biuret bond, isocyanurate bond, uretdione bond, urea bond, carbodiimide bond Uretonimine bond, polyisocynate modified products thereof obtained by modifying the like oxadiazinetrione bond.
  • epoxy compound examples include N, N, N ′, N′-tetraglycidyl-m-xylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 1,3-bis (N, N-dioxy). Glycidylaminomethyl) cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Company, Inc.).
  • Examples of the melamine resin include hexamethylol melamine.
  • Examples of the aziridine derivative include commercially available product names HDU, TAZM, TAZO (manufactured by Mutual Yakugyo Co., Ltd.) and the like.
  • metal chelate compound examples include aluminum, iron, tin, titanium, and nickel as metal components, and acetylene, methyl acetoacetate, and ethyl lactate as chelate components.
  • the content of the crosslinking agent used in the present invention is, for example, preferably 0.01 to 20 parts by weight, and preferably 0.1 to 18 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. More preferred is 0.5 to 15 parts by weight, still more preferred is 1 to 12 parts by weight.
  • the content is less than 0.01 parts by weight, the crosslinking formation by the crosslinking agent becomes insufficient, the cohesive force of the resulting pressure-sensitive adhesive layer becomes small, and sufficient heat resistance may not be obtained, It causes glue residue and tends to be inferior in repulsion resistance at the time of bonding to a curved surface such as a curved portion or an uneven portion.
  • the cohesive force of the polymer is large, the fluidity is lowered, the wettability to the adherend (for example, polarizing plate) becomes insufficient, and the adherend and the pressure-sensitive adhesive. There is a tendency to cause blisters generated between the layer (adhesive composition layer).
  • a crosslinking agent within the above range, a balance between wettability and repulsion resistance is achieved, and it becomes easier to obtain a pressure-sensitive adhesive layer excellent in followability with respect to a curved portion or an uneven portion. It becomes.
  • These crosslinking agents may be used alone or in combination of two or more.
  • the pressure-sensitive adhesive composition may further contain a cross-linking catalyst for causing any of the above-described cross-linking reactions to proceed more effectively.
  • cross-linking catalysts include tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris (acetylacetonato) iron, tris (hexane-2,4-dionato) iron, tris (heptane-2,4-dionato).
  • Iron tris (heptane-3,5-dionato) iron, tris (5-methylhexane-2,4-dionato) iron, tris (octane-2,4-dionato) iron, tris (6-methylheptane-2) , 4-Dionato) iron, tris (2,6-dimethylheptane-3,5-dionato) iron, tris (nonane-2,4-dionato) iron, tris (nonane-4,6-dionato) iron, tris ( 2,2,6,6-tetramethylheptane-3,5-dionato) iron, tris (tridecan-6,8-dionato) iron, tris (1-phenylbutane-1, -Dionato) iron, tris (hexafluoroacetylacetonato) iron, tris (ethyl acetoacetate) iron, tris (acetoacetate-n-propyl) iron, tris (isopropy
  • the content of the crosslinking catalyst is not particularly limited, but is preferably about 0.0001 to 1 part by weight, for example, 0.001 to 0.5 parts per 100 parts by weight of the (meth) acrylic polymer. Part by weight is more preferred. Within the above range, when the pressure-sensitive adhesive layer is formed, the speed of the cross-linking reaction is high, and the pot life of the pressure-sensitive adhesive composition is lengthened.
  • the pressure-sensitive adhesive composition may contain other known additives, for example, powders such as lubricants, colorants, pigments, plasticizers, tackifiers, low molecular weight polymers, surface lubrication.
  • powders such as lubricants, colorants, pigments, plasticizers, tackifiers, low molecular weight polymers, surface lubrication.
  • the pressure-sensitive adhesive sheet (surface protective film) of the present invention is characterized by having a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition on one side or both sides of a base film.
  • the crosslinking is performed after application of the pressure-sensitive adhesive composition, but it is also possible to transfer a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition after crosslinking to a substrate film or the like.
  • the method for forming the pressure-sensitive adhesive layer on the base film is not particularly limited.
  • the pressure-sensitive adhesive layer is formed by applying the pressure-sensitive adhesive composition (solution) to the base film and removing the polymerization solvent by drying. It is produced by forming on a base film. Thereafter, curing may be performed for the purpose of adjusting the component transfer of the pressure-sensitive adhesive layer or adjusting the crosslinking reaction.
  • the pressure-sensitive adhesive composition when the pressure-sensitive adhesive composition is applied on the base film to prepare a pressure-sensitive adhesive sheet, the pressure-sensitive adhesive composition includes at least one solvent other than the polymerization solvent so that the pressure-sensitive adhesive composition can be uniformly applied onto the base film. May be newly added.
  • a known method used for the production of pressure-sensitive adhesive tapes is used as a method for forming the pressure-sensitive adhesive layer when producing the pressure-sensitive adhesive sheet of the present invention.
  • a known method used for the production of pressure-sensitive adhesive tapes is used. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like.
  • the pressure-sensitive adhesive sheet of the present invention is usually prepared so that the thickness of the pressure-sensitive adhesive layer is 3 to 100 ⁇ m, preferably about 5 to 30 ⁇ m. It is preferable for the thickness of the pressure-sensitive adhesive layer to be in the above-mentioned range since it is easy to obtain an appropriate balance between removability and pressure-sensitive adhesiveness.
  • the total thickness of the pressure-sensitive adhesive sheet of the present invention is preferably 8 to 300 ⁇ m, more preferably 10 to 200 ⁇ m, and most preferably 20 to 100 ⁇ m. Within the above range, it is excellent in adhesive properties (removability, adhesiveness, etc.), workability, and appearance properties, and is a preferred embodiment.
  • the said total thickness means the sum total of the thickness containing all layers, such as a base film, an adhesive layer, a separator, and another layer.
  • the pressure-sensitive adhesive sheet disclosed herein may take the form of a pressure-sensitive adhesive product in which a separator (release liner) is bonded to the pressure-sensitive adhesive layer surface for the purpose of protecting the pressure-sensitive adhesive surface. Therefore, this specification can provide a pressure-sensitive adhesive sheet with a separator (pressure-sensitive adhesive product) including any pressure-sensitive adhesive sheet disclosed herein and a separator that protects the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet.
  • the separator is not particularly limited.
  • a separator having a release layer on the surface of a substrate such as a resin film or paper (which may be paper laminated with a resin such as polyethylene), or a fluoropolymer (polytetra
  • a separator made of a resin film formed of a low-adhesive material such as fluoroethylene or a polyolefin resin (polyethylene, polypropylene, or the like) can be used. Since it is excellent in surface smoothness, a separator having a release layer on the surface of a resin film as a substrate or a separator made of a resin film formed of a low adhesive material can be preferably employed.
  • the resin film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer.
  • films polyester films (PET film, PBT film, etc.), polyurethane films, ethylene-vinyl acetate copolymer films, and the like.
  • a silicone release treatment agent for the formation of the release layer, for example, a silicone release treatment agent, a long-chain alkyl release treatment agent, an olefin release treatment agent, a fluorine release treatment agent, a fatty acid amide release treatment agent, molybdenum sulfide, silica powder, etc.
  • a known release treating agent can be used.
  • the use of a silicone release treatment agent is particularly preferred.
  • the thickness of the release treatment agent is not particularly limited, but is usually about 0.01 to 1 ⁇ m, preferably about 0.1 to 1 ⁇ m.
  • the thickness of the separator is not particularly limited, but is usually about 5 to 200 ⁇ m (for example, about 10 to 100 ⁇ m, preferably about 20 to 80 ⁇ m). When the thickness of the separator is within the above range, it is preferable because the workability for bonding to the pressure-sensitive adhesive layer and the workability for peeling from the pressure-sensitive adhesive layer are excellent.
  • the base material for the separator can be subjected to various surface treatments such as corona discharge treatment or various surface treatments such as embossing as necessary. If necessary, fillers (inorganic fillers, organic fillers, etc.), anti-aging agents, antioxidants, UV absorbers, antistatic agents, lubricants, plasticizers, colorants (pigments, dyes, etc.), etc. These various additives may be blended.
  • ⁇ An antistatic treatment may be applied to the release agent surface of the separator or the surface to which no release agent is applied.
  • the pressure-sensitive adhesive sheet (surface protective film) disclosed herein can be implemented in a mode that further includes other layers in addition to the base film, the pressure-sensitive adhesive layer, and the separator.
  • the other layer include an undercoat layer (anchor layer) that improves the anchoring property of the antistatic layer and the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet of the present invention has a vertical sag distance L of 30 mm or more when the pressure-sensitive adhesive sheet is cut into a width of 50 mm and a length of 100 mm and fixed to a horizontal base so as to protrude 50 mm in the length direction.
  • the adhesive layer surface is bonded to glass, and the peeling force (low-speed peeling force) when pulled in the 90 ° direction at a peeling speed of 1 mm / min is 3.0 gf / 50 mm or more.
  • the vertical droop distance L is 30 mm or more, a base film having a weak stiffness is used.
  • the base film is bonded to a curved surface such as a curved portion or an uneven portion,
  • the repulsion is weak and the followability is good, which is preferable.
  • the cohesive force of an adhesive is so high that a low-speed peeling force is large, it is excellent in the repulsion resistance at the time of bonding on curved surfaces, such as a curved part and an uneven
  • the low-speed peeling force to 3.0 gf / 50 mm or more, even when pasted on a curved surface such as a curved portion or a concavo-convex portion, there is no floating, which is preferable.
  • the vertical droop distance L is preferably 32 mm or more, more preferably 32 to 50 mm, and further preferably 34 to 49 mm.
  • the peeling force is preferably 4 gf / 50 mm or more, more preferably 6 to 30 gf / 50 mm, and still more preferably 8 to 15 gf / 50 mm.
  • the peeling force adheresive force
  • the peeling force does not become too high, and the re-peelability is excellent, which is a preferred embodiment.
  • optical member of the present invention is preferably protected by the pressure-sensitive adhesive sheet.
  • the surface of the adhesive layer of the said adhesive sheet (surface protection film) can be stuck on an optical member, and an optical member can be protected.
  • grooved part is favorable, it is useful in order to protect the surface of the optical member which has a curved part or an uneven
  • the display device of the present invention is preferably protected by the pressure-sensitive adhesive sheet.
  • the surface of the adhesive layer of the said adhesive sheet can be stuck on the surface of the display (screen) which comprises a display apparatus and a display apparatus, and a display apparatus and a display can be protected.
  • grooved part is favorable, it is useful in order to protect the surface of the display apparatus and display which have a curved part or an uneven
  • Tg glass transition temperature
  • Tgn glass transition temperature of the homopolymer of each monomer.
  • Formula: 1 / (Tg + 273) ⁇ [Wn / (Tgn + 273)] (Wherein Tg (° C.) is the glass transition temperature of the copolymer, Wn ( ⁇ ) is the weight fraction of each monomer, Tgn (° C.) is the glass transition temperature of the homopolymer of each monomer, and n is the type of each monomer.
  • the bending stress (load) of the pressure-sensitive adhesive sheet is preferably 0.01 to 0.20 g, more preferably 0.03 to 0.18 g, still more preferably 0.05 to 0.15 g.
  • the bending stress (load) of the pressure-sensitive adhesive sheet is within the above range, the pressure-sensitive adhesive sheet is not too strong, the followability becomes good, and this is a preferred embodiment.
  • a bending stress (load) exceeding 0.20 g is not preferable because the stiffness becomes too strong and the followability is lowered.
  • the obtained pressure-sensitive adhesive sheet was cut into a width of 50 mm and a length of 100 mm, and the speed of 0.25 MPa and 0.3 m / min was applied to the adherend glass (manufactured by Matsunami Glass Industry Co., Ltd., blue plate edge product (OF1)). Then, the surface of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet was bonded to prepare an evaluation sample. After bonding, the sample was left in an environment of 23 ° C.
  • the polymerization reaction was carried out for about 4 hours while maintaining the vicinity to prepare a (meth) acrylic polymer (A) solution (about 35% by weight).
  • the (meth) acrylic polymer (A) had a weight average molecular weight (Mw) of 470,000 and a glass transition temperature (Tg) of ⁇ 21 ° C.
  • acrylic adhesive (1) solution An epoxy-based crosslinking agent (1,3-bis (N, N-diglycidylaminomethyl) cyclohexane as a crosslinking agent was added to 100 parts by weight of the solid content of the (meth) acrylic polymer (A) solution (about 35% by weight). 2 parts by weight of epoxy equivalent: 110, functional group number: 4, trade name “TETRAD-C”: T / C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) Acrylic adhesive (1) solution was prepared.
  • epoxy-based crosslinking agent (1,3-bis (N, N-diglycidylaminomethyl) cyclohexane as a crosslinking agent was added to 100 parts by weight of the solid content of the (meth) acrylic polymer (A) solution (about 35% by weight). 2 parts by weight of epoxy equivalent: 110, functional group number: 4, trade name “TETRAD-C”: T / C, manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • acrylic adhesive (2) solution To 100 parts by weight of the solid content of the (meth) acrylic polymer (A) solution (35% by weight), an epoxy crosslinking agent (1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 10 parts by weight of epoxy equivalent: 110, functional group number: 4, trade name “TETRAD-C”: T / C, manufactured by Mitsubishi Gas Chemical Co., Inc.) A system adhesive (2) solution was prepared.
  • acrylic adhesive (3) solution To 100 parts by weight of the solid content of the (meth) acrylic polymer (B) solution (30% by weight), an epoxy crosslinking agent (1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, Epoxy equivalent: 110, number of functional groups: 4, trade name “TETRAD-C”: T / C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 6 parts by weight were added, and the mixture was stirred at about 25 ° C. for about 1 minute. A system adhesive (3) solution was prepared.
  • an epoxy crosslinking agent (1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, Epoxy equivalent: 110, number of functional groups: 4, trade name “TETRAD-C”: T / C, manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • acrylic adhesive (4) solution To 100 parts by weight of the solid content of the (meth) acrylic polymer (C) solution (30% by weight), an epoxy crosslinking agent (1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, Epoxy equivalent: 110, number of functional groups: 4, trade name “TETRAD-C”: T / C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 11 parts by weight were added, and the mixture was stirred at about 25 ° C. for about 1 minute. A system adhesive (4) solution was prepared.
  • an epoxy crosslinking agent (1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, Epoxy equivalent: 110, number of functional groups: 4, trade name “TETRAD-C”: T / C, manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • acrylic adhesive (5) solution To 100 parts by weight of the solid content of the above (meth) acrylic polymer (D) solution (30% by weight), as a crosslinking agent, an isocyanate crosslinking agent (trimethylolpropane / tolylene diisocyanate trimer adduct, trade name “Coronate” L ”: C / L, 4 parts by weight, manufactured by Tosoh Corporation, as a crosslinking catalyst, dibutyltin dilaurate (manufactured by Tokyo Fine Chemical Co., Ltd., trade name: Encapsulizer OL-1,“ Sn ”in Table 3, 0.5% by weight) Ethyl acetate solution): 0.015 part by weight was added, and the mixture was stirred at about 25 ° C. for about 1 minute to prepare an acrylic pressure-sensitive adhesive (5) solution.
  • an isocyanate crosslinking agent trimethylolpropane / tolylene diisocyanate trimer adduct, trade name “Coronate” L
  • the acrylic pressure-sensitive adhesive solution (1) was converted into a base film I (polyethylene terephthalate, thickness: 19 ⁇ m, tensile modulus: 1.2 ⁇ 10 9 Pa, trade name: Diafoil T100-19B: manufactured by Mitsubishi Chemical Corporation) And heated at 130 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 10 ⁇ m, thereby preparing a pressure-sensitive adhesive sheet.
  • base film I polyethylene terephthalate, thickness: 19 ⁇ m, tensile modulus: 1.2 ⁇ 10 9 Pa, trade name: Diafoil T100-19B: manufactured by Mitsubishi Chemical Corporation
  • Examples 2 to 4 As shown in Table 6, in place of the acrylic pressure-sensitive adhesive (1) solution used in Example 1, the same as in Example 1 except that the acrylic pressure-sensitive adhesives (2) to (4) were used.
  • the adhesive sheet was produced by the method.
  • Example 5 As shown in Table 6, instead of the base film used in Example 1, base film II (polyethylene terephthalate, thickness: 12 ⁇ m, tensile modulus: 1.0 ⁇ 10 9 Pa, trade name: Lumirror # 12S10 (manufactured by Toray Industries, Inc.) was used in the same manner as in Example 1 to prepare a pressure-sensitive adhesive sheet in which the heating conditions and the thickness of the resulting pressure-sensitive adhesive layer were adjusted.
  • base film II polyethylene terephthalate, thickness: 12 ⁇ m, tensile modulus: 1.0 ⁇ 10 9 Pa, trade name: Lumirror # 12S10 (manufactured by Toray Industries, Inc.) was used in the same manner as in Example 1 to prepare a pressure-sensitive adhesive sheet in which the heating conditions and the thickness of the resulting pressure-sensitive adhesive layer were adjusted.
  • Example 6 As shown in Table 6, instead of the base film used in Example 1, the base film III (polyethylene terephthalate, thickness: 25 ⁇ m, tensile modulus: 7.0 ⁇ 10 8 Pa, trade name: ESR: A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that Okura Kogyo Co., Ltd. was used, and the heating conditions and the thickness of the resulting pressure-sensitive adhesive layer were adjusted.
  • the base film III polyethylene terephthalate, thickness: 25 ⁇ m, tensile modulus: 7.0 ⁇ 10 8 Pa
  • ESR A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that Okura Kogyo Co., Ltd. was used, and the heating conditions and the thickness of the resulting pressure-sensitive adhesive layer were adjusted.
  • Examples 7 and 8 As shown in Table 6, instead of the acrylic adhesive (1) solution used in Example 1, a urethane adhesive (6) solution or a silicone adhesive (7) solution was used. In the same manner as in Example 1, a pressure-sensitive adhesive sheet was prepared in which the heating conditions and the thickness of the resulting pressure-sensitive adhesive layer were adjusted.
  • ⁇ Comparative Example 1> As shown in Table 6, instead of the base film used in Example 1, a base film IV (polyethylene terephthalate, thickness: 38 ⁇ m, tensile modulus: 2.0 ⁇ 10 9 Pa, trade name: Diafoil Except that T100C-38 (manufactured by Mitsubishi Chemical Co., Ltd.) was used, a pressure-sensitive adhesive sheet was prepared by adjusting the heating conditions and the thickness of the resulting pressure-sensitive adhesive layer in the same manner as in Example 1.
  • a base film IV polyethylene terephthalate, thickness: 38 ⁇ m, tensile modulus: 2.0 ⁇ 10 9 Pa, trade name: Diafoil
  • T100C-38 manufactured by Mitsubishi Chemical Co., Ltd.
  • ⁇ Comparative Example 2> An acrylic pressure-sensitive adhesive (1) solution was applied to a 38 ⁇ m polyethylene terephthalate film coated with a silicone release treatment, and dried at 130 ° C. for 2 minutes to obtain a pressure-sensitive adhesive layer. Thereafter, the obtained pressure-sensitive adhesive layer was bonded to the base film V (unstretched polypropylene, thickness: 40 ⁇ m, tensile modulus: 4.5 ⁇ 10 8 Pa, trade name: MK-12: manufactured by Sun Tox Corporation) (Transfer) to obtain an adhesive sheet.
  • base film V unstretched polypropylene, thickness: 40 ⁇ m, tensile modulus: 4.5 ⁇ 10 8 Pa, trade name: MK-12: manufactured by Sun Tox Corporation
  • Example 3 As shown in Table 6, heating was performed in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive (5) solution was used instead of the acrylic pressure-sensitive adhesive (1) solution used in Example 1. A pressure-sensitive adhesive sheet with adjusted conditions and the thickness of the resulting pressure-sensitive adhesive layer was prepared.
  • Tables 1 to 6 show the results of the above-described blending contents, various measurements, and evaluations with the pressure-sensitive adhesive sheets according to Examples and Comparative Examples.
  • surface shows an active ingredient.
  • the thickness of the pressure-sensitive adhesive layer was prepared in the same manner as in Example 1 so that all of the Examples and Comparative Examples were 10 ⁇ m.
  • the vertical sag distance L of the pressure-sensitive adhesive sheet is 30 mm or more
  • the low-speed peeling force is also included in a desired range
  • the followability to the bending stress and the curved portion (curved surface) of the pressure-sensitive adhesive sheet is also included. It was confirmed that it was good. In addition, the appearance of the base film was also good.
  • Comparative Example 1 the vertical droop distance L was less than 30 mm, the bending stress of the adhesive sheet was inferior, and the followability to the curved portion was deteriorated.
  • Comparative Example 2 since an unstretched polypropylene film, which is a polyolefin film, was used, poor appearance was confirmed.
  • Comparative Example 3 the vertical droop distance L was 30 mm or more, but the low-speed peel force was less than 3.0 gf / 50 mm, and it was confirmed that the followability to the curved portion was poor.
  • the pressure-sensitive adhesive sheet disclosed herein is an optical member used as a component of a liquid crystal display panel, a plasma display panel (PDP), an organic electroluminescence (EL) display, and the like, during manufacture of a display device including the optical member, and during transportation It is suitable as a surface protective film for protecting the optical member.
  • PDP plasma display panel
  • EL organic electroluminescence

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention aborde le problème consistant à proposer une feuille adhésive (pellicule de protection de surface) qui comprend une combinaison d'un matériau de base qui possède un corps médiocre et une couche d'agent adhésif qui est susceptible d'épouser les contours d'une partie incurvée ou d'une partie irrégulière, et qui peut épouser les contours d'un élément optique, un dispositif d'affichage, un écran constituant le dispositif d'affichage ou similaire, c'est-à-dire un objet d'intérêt, comportant une partie incurvée ou une partie irrégulière pendant la production/le traitement, l'acheminement, l'inspection sortante, le transport et analogues de l'objet d'intérêt de façon à pouvoir protéger de manière satisfaisante l'objet d'intérêt. La feuille adhésive selon la présente invention est composée d'un film de base et d'une couche d'agent adhésif constituée d'une composition d'agent adhésif et formée sur une surface ou les deux surfaces du film de base, la feuille adhésive étant caractérisée en ce que : le film de base est un film non polyoléfinique ; lorsque la feuille adhésive est découpée en un échantillon d'une largeur de 50 mm et d'une longueur de 100 mm et que l'échantillon est fixé sur une table horizontale de façon à faire saillie de 50 mm dans la direction de la longueur, la distance d'affaissement perpendiculaire L est égale ou supérieure à 30 mm ; et, lorsque la surface de la couche d'agent adhésif est liée à un verre, puis que la couche d'agent adhésif est enlevée dans une direction formant un angle de 90 degrés avec une vitesse de pelage de 1 mm/min, la force de pelage est égale ou supérieure à 3,0 gf/50 mm.
PCT/JP2019/002924 2018-02-09 2019-01-29 Feuille adhésive, élément optique et dispositif d'affichage WO2019155939A1 (fr)

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JP2014198830A (ja) * 2013-03-29 2014-10-23 日東電工株式会社 電気化学装置用粘着テープ
JP2018159054A (ja) * 2017-03-22 2018-10-11 日東電工株式会社 表面保護フィルム

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JPH08302304A (ja) * 1995-05-15 1996-11-19 Sekisui Chem Co Ltd 耐可塑剤用両面粘着テープ
JP2002003799A (ja) * 2000-06-27 2002-01-09 Nitto Denko Corp 接着シート類
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