WO2019155939A1 - Adhesive sheet, optical member, and display device - Google Patents

Adhesive sheet, optical member, and display device 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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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
meth
adhesive sheet
acrylate
Prior art date
Application number
PCT/JP2019/002924
Other languages
French (fr)
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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Publication date
Priority claimed from JP2018192646A external-priority patent/JP2019137831A/en
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/en
Priority to CN201980012169.XA priority patent/CN111699232B/en
Publication of WO2019155939A1 publication Critical patent/WO2019155939A1/en

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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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Abstract

The present invention addresses the problem of providing an adhesive sheet (a surface protection film) which comprises a combination of a base material that has poor body and an adhesive agent layer that is likely to follow the shape of a curved part or an uneven part, and which can follow the shape of an optical member, a display device, a display constituting the display device or the like, i.e., an object of interest, having a curved part or an uneven part during the production/processing, conveyance, outgoing inspection, transportation and the like of the object of interest to thereby satisfactorily protect the object of interest. The adhesive sheet according to the present invention is composed of a base film and an adhesive agent layer made from an adhesive agent composition and formed on one surface or both surfaces of the base film, the adhesive sheet being characterized in that: the base film is a non-polyolefin film; when the adhesive sheet is cut into a specimen having a width of 50 mm and a length of 100 mm and the specimen is fixed on a horizontal table so as to protrude by 50 mm in the length direction, the perpendicularly drooping distance L is 30 mm or more; and, when the surface of the adhesive agent layer is bonded to a glass and then the adhesive agent layer is pulled in a 90-degree direction at a peeling speed of 1 mm/min, the peel force is 3.0 gf/50 mm or more.

Description

粘着シート、光学部材、及び、表示装置Adhesive sheet, optical member, and display device
　本発明は、粘着シート、特に表面保護フィルムに関する。表面保護フィルムは、光学部材や表示装置の表面に貼着して該表面を保護する用途などに好ましく用いられる。光学部材としては、ＩＴＯフィルム、偏光板、拡散板、輝度向上フィルム、カバーガラス、それらが積層されてなる有機ＥＬパネル、液晶パネルなどが挙げられる。表示装置としては、モニター、テレビ、スマートフォンなどが挙げられる。 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. Examples of 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. Examples of the display device include a monitor, a television, and a smartphone.
　一般に、表面保護フィルムは、フィルム状の基材フィルム（支持体）上に粘着剤層が設けられた構成を有する。かかる表面保護フィルムは、前記粘着剤層を介して被着体である光学部材や光学部材を含む表示装置などに貼り合わされ、光学部材や表示装置を構成する電子部材などを製造・加工時、搬送時、出荷検査時、輸送時等において、光学部材などの表面を傷や汚れから保護する目的で用いられる。その後、実際に表面保護フィルムの粘着剤層表面が光学部材や表示装置などに貼付され使用された後、この表面保護フィルムは、不要になった段階で剥離して除去される。 Generally, the surface protective film has a configuration in which an adhesive layer is provided on a film-like base film (support). Such 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.
　また、表面保護フィルムを光学部材や光学部材を含む表示装置、表示装置を構成するディスプレイ（画面）に貼付する場合、製造・加工時のハンドリング性や、ディスプレイ等に表面保護フィルムを貼り合せる観点から、厚みのある基材（例えば、ポリエチレンテレフタラート等）を使用することがあった。 Moreover, when sticking 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. In some cases, a thick substrate (for example, polyethylene terephthalate) is used.
　しかし、湾曲部や凹凸部を有する表示装置を構成するディスプレイ等に厚みのある基材を使用した表面保護フィルムを貼り合わせた場合、基材のコシが強いため、湾曲部や凹凸部に表面保護フィルムが追従できない不具合が生じていた。 However, when a surface protection film using a thick base material is bonded to a display or the like that constitutes a display device having a curved portion or an uneven portion, the base material is strong, so the surface protection is applied to the curved portion or the uneven portion. There was a problem that the film could not follow.
　一方、特許文献１及び２のように、コシの弱い無延伸ポリプロピレン（ＣＰＰ）やポリエチレン（ＰＥ）等を表面保護フィルムの基材として使用した場合、フィッシュアイと呼ばれる外観特性における不良が発生し、出荷検査時に欠点を確認できない等の不具合を生じる場合があった。 On the other hand, as in 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.
　更に、近年、湾曲部や凹凸部を有する光学部材や表示装置、表示装置を構成するディスプレイなどが増加しており、ディスプレイなどの製造工程や出荷工程において、前記湾曲部や凹凸部に対して追従し、保護することができる表面保護フィルムが必要とされている。 Furthermore, in recent years, optical members and display devices having a curved portion or an uneven portion have increased, and displays constituting the display device have increased. In the manufacturing process and the shipping process of the display, etc., the curved portion and the uneven portion have been followed. There is a need for a surface protective film that can be protected.
特許第５３２６４６９号Japanese Patent No. 5326469 特許第３９３６９２２号Japanese Patent No. 3936922
　そこで、本発明者らは、上記事情に鑑み、鋭意研究した結果、コシの弱い基材と、湾曲部や凹凸部の様な曲面に対して、追従しやすい粘着剤層とを組み合わせることにより、被着体である湾曲部や凹凸部を有するような光学部材や表示装置、表示装置を構成するディスプレイ等の製造・加工時、搬送時、出荷検査時、輸送時等に被着体に追従することができ、十分に表面保護することが可能な粘着シート（表面保護フィルム）を見出し、本発明を完成するに至った。 Therefore, in view of the above circumstances, 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.
　すなわち、本発明の粘着シートは、基材フィルムの片面又は両面に粘着剤組成物から形成された粘着剤層を有する粘着シートにおいて、前記基材フィルムが、非ポリオレフィン系フィルムであり、前記粘着シートを幅５０ｍｍ、長さ１００ｍｍに切断し、長さ方向に５０ｍｍはみ出るように、水平な台に固定したときの、垂直下垂距離Ｌが、３０ｍｍ以上であり、前記粘着剤層表面をガラスに貼り合せ、９０度方向に剥離速度１ｍｍ／ｍｉｎで引っ張った際の剥離力が、３．０ｇｆ／５０ｍｍ以上であることを特徴とする。 That is, 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.
　本発明の粘着シートは、前記粘着剤層が、アクリル系粘着剤、ウレタン系粘着剤、及び、シリコーン系粘着剤から選択される少なくとも１種を含有する粘着剤組成物から形成されることが好ましい。 In the pressure-sensitive adhesive sheet of the present invention, 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. .
　本発明の粘着シートは、前記非ポリオレフィン系フィルムの引張弾性率が、１．５×１０９Ｐａ未満であることが好ましい。 In the pressure-sensitive adhesive sheet of the present invention, the non-polyolefin film preferably has a tensile modulus of less than 1.5 × 10 9 Pa.
　本発明の粘着シートは、前記非ポリオレフィン系フィルムが、ポリエステルフィルムであることが好ましい。 In the pressure-sensitive adhesive sheet of the present invention, the non-polyolefin film is preferably a polyester film.
　本発明の光学部材は、前記粘着シートにより保護されることが好ましい。 The optical member of the present invention is preferably protected by the pressure-sensitive adhesive sheet.
　本発明の表示装置は、前記粘着シートにより保護されることが好ましい。 The display device of the present invention is preferably protected by the adhesive sheet.
　本発明の粘着シートは、コシが弱く、湾曲部や凹凸部の様な曲面に追従可能な基材フィルムと、湾曲部や凹凸部の様な曲面に対する粘着特性が良好な粘着剤層とを組み合せることにより、湾曲部や凹凸部の光学部材や表示装置、表示装置を構成するディスプレイ等の製造・加工時、搬送時、出荷検査時、輸送時等において、粘着シートが追従することができ、保護性能に優れた粘着シート（表面保護フィルム）を得ることができ、有用である。 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. By doing this, 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.
粘着シートの垂直下垂距離Ｌを測定する際の概略図。Schematic at the time of measuring the vertical droop distance L of an adhesive sheet.
　以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
　＜粘着シート（表面保護フィルム）の全体構造＞
　ここに開示される粘着シート（表面保護フィルム）は、一般に、粘着テープ、粘着ラベル、粘着フィルム等と称される形態の粘着剤層表面を、光学部材や表示装置（を構成するディスプレイ）等、特に湾曲部や凹凸部を有するディスプレイの製造・加工時、搬送時、出荷検査時、輸送時等にディスプレイの表面を保護する表面保護フィルムとして好適である。前記粘着シートにおける粘着剤層は、典型的には連続的に形成されるが、かかる形態に限定されるものではなく、例えば点状、ストライプ状等の規則的あるいはランダムなパターンに形成された粘着剤層であってもよい。また、ここに開示される粘着シートは、ロール状であってもよく、枚葉状であってもよい。 <Overall structure of adhesive sheet (surface protective film)>
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. In particular, it is suitable as 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.
　＜基材フィルム＞
　本発明の粘着シートは、基材フィルムを有し、前記基材フィルムが、非ポリオレフィン系フィルムであることを特徴とする。ポリオレフィン系フィルムは、非ポリオレフィン系フィルムよりもコシが弱いが、コシが弱い理由として、不飽和結合が少なく、炭素鎖の回転が制限されていないことが推測される。ただ、ポリオレフィン系フィルムを、表面保護フィルムを構成する基材フィルムに使用した場合、フィッシュアイと呼ばれる外観特性における不良が発生し、出荷検査時に欠点を確認できない等の不具合を生じる場合があり、好ましくない。なお、フィッシュアイとは、基材フィルムの成膜工程において、透明もしくは半透明で魚の目のような粒子が、基材フィルム中に残ることを指し、樹脂のゲル物や未溶融物などが原因となるものである。基材フィルムにポリオレフィン系フィルムを使用すると、樹脂の溶融粘度が高く、成膜工程時に高精度のフィルターに通すことができないため、未溶融物を取り除くことができず、フィッシュアイを多く含む傾向があり、好ましくない。特にポリエチレンの場合、樹脂の溶融時に、分子中にラジカルが発生するとポリエチレン分子同士が反応し、ゲル化しやすいため、特にフィッシュアイが多く発生し、光学用途への適用が困難となり、好ましくない。一方、非ポリオレフィン系フィルムは、溶融粘度が低いため、成膜時に高精度のフィルターに通すことができ、フィッシュアイの原因となる未溶融物などを取り除くことができるため、外観特性に優れたフィルムを得ることができ、光学用途に適用できる。 <Base film>
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. However, when 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. In particular, in the case of 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. On the other hand, 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.
　前記基材フィルム（基材、支持体）は、非ポリオレフィン系フィルムであり、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリブチレンテレフタレート等のポリエステル系ポリマー；ジアセチルセルロース、トリアセチルセルロース等のセルロース系ポリマー；ポリカーボネート系ポリマー；ポリメチルメタクリレート等のアクリル系ポリマー；等を主たる樹脂成分（樹脂成分のなかの主成分、典型的には５０重量％以上を占める成分）とする樹脂材料から構成されたプラスチックフィルムを、前記基材フィルムとして好ましく用いることができる。中でも、前記非ポリオレフィン系フィルムとして、ポリエステル系ポリマーを用いたポリエステルフィルムであることが好ましく、その中でも、光学特性（透明性等）、機械的強度、熱安定性、水分遮蔽性、等方性、可撓性、寸法安定性等の特性に優れたものを使用することが好ましい。特に、基材フィルムとして、コシが強すぎないポリエステルフィルムは、可撓性を有することで、ロールコーターなどによって粘着剤組成物を塗布することができ、ロール状に巻き取ることができ、有用である。また、ポリエステルフィルムとしては、２種類以上のエステル結合を有するフィルムを用いることもでき、ポリエチレンテレフタラート及びポリブチレンテレフタラートの組み合せたものを好ましく用いることができる。 The base film (base material, support) 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. Among them, 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. In particular, 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. Moreover, as a polyester film, 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.
　前記樹脂材料の他の例としては、ポリスチレン、アクリロニトリル－スチレン共重合体等の、スチレン系ポリマー；塩化ビニル系ポリマー；ナイロン６、ナイロン６，６、芳香族ポリアミド等の、アミド系ポリマー；等を樹脂材料とするものが挙げられる。前記樹脂材料のさらに他の例として、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマー等が挙げられる。上述したポリマーの２種以上のブレンド物からなる基材フィルムであってもよい。 Other examples of the resin material 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.
　本発明の粘着シートは、前記非ポリオレフィン系フィルムの引張弾性率が、１．５×１０９Ｐａ未満であることが好ましく、１．３×１０９Ｐａ以下がより好ましく、１．０×１０７～１．３×１０９Ｐａがさらに好ましく、１．０×１０８～１．３×１０９Ｐａが特に好ましい。前記引張弾性率が、１．５×１０９Ｐａ未満であることにより、ある程度コシの弱い基材フィルムを使用することになり、ディスプレイ等の湾曲部や凹凸部に対して、追従しやすくするため、好ましい態様となる。なお、前記非ポリオレフィン系フィルムの引張弾性率が、１．５×１０９Ｐａ以上であると、基材フィルムのコシが強くなり過ぎ、ディスプレイ等の湾曲部や凹凸部に対して、追従できない恐れがあり、好ましくない。 In the pressure-sensitive adhesive sheet of the present invention, 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. When the tensile elastic modulus is less than 1.5 × 10 9 Pa, 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. When the tensile modulus of the non-polyolefin film is 1.5 × 10 9 Pa or more, 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.
　前記基材フィルムを構成する樹脂材料には、必要に応じて、酸化防止剤、紫外線吸収剤、可塑剤、着色剤（顔料、染料等）等の各種添加剤が配合されていてもよい。例えば、コロナ放電処理、プラズマ処理、紫外線照射処理、酸処理、アルカリ処理、下塗り剤の塗布等の、公知または慣用の表面処理が施されていてもよい。このような表面処理は、例えば、基材フィルムと粘着剤層との密着性（粘着剤層の投錨性）を高めるための処理であり得る。 In the resin material constituting the base film, various additives such as an antioxidant, an ultraviolet absorber, a plasticizer, and a colorant (pigment, dye, etc.) may be blended as necessary. For example, 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).
　前記基材フィルムとして、帯電防止処理がなされてなるポリエステルフィルムを使用することも可能である。帯電防止処理は、基材フィルムの粘着剤層と接する面、又は、基材フィルムの粘着剤層と接しない面のどちらの面に施されていても良い。前記基材フィルムを用いることにより、剥離した際の粘着シート（表面保護フィルム）自体の帯電が抑えられるため、好ましい。また、基材フィルムがポリエステルフィルムであり、前記ポリエステルフィルムに帯電防止処理を施すことにより、粘着シート（表面保護フィルム）自体の帯電を低減し、かつ、被着体への帯電防止能が優れるものが得られる。なお、帯電防止機能を付与する方法としては、特に制限はなく、従来公知の方法を用いることができ、例えば、帯電防止剤と樹脂成分から成る帯電防止性樹脂や導電性ポリマー、導電性物質を含有する導電性樹脂を塗布する方法や導電性物質を蒸着あるいはメッキする方法、また、帯電防止剤等を練り込む方法等があげられる。 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. In addition, 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. In addition, there is no restriction | limiting in particular as a method to provide an antistatic function, A conventionally well-known method can be used, for example, 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.
　前記基材フィルムの厚みとしては、通常５～２００μｍ、好ましくは８～１５０μｍ程度、より好ましくは１０～１００μｍ、更に好ましくは１３～１００μｍ程度である。前記基材フィルムの厚みが、前記範囲内にあると、被着体への貼り合せ作業性と被着体からの剥離性や作業性に優れるため、好ましい。 The thickness of the base film is usually 5 to 200 μm, preferably about 8 to 150 μm, more preferably 10 to 100 μm, and still more preferably about 13 to 100 μm. When 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.
　＜粘着剤層＞
　本発明の粘着シートは、基材フィルムの片面又は両面に粘着剤組成物から形成された粘着剤層を有することを特徴とする。本発明で用いられる粘着剤層は、粘着性を有する粘着性ポリマーを含有する粘着剤組成物から形成されるものであれば、特に制限なく使用できる。前記粘着剤組成物としては、例えば、アクリル系粘着剤、ウレタン系粘着剤、合成ゴム系粘着剤、天然ゴム系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤等を使用することができ、中でも、アクリル系粘着剤、ウレタン系粘着剤、及び、シリコーン系粘着剤からなる群より選択される少なくとも１種を使用(含有)するものが好ましく、特に好ましくは、前記粘着性ポリマーである（メタ）アクリル系ポリマーを使用するアクリル系粘着剤を使用することである。 <Adhesive layer>
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. It is preferable to use (contain) at least one selected from the group consisting of an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive, and particularly preferably the above-mentioned pressure-sensitive adhesive polymer (meth) It is to use an acrylic pressure-sensitive adhesive that uses an acrylic polymer.
　＜アクリル系粘着剤＞
　前記粘着剤層がアクリル系粘着剤を使用する場合、前記アクリル系粘着剤を構成する粘着性ポリマーである（メタ）アクリル系ポリマーは、これを構成する原料モノマーとして、炭素数１～１４のアルキル基を有する(メタ)アクリル系モノマーを、主モノマーとして用いることができる。前記（メタ）アクリル系モノマーとしては、１種または２種以上を使用することができる。前記炭素数が１～１４であるアルキル基を有する(メタ)アクリル系モノマーを用いることにより、被着体（被保護体）に対する剥離力（粘着力）を低く制御することが容易となり、軽剥離性や再剥離性に優れた粘着シート（表面保護フィルム）が得られる。なお、本発明における（メタ）アクリル系ポリマーとは、アクリル系ポリマーおよび／またはメタクリル系ポリマーをいい、また（メタ）アクリレートとは、アクリレートおよび／またはメタクリレートをいう。 <Acrylic adhesive>
When the pressure-sensitive adhesive layer uses an acrylic pressure-sensitive adhesive, the (meth) acrylic polymer, which is a pressure-sensitive polymer constituting the acrylic pressure-sensitive adhesive, 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. By using the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, it becomes easy to control the peeling force (adhesive strength) to the adherend (protected body) to be low and light peeling. A pressure-sensitive adhesive sheet (surface protective film) having excellent properties and removability can be obtained. In the present invention, the (meth) acrylic polymer refers to an acrylic polymer and / or a methacrylic polymer, and the (meth) acrylate refers to acrylate and / or methacrylate.
　前記炭素数１～１４のアルキル基を有する(メタ)アクリル系モノマーの具体例としては、たとえば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、へキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｎ－ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｎ－デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ－ドデシル（メタ）アクリレート、ｎ－トリデシル（メタ）アクリレート、ｎ－テトラデシル（メタ）アクリレートなどがあげられる。 Specific examples of 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 (meth) acrylate, n-tetradecyl (meth) acrylate, etc. It is done.
　なかでも、本発明の粘着シートを表面保護フィルムとして使用する場合は、特に、ｎ－ブチル（メタ）アクリレート、へキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｎ－ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｎ－デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ－ドデシル（メタ）アクリレート、ｎ－トリデシル（メタ）アクリレート、ｎ－テトラデシル（メタ）アクリレートなどの炭素数４～１４のアルキル基を有する(メタ)アクリル系モノマーが好適なものとしてあげられる。特に、炭素数４～１４のアルキル基を有する(メタ)アクリル系モノマーを用いることにより、被着体への剥離力（粘着力）を低く制御することが容易となり、再剥離性に優れたものとなる。 In particular, when the pressure-sensitive adhesive sheet of the present invention is used as a surface protective film, in particular, n-butyl (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 (meth) acrylate Suitable examples include (meth) acrylic monomers having an alkyl group having 4 to 14 carbon atoms such as n-tetradecyl (meth) acrylate. In particular, by using a (meth) acrylic monomer having an alkyl group having 4 to 14 carbon atoms, it becomes easy to control the peel strength (adhesive strength) to the adherend low and has excellent removability. It becomes.
　特に、前記(メタ)アクリル系ポリマーを構成するモノマー成分全量１００重量％に対して、炭素数１～１４であるアルキル基を有する(メタ)アクリル系モノマーを、４０重量％以上含有することが好ましく、より好ましくは、４５重量％以上、更に好ましくは、４５～９９重量％、最も好ましくは５０～９８重量％である。前記範囲を外れると、粘着剤組成物の適度な濡れ性や、粘着剤層の凝集力が劣ることになり、好ましくない。 In particular, it is preferable to contain 40% by weight or more of a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms with respect to 100% by weight of the total amount of monomer components constituting the (meth) acrylic polymer. More preferred is 45% by weight or more, still more preferred is 45 to 99% by weight, and most preferred is 50 to 98% by weight. If it is out of the range, the appropriate wettability of the pressure-sensitive adhesive composition and the cohesive strength of the pressure-sensitive adhesive layer will be inferior, which is not preferable.
　また、前記(メタ)アクリル系ポリマーは、原料モノマーとして、ヒドロキシル基含有(メタ)アクリル系モノマーを用いることができる。前記ヒドロキシル基含有(メタ)アクリル系モノマーとしては、１種または２種以上を使用することができる。前記ヒドロキシル基含有(メタ)アクリル系モノマーを用いることにより、粘着剤組成物の架橋などを制御しやすくなり、ひいては流動による濡れ性の改善と剥離における剥離力（粘着力）の低減とのバランスを制御しやすくなる。 In the (meth) acrylic polymer, a hydroxyl group-containing (meth) acrylic monomer can be used as a raw material monomer. As said hydroxyl group containing (meth) acrylic-type monomer, 1 type (s) or 2 or more types can be used. By using the hydroxyl group-containing (meth) acrylic monomer, it becomes easy to control the crosslinking of the pressure-sensitive adhesive composition, and as a result, balance between improvement of wettability by flow and reduction of peeling force (adhesive strength) in peeling. It becomes easier to control.
　前記ヒドロキシル基含有(メタ)アクリル系モノマーとしては、たとえば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、１０－ヒドロキシデシル（メタ）アクリレート、１２－ヒドロキシラウリル（メタ）アクリレート、（４－ヒドロキシメチルシクロヘキシル）メチルアクリレート、Ｎ－メチロール（メタ）アクリルアミド、などがあげられる。 Examples of the hydroxyl group-containing (meth) acrylic monomer 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. .
　前記(メタ)アクリル系ポリマーを構成するモノマー成分全量１００重量％に対して、前記ヒドロキシル基含有(メタ)アクリル系モノマーを、２０重量％以下含有することが好ましく、より好ましくは、０．１～１５重量％以下、更に好ましくは、１～１０重量％である。前記範囲内にあると、粘着剤組成物の濡れ性と、得られる粘着剤層の凝集力のバランスを制御しやすくなるため、好ましい。 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. 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.
　また、その他の重合性モノマー成分として、粘着性能のバランスが取りやすい理由から、Ｔｇが０℃以下（通常－１００℃以上）になるようにして、（メタ）アクリル系ポリマーのガラス転移温度や剥離性を調整するための重合性モノマーなどを、本発明の効果を損なわない範囲で使用することができる。 As another polymerizable monomer component, 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.
　また、前記(メタ)アクリル系ポリマーは、原料モノマーとして、カルボキシル基含有(メタ)アクリル系モノマーを用いることができる。前記カルボキシル基含有(メタ)アクリル系モノマーを用いることにより、粘着剤層（粘着シート、表面保護フィルム)の経時での粘着力の上昇を抑制することができ、再剥離性、粘着力上昇防止性、及び作業性に優れる。また、粘着剤層の凝集力と共に、せん断力にも優れ、好ましい。 The (meth) acrylic polymer can use a carboxyl group-containing (meth) acrylic monomer as a raw material monomer. By using the carboxyl group-containing (meth) acrylic monomer, the pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet, surface protective film) can be prevented from increasing in adhesive strength over time, re-peelable, and adhesive strength-preventing property And excellent workability. In addition to the cohesive force of the pressure-sensitive adhesive layer, it is excellent in shearing force, which is preferable.
　前記カルボキシル基含有(メタ)アクリル系モノマーとしては、例えば、（メタ）アクリル酸、カルボキシルエチル（メタ）アクリレート、カルボキシルペンチル（メタ）アクリレートなどがあげられる。特に、カルボキシル基含有(メタ)アクリル系モノマーとして、アクリル酸を含有することによって、ガラス転移温度（Ｔｇ）が高くなり、凝集力を高めることができ、例えば、凹凸面や湾曲部の様な曲面に貼り合わせた場合、基材にコシがあるために反発するが、凝集力の高い粘着剤は変形しにくく、耐反発性に優れるため、好ましい。 Examples of the carboxyl group-containing (meth) acrylic monomer include (meth) acrylic acid, carboxylethyl (meth) acrylate, carboxylpentyl (meth) acrylate, and the like. In particular, by containing 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. For example, 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.
　前記(メタ)アクリル系ポリマーを構成するモノマー成分全量１００重量％に対して、前記カルボキシル基含有(メタ)アクリル系モノマーを、２０重量％以下であることが好ましく、１～１５重量％であることがより好ましく、２～１２重量％であることが更に好ましい。前記範囲内にあると、粘着剤組成物の濡れ性と、得られる粘着剤層の凝集力のバランスを制御しやすくなるため、好ましい。 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.
　更に、前記（メタ）アクリル系ポリマーは、前記原料モノマー以外のその他の重合性モノマーを、本発明の特性を損なわない範囲内であれば、特に限定することなく用いることができる。たとえば、前記その他の重合性モノマーとして、シアノ基含有モノマー、ビニルエステルモノマー、芳香族ビニルモノマーなどの凝集力・耐熱性向上成分や、アミド基含有モノマー、イミド基含有モノマー、アミノ基含有モノマー、エポキシ基含有モノマー、Ｎ－アクリロイルモルホリン、ビニルエーテルモノマーなどの剥離力（粘着力）の向上や架橋化基点として働く官能基を有する成分を適宜用いることができる。中でも、シアノ基含有モノマー、アミド基含有モノマー、イミド基含有モノマー、アミノ基含有モノマー、及び、Ｎ－アクリロイルモルホリンなどの窒素含有モノマーを用いることが好ましい。窒素含有モノマーを用いることにより、浮きや剥がれなどが生じない適度な剥離力（粘着力）を確保でき、更にせん断力に優れた粘着シート（表面保護フィルム）を得ることができるため、有用である。これら重合性モノマーは、１種また２種以上を使用することができる。 Furthermore, 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. For example, as the other polymerizable monomer, 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. Among these, it is preferable to use 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. Use of 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.
　前記シアノ基含有モノマーとしては、たとえば、アクリロニトリル、メタクリロニトリルがあげられる。 Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
　前記アミド基含有モノマーとしては、たとえば、アクリルアミド、メタクリルアミド、ジエチルアクリルアミド、Ｎ－ビニルピロリドン、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジメチルメタクリルアミド、Ｎ，Ｎ－ジエチルアクリルアミド、Ｎ，Ｎ－ジエチルメタクリルアミド、Ｎ，Ｎ’－メチレンビスアクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピルアクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピルメタクリルアミド、ジアセトンアクリルアミドなどがあげられる。 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.
　前記イミド基含有モノマーとしては、たとえば、シクロヘキシルマレイミド、イソプロピルマレイミド、Ｎ－シクロヘキシルマレイミド、イタコンイミドなどがあげられる。 Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconimide.
　前記アミノ基含有モノマーとしては、たとえば、アミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレートなどがあげられる。 Examples of the amino group-containing monomer include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like.
　前記ビニルエステルモノマーとしては、たとえば、酢酸ビニル、プロピオン酸ビニル、ラウリン酸ビニルなどがあげられる。 Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, and vinyl laurate.
　前記芳香族ビニルモノマーとしては、たとえば、スチレン、クロロスチレン、クロロメチルスチレン、α－メチルスチレン、その他の置換スチレンなどがあげられる。 Examples of the aromatic vinyl monomer include styrene, chlorostyrene, chloromethyl styrene, α-methyl styrene, and other substituted styrene.
　前記エポキシ基含有モノマーとしては、たとえば、グリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレート、アリルグリシジルエーテルなどがあげられる。 Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and allyl glycidyl ether.
　前記ビニルエーテルモノマーとしては、たとえば、メチルビニルエーテル、エチルビニルエーテル、イソブチルビニルエーテルなどがあげられる。 Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.
　本発明において、前記その他の重合性モノマーは、前記(メタ)アクリル系ポリマーを構成するモノマー成分全量１００重量％に対して、０～３０重量％であることが好ましく、０～１０重量％であることがより好ましい。前記その他の重合性モノマーは所望の特性を得るために、適宜調節することができる。 In the present invention, 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.
　前記（メタ）アクリル系ポリマーが、更に、モノマー成分としてアルキレンオキシド基含有反応性モノマーを含有してもよい。 The (meth) acrylic polymer may further contain an alkylene oxide group-containing reactive monomer as a monomer component.
　また、前記アルキレンオキシド基含有反応性モノマーのオキシアルキレン単位の平均付加モル数としては、オキシアルキレン基含有化合物との相溶性の観点から、１～４０であることが好ましく、３～４０であることがより好ましく、４～３５であることがさらに好ましく、５～３０であることが特に好ましい。前記平均付加モル数が１以上の場合、被着体（被保護体）の汚染低減効果が効率よく得られる傾向がある。また、前記平均付加モル数が４０より大きい場合、オキシアルキレン基含有化合物との相互作用が大きく、粘着剤組成物の粘度が上昇して塗工が困難となる傾向があるため好ましくない。なお、オキシアルキレン鎖の末端は、水酸基のままや、他の官能基などで置換されていてもよい。 In addition, 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. When 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. Moreover, when 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. Note that the terminal of the oxyalkylene chain may be a hydroxyl group or may be substituted with another functional group.
　前記アルキレンオキシド基含有反応性モノマーは単独で使用してもよく、また２種以上を混合して使用してもよいが、全体としての含有量は、前記（メタ）アクリル系ポリマーのモノマー成分全量中、０～２０重量％であることが好ましく、０～１０重量％であることがより好ましい。アルキレンオキシド基含有反応性モノマーの含有量が２０重量％を超えると、被着体への汚染性が悪化するため、好ましくない。 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.
　前記アルキレンオキシド基含有反応性モノマーのオキシアルキレン単位としては、炭素数１～６のアルキレン基を有するものがあげられ、たとえば、オキシメチレン基、オキシエチレン基、オキシプロピレン基、オキシブチレン基などがあげられる。オキシアルキレン鎖の炭化水素基は直鎖でもよく、分岐していてもよい。 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.
　また、前記アルキレンオキシド基含有反応性モノマーがエチレンオキシド基を有する反応性モノマーであることがより好ましい。エチレンオキシド基を有する反応性モノマー含有(メタ)アクリル系ポリマーをベースポリマーとして用いることにより、ベースポリマーとオキシアルキレン基含有化合物との相溶性が向上し、被着体へのブリードが好適に抑制され、低汚染性の粘着剤組成物が得られる。 It is more preferable that the alkylene oxide group-containing reactive monomer is a reactive monomer having an ethylene oxide group. By using 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.
　前記アルキレンオキシド基含有反応性モノマーとしては、たとえば、（メタ）アクリル酸アルキレンオキシド付加物や、分子中にアクリロイル基、メタクリロイル基、アリル基などの反応性置換基を有する反応性界面活性剤などがあげられる。 Examples of the alkylene oxide group-containing reactive monomer 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.
　前記（メタ）アクリル酸アルキレンオキシド付加物の具体例としては、たとえば、ポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、ポリエチレングリコール－ポリプロピレングリコール（メタ）アクリレート、ポリエチレングリコール－ポリブチレングリコール（メタ）アクリレート、ポリプロピレングリコール－ポリブチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、エトキシポリエチレングリコール（メタ）アクリレート、ブトキシポリエチレングリコール（メタ）アクリレート、オクトキシポリエチレングリコール（メタ）アクリレート、ラウロキシポリエチレングリコール（メタ）アクリレート、ステアロキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、オクトキシポリエチレングリコール－ポリプロピレングリコール（メタ）アクリレートなどがあげられる。 Specific examples of 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 - polypropylene glycol (meth) acrylate.
　また、前記反応性界面活性剤の具体例としては、たとえば、（メタ）アクリロイル基またはアリル基を有するアニオン型反応性界面活性剤、ノニオン型反応性界面活性剤、カチオン型反応性界面活性剤などがあげられる。 Specific examples of 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.
　前記（メタ）アクリル系ポリマーは、重量平均分子量（Ｍｗ）が１０万～２００万が好ましく、より好ましくは２０万～１５０万、さらに好ましくは３０万～１２０万、特に好ましくは３０万～１００万であり、最も好ましくは４０万～８０万である。重量平均分子量が１０万より小さい場合は、粘着剤層の凝集力が小さくなることにより糊残りを生じる傾向がある。一方、重量平均分子量が２００万を超える場合は、ポリマーの流動性が低下し、被着体（例えば、偏光板）への濡れが不十分となり、被着体と粘着シート（表面保護フィルム）の粘着剤層との間に発生するフクレの原因となる傾向がある。なお、重量平均分子量は、ＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）により測定して得られたものをいう。 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. When the weight average molecular weight is smaller than 100,000, the adhesive force tends to be generated due to the reduced cohesive force of the pressure-sensitive adhesive layer. On the other hand, when 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. In addition, a weight average molecular weight means what was obtained by measuring by GPC (gel permeation chromatography).
　また、前記（メタ）アクリル系ポリマーのガラス転移温度（Ｔｇ）は、－６０～０℃が好ましく、より好ましくは－５０～－１０℃である。ガラス転移温度が０℃より高い場合、ポリマーが流動しにくく、例えば、光学部材である偏光板への濡れが不十分となり、偏光板と粘着シート（表面保護フィルム）の粘着剤層との間に発生するフクレの原因となる傾向がある。ガラス転移温度（Ｔｇ）が－６０℃より低い場合、粘着剤の凝集力が低くなり、例えば、湾曲や凹凸面の様な曲面に貼り合わせした場合、基材の反発力に負けて、粘着剤層が浮く傾向がある。前記ガラス転移温度（Ｔｇ）上記範囲に調整することで、濡れ性と凝集力のバランスのとれた粘着剤層が得られやすくなる。なお、（メタ）アクリル系ポリマーのガラス転移温度は、用いるモノマー成分や組成比を適宜変えることにより前記範囲内に調整することができる。 The glass transition temperature (Tg) of the (meth) acrylic polymer is preferably −60 to 0 ° C., more preferably −50 to −10 ° C. When 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. When the glass transition temperature (Tg) is lower than −60 ° C., the cohesive force of the pressure-sensitive adhesive becomes low. For example, 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. By adjusting the glass transition temperature (Tg) to the above range, a pressure-sensitive adhesive layer having a good balance between wettability and cohesive force can be easily obtained. In addition, 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.
　前記（メタ）アクリル系ポリマーの重合方法は、特に制限されるものではなく、溶液重合、乳化重合、塊状重合、懸濁重合などの公知の方法により重合できるが、特に作業性の観点や、被着体（被保護体）への低汚染性など特性面から、溶液重合がより好ましい態様である。また、得られるポリマーは、ランダム共重合体、ブロック共重合体、交互共重合体、グラフト共重合体などいずれでもよい。 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.
　＜ウレタン系粘着剤＞
　前記粘着剤層にウレタン系粘着剤を使用する場合、任意の適切なウレタン系粘着剤を採用し得る。このようなウレタン系粘着剤としては、好ましくは、ポリオールとポリイソシアネート化合物を反応させて得られる粘着性ポリマーであるウレタン系ポリマーからなるものが挙げられる。ポリオールとしては、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリカプロラクトンポリオールなどが挙げられる。ポリイソシアネート化合物としては、例えば、ジフェニルメタンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネートなどが挙げられる。 <Urethane adhesive>
When using a urethane-type adhesive for the said adhesive layer, arbitrary appropriate urethane-type adhesives can be employ | adopted. As such 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. Examples of the polyol include polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol. Examples of the polyisocyanate compound include diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and the like.
　＜シリコーン系粘着剤＞
　前記粘着剤層にシリコーン系粘着剤を使用する場合、任意の適切なシリコーン系粘着剤を採用し得る。このようなシリコーン系粘着剤としては、好ましくは、粘着性ポリマーであるシリコーン系ポリマーをブレンドまたは凝集させることにより得られるものを採用し得る。 <Silicon adhesive>
When using a silicone type adhesive for the said adhesive layer, arbitrary appropriate silicone type adhesives can be employ | adopted. As such 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.
　また、前記シリコーン系粘着剤としては、付加反応硬化型シリコーン系粘着剤や過酸化物硬化型シリコーン系粘着剤が挙げられる。これらのシリコーン系粘着剤の中でも、過酸化物（過酸化ベンゾイルなど）を使用せず、分解物が発生しないことから、付加反応硬化型シリコーン系粘着剤が好ましい。 Further, examples of the silicone pressure-sensitive adhesive include addition reaction curable silicone pressure-sensitive adhesives and peroxide curable silicone pressure-sensitive adhesives. Among these silicone pressure-sensitive adhesives, peroxides (benzoyl peroxide and the like) are not used, and decomposition products are not generated. Therefore, an addition reaction curable silicone pressure-sensitive adhesive is preferable.
　前記付加反応硬化型シリコーン系粘着剤の硬化反応としては、例えば、ポリアルキルシリコーン系粘着剤を得る場合、一般的に、ポリアルキル水素シロキサン組成物を白金触媒により硬化させる方法が挙げられる。 As 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.
　＜オキシアルキレン基含有化合物＞
　本発明で用いる粘着剤組成物は、オキシアルキレン基含有化合物を含有することも可能である。オキシアルキレン基含有化合物を含有することにより、更に軽剥離性を発現させることが可能である。オキシアルキレン基含有化合物としては、オキシアルキレン鎖を有するオルガノポリシロキサンやオルガノポリシロキサンを含まないオキシアルキレン基含有化合物が挙げられる。 <Oxyalkylene group-containing compound>
The pressure-sensitive adhesive composition used in the present invention can also contain an oxyalkylene group-containing compound. By containing the oxyalkylene group-containing compound, it is possible to further develop light peelability. Examples of the oxyalkylene group-containing compound include an organopolysiloxane having an oxyalkylene chain and an oxyalkylene group-containing compound not containing an organopolysiloxane.
　前記オキシアルキレン鎖を有するオルガノポリシロキサンの具体例としては、主鎖にオキシアルキレン鎖を有するオルガノポリシロキサンの具体例として、たとえば、市販品として、商品名が、Ｘ－２２－４９５２、Ｘ－２２－４２７２、Ｘ－２２－６２６６、ＫＦ－６００４、ＫＦ－８８９（以上、信越化学工業社製）、ＢＹ１６－２０１、ＳＦ８４２７（以上、東レ・ダウコーニング社製）、ＩＭ２２（旭化成ワッカー社製）などがあげられる。また、側鎖にオキシアルキレン鎖を有するオルガノシロキサンとしては、たとえば、市販品としての商品名ＫＦ－３５１Ａ、ＫＦ－３５２Ａ、ＫＦ－３５３、ＫＦ－３５４Ｌ、ＫＦ－３５５Ａ、ＫＦ－６１５Ａ、ＫＦ－９４５、ＫＦ－６４０、ＫＦ－６４２、ＫＦ－６４３、ＫＦ－６０２２、Ｘ－２２－６１９１、Ｘ－２２－４５１５、ＫＦ－６０１１、ＫＦ－６０１２、ＫＦ－６０１５、ＫＦ－６０１７、Ｘ－２２－２５１６（以上、信越化学工業社製）ＳＦ８４２８、ＦＺ－２１６２、ＳＨ３７４９、ＦＺ－７７、Ｌ－７００１、ＦＺ－２１０４、ＦＺ－２１１０、Ｌ－７００２、ＦＺ－２１２２、ＦＺ－２１６４、ＦＺ－２２０３、ＦＺ－７００１、ＳＨ８４００、ＳＨ８７００、ＳＦ８４１０、ＳＦ８４２２（以上、東レ・ダウコーニング社製）、ＴＳＦ－４４４０、ＴＳＦ－４４４１、ＴＳＦ－４４４５、ＴＳＦ－４４５０、ＴＳＦ－４４４６、ＴＳＦ－４４５２、ＴＳＦ－４４６０（モメンティブパフォーマンスマテリアルズ社製）、ＢＹＫ－３３３、ＢＹＫ－３０７、ＢＹＫ－３７７、ＢＹＫ－ＵＶ３５００、ＢＹＫ－ＵＶ３５７０（ビックケミー・ジャパン社製）などがあげられる。これらの化合物は、単独で使用してもよく、また２種以上を混合して使用してもよい。 Specific examples of the organopolysiloxane having an oxyalkylene chain 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. Examples of the organosiloxane having an oxyalkylene chain in the side chain include, for example, trade names KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945. , KF-640, KF-642, KF-643, KF-6022, X-22-6191, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, X-22-2516 (Shin-Etsu Chemical Co., Ltd.) SF8428, FZ-2162, SH3749, FZ-77, L-7001, FZ-2104, FZ-2110, L-7002, FZ-2122, FZ-2164, FZ-2203, FZ -7001, SH8400, SH8700, SF8410, SF8422 (above, Toray Dowco , TSF-4440, TSF-4441, TSF-4445, TSF-4450, TSF-4446, TSF-4442, TSF-4460 (manufactured by Momentive Performance Materials), BYK-333, BYK-307, BYK -377, BYK-UV3500, BYK-UV3570 (manufactured by Big Chemie Japan) and the like. These compounds may be used alone or in combination of two or more.
　前記オルガノポリシロキサンを含まないオキシアルキレン基含有化合物の具体例としては、たとえば、ポリオキシアルキレンアルキルアミン、ポリオキシアルキレンジアミン、ポリオキシアルキレン脂肪酸エステル、ポリオキシアルキレンソルビタン脂肪酸エステル、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルアリルエーテル、ポリオキシアルキレンアルキルフェニルアリルエーテル等の非イオン性界面活性剤；ポリオキシアルキレンアルキルエーテル硫酸エステル塩、ポリオキシアルキレンアルキルエーテルリン酸エステル塩、ポリオキシアルキレンアルキルフェニルエーテル硫酸エステル塩、ポリオキシアルキレンアルキルフェニルエーテルリン酸エステル塩等のアニオン性界面活性剤；その他、ポリオキシアルキレン鎖（ポリアルキレンオキシド鎖）を有するカチオン性界面活性剤や両イオン性界面活性剤、ポリオキシアルキレン鎖を有するポリエーテル系化合物（およびその誘導体を含む）、ポリオキシアルキレン鎖を有するアクリル化合物（およびその誘導体を含む）等が挙げられる。また、ポリオキシアルキレン鎖含有モノマーを、ポリオキシアルキレン鎖含有化合物として配合してもよい。かかるポリオキシアルキレン鎖含有化合物は、単独で使用してもよく、２種以上を組み合わせて使用してもよい。 Specific examples of the oxyalkylene group-containing compound not containing the organopolysiloxane 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 | blend a polyoxyalkylene chain containing monomer as a polyoxyalkylene chain containing compound. Such polyoxyalkylene chain-containing compounds may be used alone or in combination of two or more.
　前記ポリオキシアルキレン鎖を有するポリエーテル系化合物（ポリエーテル成分）の具体例としては、ポリプロピレングリコール（ＰＰＧ）－ポリエチレングリコール（ＰＥＧ）のブロック共重合体、ＰＰＧ－ＰＥＧ－ＰＰＧのブロック共重合体、ＰＥＧ－ＰＰＧ－ＰＥＧのブロック共重合体等が挙げられる。前記ポリオキシアルキレン鎖を有するポリエーテル系化合物の誘導体としては、末端がエーテル化されたオキシプロピレン基含有化合物（ＰＰＧモノアルキルエーテル、ＰＥＧ－ＰＰＧモノアルキルエーテル等）、末端がアセチル化されたオキシプロピレン基含有化合物（末端アセチル化ＰＰＧ等）、等が挙げられる。 Specific examples of the polyether compound (polyether component) having a polyoxyalkylene chain 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. Examples of 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.
　また、前記ポリオキシアルキレン鎖を有するアクリル化合物の具体例としては、オキシアルキレン基を有する（メタ）アクリレート重合体が挙げられる。前記オキシアルキレン基としては、オキシアルキレン単位の付加モル数が、１～５０が好ましく、２～３０がより好ましく、２～２０がさらに好ましい。また、前記オキシアルキレン鎖の末端は、水酸基のままや、アルキル基、フェニル基等で置換されていてもよい。 Further, specific examples of 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.
　前記オキシアルキレン基を有する（メタ）アクリレート重合体は、モノマー成分として、（メタ）アクリル酸アルキレンオキサイドを含む重合体であることが好ましく、前記（メタ）アクリル酸アルキレンオキサイドの具体例としては、エチレングリコール基含有（メタ）アクリレートとしては、たとえば、メトキシ－ジエチレングリコール（メタ）アクリレート、メトキシ－トリエチレングリコール（メタ）アクリレートなどのメトキシ－ポリエチレングリコール（メタ）アクリレート型、エトキシ－ジエチレングリコール（メタ）アクリレート、エトキシ－トリエチレングリコール（メタ）アクリレートなどのエトキシ－ポリエチレングリコール（メタ）アクリレート型、ブトキシ－ジエチレングリコール（メタ）アクリレート、ブトキシ－トリエチレングリコール（メタ）アクリレートなどのブトキシ－ポリエチレングリコール（メタ）アクリレート型、フェノキシ－ジエチレングリコール（メタ）アクリレート、フェノキシ－トリエチレングリコール（メタ）アクリレートなどのフェノキシ－ポリエチレングリコール（メタ）アクリレート型、２－エチルヘキシル－ポリエチレングリコール（メタ）アクリレート、ノニルフェノール－ポリエチレングリコール（メタ）アクリレート型、メトキシ－ジプロピレングリコール（メタ）アクリレートなどのメトキシ－ポリプロピレングリコール（メタ）アクリレート型などがあげられる。 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. Examples of 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 such as phenoxy-diethylene glycol (meth) acrylate, phenoxy-triethylene glycol (meth) acrylate, Examples include 2-ethylhexyl-polyethylene glycol (meth) acrylate, nonylphenol-polyethylene glycol (meth) acrylate type, and methoxy-polypropylene glycol (meth) acrylate type such as methoxy-dipropylene glycol (meth) acrylate.
　また、前記モノマー成分として、前記（メタ）アクリル酸アルキレンオキサイド以外のその他モノマー成分も用いることができる。その他モノマー成分の具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｎ－ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｎ－デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ－ドデシル（メタ）アクリレート、ｎ－トリデシル（メタ）アクリレート、ｎ－テトラデシル（メタ）アクリレートなどの炭素数１～１４のアルキル基を有すアクリレートおよび／またはメタクリレートが挙げられる。 Further, as 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. 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 Acrylates having 1 to 14 carbon atoms and / or methacrylates, such as isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, and n-tetradecyl (meth) acrylate Door and the like.
　さらに、前記（メタ）アクリル酸アルキレンオキサイド以外のその他モノマー成分として、カルボキシル基含有（メタ）アクリレート、リン酸基含有（メタ）アクリレート、シアノ基含有（メタ）アクリレート、ビニルエステル類、芳香族ビニル化合物、酸無水物基含有（メタ）アクリレート、ヒドロキシル基含有（メタ）アクリレート、アミド基含有（メタ）アクリレート、アミノ基含有（メタ）アクリレート、エポキシ基含有（メタ）アクリレート、Ｎ－アクリロイルモルホリン、ビニルエーテル類等を、適宜用いることも可能である。 Furthermore, as other monomer components other than the (meth) acrylic acid alkylene oxide, carboxyl group-containing (meth) acrylate, phosphoric acid group-containing (meth) acrylate, cyano group-containing (meth) acrylate, vinyl esters, aromatic vinyl compounds , Acid anhydride group-containing (meth) acrylate, hydroxyl group-containing (meth) acrylate, amide group-containing (meth) acrylate, amino group-containing (meth) acrylate, epoxy group-containing (meth) acrylate, N-acryloylmorpholine, vinyl ethers Etc. can be used as appropriate.
　＜架橋剤＞
　本発明の粘着シートは、前記粘着剤組成物が、架橋剤を含有することが好ましい。また、本発明においては、前記粘着剤組成物を用いて、粘着剤層とすることができる。例えば、前記粘着剤組成物が、前記（メタ）アクリル系ポリマーを含有するアクリル系粘着剤の場合、前記（メタ）アクリル系ポリマーの構成単位、構成比率、架橋剤の選択および添加比率等を適宜調節して架橋することにより、より耐熱性、及び、湾曲部や凹凸部の様な曲面への追従性に優れた粘着剤層(粘着シート、表面保護フィルム)を得ることができる。 <Crosslinking agent>
In the pressure-sensitive adhesive sheet of the present invention, 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. For example, in the case where 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. By adjusting and crosslinking, a pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet, surface protective film) having more excellent heat resistance and followability to a curved surface such as a curved portion or an uneven portion can be obtained.
　本発明に用いられる架橋剤としては、イソシアネート化合物、エポキシ化合物、メラミン系樹脂、アジリジン誘導体、および金属キレート化合物などを用いてもよく、特にエポキシ化合物の使用は、粘着剤の凝集力が高まり、好ましい態様となる。また、これらの化合物は単独で使用してもよく、２種以上を混合して使用してもよい。 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. In particular, the use of an epoxy compound is preferable because the cohesive force of the adhesive increases. It becomes an aspect. Moreover, these compounds may be used independently and may be used in mixture of 2 or more types.
　前記イソシアネート化合物としては、たとえば、トリメチレンジイソシアネート、ブチレンジイソシアネート、ヘキサメチレンジイソシアネート（ＨＤＩ）、ダイマー酸ジイソシアネートなどの脂肪族ポリイソシアネート類、シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、イソホロンジイソシアネート（ＩＰＤＩ）、１，３－ビス（イソシアナトメチル）シクロヘキサンなどの脂環族イソシアネート類、２，４－トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、キシリレンジイソシアネート（ＸＤＩ）などの芳香族イソシアネート類、前記イソシアネート化合物をアロファネート結合、ビウレット結合、イソシアヌレート結合、ウレトジオン結合、ウレア結合、カルボジイミド結合、ウレトンイミン結合、オキサジアジントリオン結合などにより変性したポリイソシネート変性体が挙げられる。たとえば、市販品として、商品名タケネート３００Ｓ、タケネート５００、タケネート６００、タケネートＤ１６５Ｎ、タケネートＤ１７８Ｎ（以上、三井化学社製）、スミジュールＴ８０、スミジュールＬ、デスモジュールＮ３４００（以上、住化バイエルウレタン社製）、ミリオネートＭＲ、ミリオネートＭＴ、コロネートＬ、コロネートＨＬ、コロネートＨＸ（以上、東ソー社製）などがあげられる。これらイソシアネート化合物は、単独で使用してもよく、２種以上混合して使用してもよく、２官能のイソシアネート化合物と３官能以上のイソシアネート化合物を併用して用いることも可能である。架橋剤を併用して用いることにより粘着性と耐反発性（湾曲部や凹凸部の様な曲面に対する粘着性）を両立することが可能となり、より粘着信頼性に優れた粘着剤層(粘着シート、表面保護フィルム)を得ることができる。 Examples of the isocyanate compound 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. For example, as commercial products, trade names Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (above, made by Mitsui Chemicals), Sumijoule T80, Sumijoule L, Death Module N3400 (above, Sumika Bayer Urethane Co., Ltd.) Millionate MR, Millionate MT, Coronate L, Coronate HL, Coronate HX (above, manufactured by Tosoh Corporation), and the like. These isocyanate compounds may be used alone, or may be used in combination of two or more, and a bifunctional isocyanate compound and a trifunctional or higher isocyanate compound may be used in combination. By using a cross-linking agent in combination, it is possible to achieve both adhesiveness and repulsion resistance (adhesion to curved surfaces such as curved parts and uneven parts), and an adhesive layer (adhesive sheet) with superior adhesive reliability , Surface protective film) can be obtained.
　前記エポキシ化合物としては、たとえば、Ｎ,Ｎ,Ｎ’,Ｎ’－テトラグリシジル－ｍ－キシレンジアミン（商品名ＴＥＴＲＡＤ－Ｘ、三菱瓦斯化学社製）や１，３－ビス（Ｎ,Ｎ－ジグリシジルアミノメチル）シクロヘキサン（商品名ＴＥＴＲＡＤ－Ｃ、三菱瓦斯化学社製）などがあげられる。 Examples of the epoxy compound 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.).
　前記メラミン系樹脂としてはヘキサメチロールメラミンなどがあげられる。アジリジン誘導体としては、たとえば、市販品としての商品名ＨＤＵ、ＴＡＺＭ、ＴＡＺＯ（以上、相互薬工社製）などがあげられる。 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.
　前記金属キレート化合物としては、金属成分としてアルミニウム、鉄、スズ、チタン、ニッケルなど、キレート成分としてアセチレン、アセト酢酸メチル、乳酸エチルなどがあげられる。 Examples of the metal chelate compound include aluminum, iron, tin, titanium, and nickel as metal components, and acetylene, methyl acetoacetate, and ethyl lactate as chelate components.
　本発明に用いられる架橋剤の含有量は、例えば、前記（メタ）アクリル系ポリマー１００重量部に対して、０．０１～２０重量部であることが好ましく、０．１～１８重量部であることがより好ましく、０．５～１５重量部であることがさらに好ましく、１～１２重量部であることが最も好ましい。前記含有量が０．０１重量部よりも少ない場合、架橋剤による架橋形成が不十分となり、得られる粘着剤層の凝集力が小さくなって、十分な耐熱性が得られない場合もあり、また糊残りの原因となり、また、湾曲部や凹凸部の様な曲面への貼り合わせ時の耐反発性に劣る傾向がある。一方、含有量が２０重量部を超える場合、ポリマーの凝集力が大きく、流動性が低下し、被着体（例えば、偏光板）への濡れが不十分となって、被着体と粘着剤層（粘着剤組成物層）との間に発生するフクレの原因となる傾向がある。また、前記範囲内で架橋剤を使用することにより、濡れ性と耐反発性のバランスがとれ、湾曲部や凹凸部に対しての追従性に優れた粘着剤層を得られやすくなり、好ましい態様となる。これらの架橋剤は単独で使用してもよく、また２種以上を混合して使用してもよい。 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. When 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. On the other hand, when the content exceeds 20 parts by weight, 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). In addition, by using 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.
　＜架橋触媒＞
　前記粘着剤組成物には、さらに、上述したいずれかの架橋反応をより効果的に進行させるための架橋触媒を含有させることができる。かかる架橋触媒として、例えば、ジラウリン酸ジブチルスズ、ジラウリン酸ジオクチルスズなどのスズ系触媒、トリス（アセチルアセトナト）鉄、トリス（ヘキサン－２，４－ジオナト）鉄、トリス（ヘプタン－２，４－ジオナト）鉄、トリス（ヘプタン－３，５－ジオナト）鉄、トリス（５－メチルヘキサン－２，４－ジオナト）鉄、トリス（オクタン－２，４－ジオナト）鉄、トリス（６－メチルヘプタン－２，４－ジオナト）鉄、トリス（２，６－ジメチルヘプタン－３，５－ジオナト）鉄、トリス（ノナン－２，４－ジオナト）鉄、トリス（ノナン－４，６－ジオナト）鉄、トリス（２，２，６，６－テトラメチルヘプタン－３，５－ジオナト）鉄、トリス（トリデカン－６，８－ジオナト）鉄、トリス（１－フェニルブタン－１，３－ジオナト）鉄、トリス（ヘキサフルオロアセチルアセトナト）鉄、トリス（アセト酢酸エチル）鉄、トリス（アセト酢酸－ｎ－プロピル）鉄、トリス（アセト酢酸イソプロピル）鉄、トリス（アセト酢酸－ｎ－ブチル）鉄、トリス（アセト酢酸－sec－ブチル）鉄、トリス（アセト酢酸－tert－ブチル）鉄、トリス（プロピオニル酢酸メチル）鉄、トリス（プロピオニル酢酸エチル）鉄、トリス（プロピオニル酢酸－ｎ－プロピル）鉄、トリス（プロピオニル酢酸イソプロピル）鉄、トリス（プロピオニル酢酸－ｎ－ブチル）鉄、トリス（プロピオニル酢酸－sec－ブチル）鉄、トリス（プロピオニル酢酸－tert－ブチル）鉄、トリス（アセト酢酸ベンジル）鉄、トリス（マロン酸ジメチル）鉄、トリス（マロン酸ジエチル）鉄、トリメトキシ鉄、トリエトキシ鉄、トリイソプロポキシ鉄、塩化第二鉄などの鉄系触媒を用いることができる。これら架橋触媒は、１種でもよく、２種以上を併用してもよい。 <Crosslinking catalyst>
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. Examples of such 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 (isopropyl acetoacetate) iron, tris (acetoacetate-n-butyl) ) Iron, Tris (acetoacetate-sec-butyl) iron, Tris (acetoacetate-tert-butyl) iron, Tris (methyl propionyl acetate) iron, Tris (propionyl acetate ethyl) iron, Tris (propionyl acetate-n-propyl) Iron, tris (propionyl acetate isopropyl) iron, tris (propionyl acetate-n-butyl) iron, tris (propionyl acetate-sec-butyl) iron, tris (propionyl acetate-tert-butyl) iron, tris (benzyl acetoacetate) iron , Tris (dimethyl malonate) iron, tris (diethyl malonate) iron, trimethoxy iron Iron-based catalysts such as triethoxy iron, triisopropoxy iron, and ferric chloride can be used. These crosslinking catalysts may be used alone or in combination of two or more.
　前記架橋触媒の含有量は、特に制限されないが、例えば、前記(メタ)アクリル系ポリマー１００重量部に対して、およそ０．０００１～１重量部とすることが好ましく、０．００１～０．５重量部がより好ましい。前記範囲内にあると、粘着剤層を形成した際に架橋反応の速度が速く、粘着剤組成物のポットライフも長くなり、好ましい態様となる。 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.
　さらに、前記粘着剤組成物には、その他の公知の添加剤を含有していてもよく、たとえば、滑剤、着色剤、顔料などの粉体、可塑剤、粘着付与剤、低分子量ポリマー、表面潤滑剤、レベリング剤、酸化防止剤、腐食防止剤、光安定剤、紫外線吸収剤、重合禁止剤、シランカップリンング剤、帯電防止剤、無機または有機の充填剤、金属粉、粒子状、箔状物などを使用する用途に応じて適宜添加することができる。 Further, 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. Agent, leveling agent, antioxidant, corrosion inhibitor, light stabilizer, UV absorber, polymerization inhibitor, silane coupling agent, antistatic agent, inorganic or organic filler, metal powder, particulate, foil It can be added as appropriate depending on the purpose of using the product.
　＜粘着シート（表面保護フィルム）＞
　本発明の粘着シート（表面保護フィルム）は、基材フィルムの片面又は両面に粘着剤組成物から形成された粘着剤層を有することを特徴とするものであるが、その際、粘着剤組成物の架橋は、粘着剤組成物の塗布後に行うのが一般的であるが、架橋後の粘着剤組成物からなる粘着剤層を基材フィルムなどに転写することも可能である。 <Adhesive sheet (surface protective film)>
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. In general, 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.
　また、基材フィルム上に粘着剤層を形成する方法は特に問わないが、たとえば、前記粘着剤組成物（溶液）を基材フィルムに塗布し、重合溶剤などを乾燥除去して粘着剤層を基材フィルム上に形成することにより作製される。その後、粘着剤層の成分移行の調整や架橋反応の調整などを目的として養生をおこなってもよい。また、粘着剤組成物を基材フィルム上に塗布して粘着シートを作製する際には、基材フィルム上に均一に塗布できるよう、前記粘着剤組成物中に重合溶剤以外の一種以上の溶剤を新たに加えてもよい。 The method for forming the pressure-sensitive adhesive layer on the base film is not particularly limited. For example, 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. In addition, 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.
　また、本発明の粘着シートを製造する際の粘着剤層の形成方法としては、粘着テープ類の製造に用いられる公知の方法が用いられる。具体的には、たとえば、ロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、エアーナイフコート法、ダイコーターなどによる押出しコート法などがあげられる。 In addition, 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.
　本発明の粘着シートは、通常、前記粘着剤層の厚みが３～１００μｍ、好ましくは５～３０μｍ程度となるように作製する。粘着剤層の厚みが、前記範囲内にあると、適度な再剥離性と粘着性のバランスを得やすいため、好ましい。 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 μm, preferably about 5 to 30 μm. 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.
　また、本発明の粘着シートは、総厚みが、８～３００μｍであることが好ましく、１０～２００μｍであることがより好ましく、２０～１００μｍであることが最も好ましい。前記範囲内であると、粘着特性(再剥離性、粘着性など)、作業性、外観特性に優れ、好ましい態様となる。なお、前記総厚みとは、基材フィルム、粘着剤層、セパレータ、及び、その他の層などの全ての層を含む厚みの合計を意味する。 The total thickness of the pressure-sensitive adhesive sheet of the present invention is preferably 8 to 300 μm, more preferably 10 to 200 μm, and most preferably 20 to 100 μm. Within the above range, it is excellent in adhesive properties (removability, adhesiveness, etc.), workability, and appearance properties, and is a preferred embodiment. In addition, 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.
　＜セパレータ＞
　ここに開示される粘着シートは、粘着面を保護する目的で粘着剤層表面にセパレータ（剥離ライナー）が貼り合わされた粘着製品の形態をとり得る。したがって、この明細書により、ここに開示されるいずれかの粘着シートと、該粘着シートの粘着面を保護するセパレータとを含むセパレータ付き粘着シート（粘着製品）が提供され得る。 <Separator>
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.
　セパレータとしては、特に限定されず、例えば、樹脂フィルムや紙（ポリエチレン等の樹脂がラミネートされた紙であり得る。）等の基材の表面に剥離層を有するセパレータや、フッ素系ポリマー（ポリテトラフルオロエチレン等）やポリオレフィン系樹脂（ポリエチレン、ポリプロピレン等）のような低接着性材料により形成された樹脂フルムからなるセパレータ等を用いることができる。表面平滑性に優れることから、基材としての樹脂フィルムの表面に剥離層を有するセパレータや、低接着性材料により形成された樹脂フィルムからなるセパレータを好ましく採用し得る。樹脂フィルムとしては、粘着剤層を保護し得るフィルムであれば特に限定されず、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエステルフィルム（ＰＥＴフィルム、ＰＢＴフィルム等）、ポリウレタンフィルム、エチレン－酢酸ビニル共重合体フィルムなどが挙げられる。上記剥離層の形成には、例えば、シリコーン系剥離処理剤、長鎖アルキル系剥離処理剤、オレフィン系剥離処理剤、フッ素系剥離処理剤、脂肪酸アミド系剥離処理剤、硫化モリブデン、シリカ粉等の、公知の剥離処理剤を用いることができる。シリコーン系剥離処理剤の使用が特に好ましい。剥離処理剤の厚さは、特に制限されないが、通常、０．０１～１μｍ程度が適当であり、０．１～１μｍ程度が好ましい。 The separator is not particularly limited. For example, 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. For example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer. Examples include films, polyester films (PET film, PBT film, etc.), polyurethane films, ethylene-vinyl acetate copolymer films, and the like. 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 μm, preferably about 0.1 to 1 μm.
　セパレータの厚さは、特に限定されないが、通常は５～２００μｍ程度（例えば１０～１００μｍ程度、好ましくは２０～８０μｍ程度）が適当である。セパレータの厚さが上記範囲内にあると、粘着剤層への貼り合わせ作業性と粘着剤層からの剥離作業性に優れるため、好ましい。 The thickness of the separator is not particularly limited, but is usually about 5 to 200 μm (for example, about 10 to 100 μm, preferably about 20 to 80 μm). 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.
　前記セパレータ用の基材には、必要に応じて、その表面をコロナ放電処理などの各種表面処理を施したり、エンボス加工などの各種表面加工を施したりすることができる。また、必要に応じて、充填剤（無機充填剤、有機充填剤など）、老化防止剤、酸化防止剤、紫外線吸収剤、帯電防止剤、滑剤、可塑剤、着色剤（顔料、染料など）等の各種添加剤が配合されていてもよい。 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.
　前記セパレータの剥離処理剤面、もしくは、剥離処理剤が施されていない面に、帯電防止処理が施されていても良い。 ¡An antistatic treatment may be applied to the release agent surface of the separator or the surface to which no release agent is applied.
　ここに開示される粘着シート（表面保護フィルム）は、基材フィルム、粘着剤層、及び、セパレータに加えて、さらに他の層を含む態様でも実施され得る。前記他の層としては、帯電防止層や粘着剤層の投錨性を高める下塗り層（アンカー層）などが挙げられる。 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. Examples of the other layer include an undercoat layer (anchor layer) that improves the anchoring property of the antistatic layer and the pressure-sensitive adhesive layer.
　本発明の粘着シートは、前記粘着シートを幅５０ｍｍ、長さ１００ｍｍに切断し、長さ方向に５０ｍｍはみ出るように水平な台に固定したときの垂直下垂距離Ｌが、３０ｍｍ以上であり、前記粘着剤層表面をガラスに貼り合せ、９０度方向に剥離速度１ｍｍ／ｍｉｎで引っ張った際の剥離力（低速剥離力）が、３．０ｇｆ／５０ｍｍ以上であることを特徴とする。前記垂直下垂距離Ｌが、３０ｍｍ以上とすることで、基材フィルムとしてコシが弱いものを使用することになるため、湾曲部や凹凸部の様な曲面に貼り合わせた際に、基材フィルムの反発が弱く、追従性が良好となり好ましい。また、低速剥離力が大きいほど、粘着剤の凝集力が高いため、湾曲部や凹凸部の様な曲面に貼り合わせた際の耐反発性に優れ、曲面への粘着性に優れる。特に、前記低速剥離力を３．０ｇｆ／５０ｍｍ以上とすることで、湾曲部や凹凸部の様な曲面に貼り合わせても、浮きが生じず、密着できる様態となり、好ましい。また、前記垂直下垂距離Ｌが、３２ｍｍ以上であることが好ましく、３２～５０ｍｍであることがより好ましく、３４～４９ｍｍであることがさらに好ましい。また、前記剥離力としては、４ｇｆ／５０ｍｍ以上であることが好ましく、６～３０ｇｆ／５０ｍｍであることがより好ましく、８～１５ｇｆ／５０ｍｍであることがさらに好ましい。前記剥離力の上限値が３０ｇｆ／５０ｍｍ以下であることにより、剥離力（粘着力）が高くなり過ぎず、再剥離性に優れ、好ましい態様となる。 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. When the vertical droop distance L is 30 mm or more, a base film having a weak stiffness is used. Therefore, when 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. Moreover, since 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 | corrugated | grooved part, and is excellent in the adhesiveness to a curved surface. In particular, by setting 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. When the upper limit value of the peeling force is 30 gf / 50 mm or less, the peeling force (adhesive force) does not become too high, and the re-peelability is excellent, which is a preferred embodiment.
　＜光学部材＞
　本発明の光学部材は、前記粘着シートにより保護されることが好ましい。本発明において、前記粘着シート（表面保護フィルム）の粘着剤層の表面を光学部材に貼付し、光学部材を保護することができる。また、湾曲部や凹凸部への追従性が良好なため、湾曲部や凹凸部を有する光学部材の表面を保護するために、有用である。 <Optical member>
The optical member of the present invention is preferably protected by the pressure-sensitive adhesive sheet. In this invention, 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. Moreover, since followability to a curved part or an uneven | corrugated | 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 | corrugated | grooved part.
　＜表示装置＞
　本発明の表示装置は、前記粘着シートにより保護されることが好ましい。本発明において、前記粘着シート（表面保護フィルム）の粘着剤層の表面を、表示装置や表示装置を構成するディスプレイ（画面）の表面に貼付し、表示装置やディスプレイを保護することができる。また、湾曲部や凹凸部への追従性が良好なため、湾曲部や凹凸部を有する表示装置やディスプレイの表面を保護するために、有用である。 <Display device>
The display device of the present invention is preferably protected by the pressure-sensitive adhesive sheet. In this invention, the surface of the adhesive layer of the said adhesive sheet (surface protective film) 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. Moreover, since the followability to a curved part and an uneven | corrugated | 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 | corrugated | grooved part.
　以下、本発明に関連するいくつかの実施例を説明するが、本発明をかかる具体例に示すものに限定することを意図したものではない。なお、以下の説明中の「部」および「％」は、特に断りがない限り重量基準である。また、表中の配合量(添加量)を示した。また、測定(評価)において、特に、測定条件(温度、湿度、時間)を明記していない場合は、２３℃×５０％ＲＨで３０分間静置した後に測定(評価)した。 Hereinafter, some examples related to the present invention will be described. However, the present invention is not intended to be limited to the specific examples. In the following description, “parts” and “%” are based on weight unless otherwise specified. Further, the blending amount (addition amount) in the table is shown. Further, in the measurement (evaluation), when the measurement conditions (temperature, humidity, time) were not specified, the measurement (evaluation) was carried out after standing at 23 ° C. × 50% RH for 30 minutes.
　また、以下の説明中の各特性は、それぞれ次のようにして、測定及び評価した。 Also, each characteristic in the following description was measured and evaluated as follows.
　＜（メタ）アクリル系ポリマーガラス転移温度（Ｔｇ）の測定＞
　ガラス転移温度（Ｔｇ）（℃）は、各モノマーによるホモポリマーのガラス転移温度Ｔｇｎ（℃）として、下記の文献値を用い、下記の式により求めた。
　式：１／（Ｔｇ＋２７３）＝Σ[Ｗｎ／（Ｔｇｎ＋２７３）]
　（式中、Ｔｇ（℃）は共重合体のガラス転移温度、Ｗｎ（－）は各モノマーの重量分率、Ｔｇｎ（℃）は各モノマーによるホモポリマーのガラス転移温度、ｎは各モノマーの種類を表す。）
　文献値：
　２－エチルヘキシルアクリレート（２ＥＨＡ）：－７０℃
　ブチルアクリレート（ＢＡ）：－５５℃
　酢酸ビニル（ＶＡｃ）：３２℃
　２－ヒドロキシエチルアクリレート（ＨＥＡ）：－１５℃
　アクリル酸（ＡＡ）：１０６℃
　なお、文献値として「アクリル樹脂の合成・設計と新用途開発」（中央経営開発センター出版部発行）を参照した。 <Measurement of (meth) acrylic polymer glass transition temperature (Tg)>
The glass transition temperature (Tg) (° C.) was determined by the following formula using the following literature values as the glass transition temperature Tgn (° C.) of the homopolymer of each monomer.
Formula: 1 / (Tg + 273) = Σ [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. Represents.)
Literature values:
2-Ethylhexyl acrylate (2EHA): -70 ° C
Butyl acrylate (BA): -55 ° C
Vinyl acetate (VAc): 32 ° C
2-hydroxyethyl acrylate (HEA): -15 ° C
Acrylic acid (AA): 106 ° C
In addition, as a reference value, “Synthesis / design of acrylic resin and development of new application” (published by Central Management Development Center Publishing Department) was referred.
　＜（メタ）アクリル系ポリマーの重量平均分子量（Ｍｗ）の測定＞
　使用する(メタ)アクリル系ポリマーの重量平均分子量（Ｍｗ）は、東ソー株式会社製ＧＰＣ装置（ＨＬＣ－８２２０ＧＰＣ）を用いて測定を行った。測定条件は下記の通りである。
　サンプル濃度：０．２重量％（ＴＨＦ溶液）
　サンプル注入量：１０μl
　溶離液：ＴＨＦ
　流速：０．６ｍｌ／ｍｉｎ
　測定温度：４０℃
　カラム：
　　サンプルカラム；ＴＳＫｇｕａｒｄｃｏｌｕｍｎ　ＳｕｐｅｒＨＺ－Ｈ（１本）＋ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｈ（２本）
　　リファレンスカラム；ＴＳＫｇｅｌ　ＳｕｐｅｒＨ－ＲＣ（１本）
　検出器：示差屈折計（ＲＩ）
　なお、重量平均分子量はポリスチレン換算値にて求めた。 <Measurement of weight average molecular weight (Mw) of (meth) acrylic polymer>
The weight average molecular weight (Mw) of the (meth) acrylic polymer used was measured using a GPC apparatus (HLC-8220GPC) manufactured by Tosoh Corporation. The measurement conditions are as follows.
Sample concentration: 0.2% by weight (THF solution)
Sample injection volume: 10 μl
Eluent: THF
Flow rate: 0.6 ml / min
Measurement temperature: 40 ° C
column:
Sample column; TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)
Reference column; TSKgel SuperH-RC (1 piece)
Detector: Differential refractometer (RI)
The weight average molecular weight was determined in terms of polystyrene.
　＜基材フィルムの引張弾性率＞
　各種基材フィルムを、幅１５ｍｍ、長さ５０ｍｍに切り出してサンプルとし、このサンプルに対して、２３℃×５０％ＲＨの環境下で、チャック間距離２０ｍｍ、引張速度１００ｍｍ／ｍｉｎで引張試験（島津製作所製、引張試験機　オートグラフＡＧ－２０ｋＮＸ）を行い、当該サンプルが伸長したことによるその変化量（ｍｍ）を測定した。これにより、得られたＳ－Ｓ（Strain-Strength）曲線において、その初期の立ち上がりの部分に接線を引き、その接線が１００％の伸びに相当するときの引張強度を各基材フィルムの断面積で除し、得られた値を引張弾性率（Ｐａ）とした。 <Tensile modulus of base film>
Various substrate films were cut into a width of 15 mm and a length of 50 mm to obtain a sample, and a tensile test (Shimadzu) was performed at a distance between chucks of 20 mm and a tensile speed of 100 mm / min in an environment of 23 ° C. × 50% RH. Manufactured by Seisakusho, tensile tester Autograph AG-20kNX) was performed, and the amount of change (mm) due to the extension of the sample was measured. As a result, in the obtained SS (Strain-Strength) curve, a tangent line is drawn at the initial rising portion, and the tensile strength when the tangent line corresponds to 100% elongation is expressed as the cross-sectional area of each base film. The value obtained was taken as the tensile elastic modulus (Pa).
　＜粘着シートの曲げ応力＞
　各種粘着シートを、幅６ｍｍ、長さ５０ｍｍに切り出してサンプルとし、このサンプルを支点間距離２５ｍｍの３点曲げ冶具の上に置き、２３℃×５０％ＲＨの環境下で、押し込み速度０．５ｍｍ／ｓｅｃで押し込み試験（ＴＡ　Ｉｎｓｔｒｕｍｅｎｔｓ社製、動的粘弾性計測装置　ＲＳＡ－ＩＩＩ）を行い、当該サンプルを５ｍｍ押し込んだときの荷重（ｇ）を粘着シートの曲げ応力として測定（評価）した。 <Bending stress of adhesive sheet>
Various pressure-sensitive adhesive sheets were cut into a width of 6 mm and a length of 50 mm to form a sample. This sample was placed on a three-point bending jig with a fulcrum distance of 25 mm, and an indentation speed of 0.5 mm in an environment of 23 ° C. × 50% RH An indentation test (manufactured by TA Instruments, dynamic viscoelasticity measuring device RSA-III) was performed at / sec, and the load (g) when the sample was indented 5 mm was measured (evaluated) as the bending stress of the adhesive sheet.
　本発明の粘着シートは、前記粘着シートの曲げ応力（荷重）としては、好ましくは、０．０１～０．２０ｇであり、より好ましくは、０．０３～０．１８ｇであり、更に好ましくは、０．０５～０．１５ｇである。前記粘着シートの曲げ応力（荷重）が前記範囲内であることにより、粘着シートのコシが強すぎず、追従性が良好となり、好ましい態様となる。なお、曲げ応力（荷重）が０．２０ｇを超えると、コシが強くなりすぎ、追従性の低下につながるため、好ましくない。 In the pressure-sensitive adhesive sheet of the present invention, 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. When 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.
　＜粘着シートの垂直下垂距離Ｌ＞
　図１に示すように、２３℃×５０％ＲＨの環境下に３０分間放置した後、得られた粘着シート１を幅５０ｍｍ、長さ１００ｍｍに切断し、長さ方向に５０ｍｍはみ出るように水平な固定台３に粘着シートを構成する粘着剤層表面を貼り付け、粘着シートの上に１００ｇの重り２を置いて動かないように固定した。その後、粘着シートの厚み方向から粘着シートの高さに目線を合わせ、定規を用いて垂直下垂距離Ｌ（ｍｍ）を測定した。測定は、２３℃×５０％ＲＨの環境下で行った。前記垂直下垂距離Ｌが、３０ｍｍ以上であることで、基材フィルムとしてコシが弱いものを使用することになり、湾曲部や凹凸部の様な曲面に貼り合わせた際に、基材フィルムの反発が弱く、追従性が良好となり好ましい。 <Vertical drop distance L of the adhesive sheet>
As shown in FIG. 1, after leaving for 30 minutes in an environment of 23 ° C. × 50% RH, the obtained pressure-sensitive adhesive sheet 1 was cut into a width of 50 mm and a length of 100 mm, and horizontal so as to protrude 50 mm in the length direction. The adhesive layer surface which comprises an adhesive sheet was affixed on the fixing stand 3, and the weight 2 of 100g was put on the adhesive sheet, and it fixed so that it might not move. Thereafter, the line of sight was aligned with the height of the pressure-sensitive adhesive sheet from the thickness direction of the pressure-sensitive adhesive sheet, and the vertical drop distance L (mm) was measured using a ruler. The measurement was performed in an environment of 23 ° C. × 50% RH. When the vertical sag distance L is 30 mm or more, a base film having a weak stiffness is used, and when it is bonded to a curved surface such as a curved part or an uneven part, the base film is repelled. Is weak and good followability is preferable.
　＜低速剥離力の測定＞
　得られた粘着シートを幅５０ｍｍ、長さ１００ｍｍにカットし、被着体であるガラス（松浪硝子工業社製、青板縁磨品(ＯＦ１)）に０．２５ＭＰａ、０．３ｍ／ｍｉｎの速度で粘着シートを構成する粘着剤層表面を貼り合わせ、評価サンプルを作製した。貼り合わせ後、２３℃×５０％ＲＨの環境下に３０分間放置した後、引張試験機（ミネベア社製　引張圧縮試験機　ＴＣＭ－１ｋＮＢ）にて引張速度１ｍｍ／ｍｉｎ（低速）、剥離角度９０度にて剥離力（ｇｆ／５０ｍｍ）を測定した。測定は、２３℃×５０％ＲＨの環境下で行った。前記低速粘着力が３．０ｇｆ／５０ｍｍ以上であることで、湾曲部や凹凸部の様な曲面に貼り合わせても浮きが生じず、密着できる様態となる。 <Measurement of low speed peeling force>
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. × 50% RH for 30 minutes, and then a tensile tester (tensile compression tester TCM-1kNB manufactured by Minebea Co., Ltd.) with a tensile speed of 1 mm / min (low speed) and a peeling angle of 90 degrees. The peel force (gf / 50 mm) was measured at. The measurement was performed in an environment of 23 ° C. × 50% RH. When the low-speed adhesive force is 3.0 gf / 50 mm or more, even when pasted on a curved surface such as a curved portion or a concavo-convex portion, the low-pressure adhesive force does not occur and can be in close contact.
　＜湾曲部への追従性＞
　長辺１２０ｍｍ、短辺６５ｍｍ、厚み０．５５ｍｍで、端部が曲率半径Ｒ＝５ｍｍで高さ方向に２ｍｍ湾曲(下向き)している湾曲ガラス（日本板硝子社製）を用いて、湾曲部への追従性の評価を行った。
　まず、得られた粘着シートを湾曲ガラスと同じ大きさに切り出しサンプルとした後、２３℃×５０％ＲＨの環境下にて、当該サンプルをハンドローラーにて貼りつけ、湾曲ガラスの湾曲部分まで密着するか、目視にて観察し、以下の基準で評価した。
　(評価基準)
　○：湾曲部で浮きが生じず貼り合せできた場合。
　×：湾曲部で浮きが生じた場合。 <Followability to curved part>
Using curved glass (manufactured by Nippon Sheet Glass Co., Ltd.) that has a long side of 120 mm, a short side of 65 mm, a thickness of 0.55 mm, and a radius of curvature of R = 5 mm and 2 mm in the height direction (downward). The following ability was evaluated.
First, the obtained pressure-sensitive adhesive sheet was cut out to the same size as the curved glass and used as a sample, and then the sample was attached with a hand roller in an environment of 23 ° C. × 50% RH, and adhered to the curved portion of the curved glass. Or visually observed and evaluated according to the following criteria.
(Evaluation criteria)
◯: When the curved portion can be bonded without causing a lift.
X: When a float arises in a curved part.
　＜外観（凹み・ゲル物の有無）＞
　得られた粘着シートを構成する基材フィルムの表面を目視にて観察するため、得られた粘着シートの縦１０ｃｍ×横１０ｃｍの観察範囲内の欠点（凹み及びゲル物）の個数を測定し、以下の基準で評価した。
　欠点個数が０～５０個：外観が良好である（○）。
　欠点個数が５１個以上：外観が悪い（×）。 <Appearance (existence of dents / gels)>
In order to visually observe the surface of the base film constituting the obtained pressure-sensitive adhesive sheet, the number of defects (dents and gels) within the observation range of 10 cm in length × 10 cm in width of the obtained pressure-sensitive adhesive sheet is measured, Evaluation was made according to the following criteria.
Number of defects: 0 to 50: Good appearance (◯).
The number of defects is 51 or more: The appearance is poor (x).
　＜（メタ）アクリル系ポリマー（Ａ）の調整＞
　攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つロフラスコに、２－エチルヘキシルアクリレート（２ＥＨＡ）５４重量部、酢酸ビニル（ＶＡｃ）４３重量部、アクリル酸（ＡＡ）３重量部、重合開始剤として２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）０．２重量部、トルエン１８６量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を６３℃付近に保って約４時間重合反応を行い、（メタ）アクリル系ポリマー（Ａ）溶液（約３５重量％）を調製した。前記（メタ）アクリル系ポリマー（Ａ）の重量平均分子量（Ｍｗ）は４７万であり、ガラス転移温度（Ｔｇ）は－２１℃であった。 <Preparation of (meth) acrylic polymer (A)>
In a four-flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a condenser, 54 parts by weight of 2-ethylhexyl acrylate (2EHA), 43 parts by weight of vinyl acetate (VAc), 3 parts by weight of acrylic acid (AA), As a polymerization initiator, 0.2 part by weight of 2,2′-azobisisobutyronitrile (AIBN) and 186 parts by weight of toluene were charged, nitrogen gas was introduced while gently stirring, and the liquid temperature in the flask was 63 ° 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.
　＜（メタ）アクリル系ポリマー（Ｂ）の調製＞
　攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに、ブチルアクリレート（ＢＡ）９５重量部、アクリル酸（ＡＡ）５重量部、重合開始剤として２，２’－アゾビスイソブチロニトリル０．１重量部、酢酸エチル２３４重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を６５℃付近に保って６時間重合反応を行い、（メタ）アクリル系ポリマー（Ｂ）溶液（約３０重量％）を調製した。前記（メタ）アクリル系ポリマー（Ｂ）の重量平均分子量（Ｍｗ）は、６０万であり、ガラス転移温度（Ｔｇ）は、－４７℃であった。 <Preparation of (meth) acrylic polymer (B)>
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 95 parts by weight of butyl acrylate (BA), 5 parts by weight of acrylic acid (AA), and 2,2′-azo as a polymerization initiator Charge 0.1 parts by weight of bisisobutyronitrile and 234 parts by weight of ethyl acetate, introduce nitrogen gas while gently stirring, and perform a polymerization reaction for 6 hours while maintaining the liquid temperature in the flask at around 65 ° C. ( A (meth) acrylic polymer (B) solution (about 30% by weight) was prepared. The (meth) acrylic polymer (B) had a weight average molecular weight (Mw) of 600,000 and a glass transition temperature (Tg) of −47 ° C.
　＜（メタ）アクリル系ポリマー（Ｃ）の調整＞
　攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに、ブチルアクリレート（ＢＡ）９０重量部、アクリル酸（ＡＡ）１０重量部、重合開始剤として２，２’－アゾビスイソブチロニトリル０．１重量部、酢酸エチル２３４重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を６５℃付近に保って６時間重合反応を行い、（メタ）アクリル系ポリマー（Ｃ）溶液（約３０重量％）を調製した。前記（メタ）アクリル系ポリマー（Ｃ）の重量平均分子量（Ｍｗ）は、６１万であり、ガラス転移温度（Ｔｇ）は、－４０℃であった。 <Preparation of (meth) acrylic polymer (C)>
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 90 parts by weight of butyl acrylate (BA), 10 parts by weight of acrylic acid (AA), and 2,2′-azo as a polymerization initiator Charge 0.1 parts by weight of bisisobutyronitrile and 234 parts by weight of ethyl acetate, introduce nitrogen gas while gently stirring, and perform a polymerization reaction for 6 hours while maintaining the liquid temperature in the flask at around 65 ° C. ( A (meth) acrylic polymer (C) solution (about 30% by weight) was prepared. The (meth) acrylic polymer (C) had a weight average molecular weight (Mw) of 610,000 and a glass transition temperature (Tg) of −40 ° C.
　＜（メタ）アクリル系ポリマー（Ｄ）の調製＞
　攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つロフラスコに、２－エチルヘキシルアクリレート（２ＥＨＡ）９６重量部、２－ヒドロキシエチルアクリレート（ＨＥＡ）４重量部、重合開始剤として２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）０．２重量部、酢酸エチル２０５重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を６３℃付近に保って約４時間重合反応を行い、（メタ）アクリル系ポリマー（Ｄ）溶液（約３５重量％）を調製した。前記（メタ）アクリル系ポリマー（Ｄ）の重量平均分子量（Ｍｗ）は６５万であり、ガラス転移温度（Ｔｇ）は－６８℃であった。 <Preparation of (meth) acrylic polymer (D)>
Into a four-flask equipped with a stirring blade, thermometer, nitrogen gas inlet tube and condenser, 96 parts by weight of 2-ethylhexyl acrylate (2EHA), 4 parts by weight of 2-hydroxyethyl acrylate (HEA), 2, Charge 0.2 'part of 2'-azobisisobutyronitrile (AIBN) and 205 parts by weight of ethyl acetate, introduce nitrogen gas with gentle stirring, and keep the liquid temperature in the flask at about 63 ° C. A polymerization reaction was carried out for 4 hours to prepare a (meth) acrylic polymer (D) solution (about 35% by weight). The (meth) acrylic polymer (D) had a weight average molecular weight (Mw) of 650,000 and a glass transition temperature (Tg) of −68 ° C.
　〔アクリル系粘着剤（１）溶液の調製〕
　上記（メタ）アクリル系ポリマー（Ａ）溶液（約３５重量％）の固形分１００重量部に、架橋剤として、エポキシ系架橋剤（１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、エポキシ当量：１１０、官能基数：４、商品名「ＴＥＴＲＡＤ－Ｃ」：Ｔ／Ｃ、三菱ガス化学社製）２重量部を加えて、２５℃付近に保って約１分間混合攪拌を行い、アクリル系粘着剤（１）溶液を調製した。 [Preparation of 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.
　〔アクリル系粘着剤（２）溶液の調製〕
　上記（メタ）アクリル系ポリマー（Ａ）溶液（３５重量％）の固形分１００重量部に、架橋剤として、エポキシ系架橋剤（１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、エポキシ当量：１１０、官能基数：４、商品名「ＴＥＴＲＡＤ－Ｃ」：Ｔ／Ｃ、三菱ガス化学社製）１０重量部を加えて、２５℃付近に保って約１分間混合攪拌を行い、アクリル系粘着剤（２）溶液を調製した。 [Preparation of 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.
　〔アクリル系粘着剤（３）溶液の調製〕
　上記（メタ）アクリル系ポリマー（Ｂ）溶液（３０重量％）の固形分１００重量部に、架橋剤として、エポキシ系架橋剤（１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、エポキシ当量：１１０、官能基数：４、商品名「ＴＥＴＲＡＤ－Ｃ」：Ｔ／Ｃ、三菱ガス化学社製）６重量部を加えて、２５℃付近に保って約１分間混合攪拌を行い、アクリル系粘着剤（３）溶液を調製した。 [Preparation of 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.
　〔アクリル系粘着剤（４）溶液の調製〕
　上記（メタ）アクリル系ポリマー（Ｃ）溶液（３０重量％）の固形分１００重量部に、架橋剤として、エポキシ系架橋剤（１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、エポキシ当量：１１０、官能基数：４、商品名「ＴＥＴＲＡＤ－Ｃ」：Ｔ／Ｃ、三菱ガス化学社製）１１重量部を加えて、２５℃付近に保って約１分間混合攪拌を行い、アクリル系粘着剤（４）溶液を調製した。 [Preparation of 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.
　〔アクリル系粘着剤（５）溶液の調製〕
　上記（メタ）アクリル系ポリマー（Ｄ）溶液（３０重量％）の固形分１００重量部に、架橋剤として、イソシアネート系架橋剤（トリメチロールプロパン／トリレンジイソシアネート３量体付加物、商品名「コロネートＬ」：Ｃ／Ｌ、東ソー社製）４重量部、架橋触媒として、ジラウリン酸ジブチルスズ（東京ファインケミカル社製、商品名：エンビライザーＯＬ－１、表３中の「Ｓｎ」、０．５重量％酢酸エチル溶液）：０．０１５重量部を加えて、２５℃付近に保って約１分間混合攪拌を行い、アクリル系粘着剤（５）溶液を調製した。 [Preparation of 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.
　〔ウレタン系粘着剤（６）溶液の調製〕
　ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１(旭硝子社製、Ｍｎ＝１００００）１００重量部、架橋剤として、３官能イソシアネート化合物であるヘキサメチレンジイソシアネートのアダクト体（コロネートＨＬ：Ｃ／ＨＬ、東ソー社製)７．４重量部、触媒として、鉄（ＩＩＩ)アセチルアセトナート(トリス（アセチルアセトナト）鉄、表４中の「Ｆｅ」、東京化成工業社製)０．１２重量部、酸化防止剤としてＩｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、希釈溶剤として酢酸エチル２１０重量部を加えて、２５℃付近に保って約１分間混合攪拌を行い、ウレタン系粘着剤（６）溶液を得た。 [Preparation of urethane-based adhesive (6) solution]
As a polyol, 100 parts by weight of preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000), which is a polyol having three hydroxyl groups, and as a crosslinking agent, an adduct of hexamethylene diisocyanate, which is a trifunctional isocyanate compound (Coronate HL: C / HL). 7.4 parts by weight, manufactured by Tosoh Corporation), as a catalyst, iron (III) acetylacetonate (tris (acetylacetonato) iron, "Fe" in Table 4, Tokyo Chemical Industry Co., Ltd.) 0.12 parts by weight, Add 0.5 parts by weight of Irganox 1010 (manufactured by BASF) as an antioxidant and 210 parts by weight of ethyl acetate as a diluent solvent, and mix and stir for about 1 minute while maintaining at around 25 ° C. to obtain a urethane-based adhesive (6) solution Got.
　〔シリコーン系粘着剤（７）溶液の調製〕
　シリコーン系粘着剤として、シリコーン系ポリマーであるＳＤ４５８７　Ｌ　ＰＳＡ (固形分４０重量％、東レ・ダウコーニング社製）を固形分で１００重量部、触媒として、ＮＸ－３５　Ｃａｔａｌｙｓｔ(東レ・ダウコーニング社製)０．５重量部、希釈溶剤としてトルエン１００重量部を加えて、２５℃付近に保って約１分間混合攪拌を行い、シリコーン系粘着剤（７）溶液を得た。 [Preparation of Silicone Adhesive (7) Solution]
SD4587 L PSA (solid content 40% by weight, manufactured by Toray Dow Corning) as a silicone-based adhesive is 100 parts by weight in solid content, and NX-35 Catalyst (manufactured by Toray Dow Corning) as a catalyst. ) 0.5 parts by weight and 100 parts by weight of toluene as a diluent solvent were added, and the mixture was stirred at about 25 ° C. for about 1 minute to obtain a silicone-based pressure-sensitive adhesive (7) solution.
　＜実施例１＞
　上記アクリル系粘着剤溶液（１）を、基材フィルムＩ（ポリエチレンテレフタラート、厚み；１９μｍ、引張弾性率：１．２×１０９Ｐａ、商品名：ダイアホイルＴ１００－１９Ｂ：三菱ケミカル社製）に塗布し、１３０℃で２分間加熱して、厚さ１０μｍの粘着剤層を形成し、粘着シートを作製した。 <Example 1>
The acrylic pressure-sensitive adhesive solution (1) was converted into a base film I (polyethylene terephthalate, thickness: 19 μm, 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 μm, thereby preparing a pressure-sensitive adhesive sheet.
　＜実施例２～４＞
　表６に示すように、実施例１で用いたアクリル系粘着剤（１）溶液の代わりに、アクリル系粘着剤（２）～（４）溶液を使用したこと以外は、実施例１と同様の方法で、粘着シートを作製した。 <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.
　＜実施例５＞
　表６に示すように、実施例１で用いた基材フィルムの代わりに、基材フィルムＩＩ（ポリエチレンテレフタラート、厚み；１２μｍ、引張弾性率：１．０×１０９Ｐａ、商品名：ルミラー＃１２Ｓ１０：東レ社製）を使用したこと以外は、実施例１と同様の方法で、加熱条件等や得られる粘着剤層の厚みを調整した粘着シートを作製した。 <Example 5>
As shown in Table 6, instead of the base film used in Example 1, base film II (polyethylene terephthalate, thickness: 12 μm, 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.
　＜実施例６＞
　表６に示すように、実施例１で用いた基材フィルムの代わりに、基材フィルムＩＩＩ（ポリエチレンテレフタラート、厚み；２５μｍ、引張弾性率：７．０×１０８Ｐａ、商品名：ＥＳＲ：大蔵工業社製）を使用したこと以外は、実施例１と同様の方法で、加熱条件等や得られる粘着剤層の厚みを調整した粘着シートを作製した。 <Example 6>
As shown in Table 6, instead of the base film used in Example 1, the base film III (polyethylene terephthalate, thickness: 25 μm, 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.
　＜実施例７及び８＞
　表６に示すように、実施例１で用いたアクリル系粘着剤（１）溶液の代わりに、ウレタン系粘着剤（６）溶液、又は、シリコーン系粘着剤（７）溶液を使用したこと以外は、実施例１と同様の方法で、加熱条件等や得られる粘着剤層の厚みを調整した粘着シートを作製した。 <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.
　＜比較例１＞
　表６に示すように、実施例１で用いた基材フィルムの代わりに、基材フィルムＩＶ（ポリエチレンテレフタラート、厚み；３８μｍ、引張弾性率：２．０×１０９Ｐａ、商品名：ダイアホイルＴ１００Ｃ－３８：三菱ケミカル社製）を使用したこと以外は、実施例１と同様の方法で、加熱条件等や得られる粘着剤層の厚みを調整した粘着シートを作製した。 <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 μm, 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.
　＜比較例２＞
　シリコーン系離形処理が塗布された３８μｍのポリエチレンテレフタラートフィルムに、アクリル系粘着剤（１）溶液を塗布し、１３０℃で２分間乾燥させ、粘着剤層を得た。その後、基材フィルムＶ（無延伸ポリプロピレン、厚み；４０μｍ、引張弾性率：４．５×１０８Ｐａ、商品名：ＭＫ－１２：サン・トックス社製）に得られた粘着剤層を貼り合せ（転写し）、粘着シートを得た。 <Comparative Example 2>
An acrylic pressure-sensitive adhesive (1) solution was applied to a 38 μm 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 μm, tensile modulus: 4.5 × 10 8 Pa, trade name: MK-12: manufactured by Sun Tox Corporation) (Transfer) to obtain an adhesive sheet.
　＜比較例３＞
　表６に示すように、実施例１で用いたアクリル系粘着剤（１）溶液の代わりに、アクリル系粘着剤（５）溶液を使用したこと以外は、実施例１と同様の方法で、加熱条件等や得られる粘着剤層の厚みを調整した粘着シートを作製した。 <Comparative 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.
　実施例及び比較例に係る粘着シートつき、上述した配合内容、各種測定および評価を行った結果を、表１～表６に示した。なお、表中の配合量は有効成分を示す。また、粘着剤層の厚みは、実施例１と同様に、実施例及び比較例のすべてが、１０μｍになるように調製した。 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. In addition, the compounding quantity in a table | surface shows an active ingredient. Moreover, 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 μm.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000003
  
Figure JPOXMLDOC01-appb-T000003
  
Figure JPOXMLDOC01-appb-T000004
  
Figure JPOXMLDOC01-appb-T000004
  
Figure JPOXMLDOC01-appb-T000005
  
Figure JPOXMLDOC01-appb-T000005
  
Figure JPOXMLDOC01-appb-T000006
  
Figure JPOXMLDOC01-appb-T000006
  
　上記表６より、全ての実施例において、粘着シートの垂直下垂距離Ｌは３０ｍｍ以上であり、低速剥離力も所望の範囲に含まれ、粘着シートの曲げ応力や湾曲部（曲面）への追従性も良好であることが確認できた。併せて基材フィルムの外観も良好であった。 From Table 6 above, in all Examples, 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, and 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.
　一方、比較例１では、垂直下垂距離Ｌが３０ｍｍ未満となり、粘着シートの曲げ応力も劣り、湾曲部への追従性が悪化した。比較例２では、ポリオレフィン系フィルムである無延伸ポリプロピレンフィルムを使用したため、外観不良が確認された。比較例３では、垂直下垂距離Ｌは３０ｍｍ以上であったが、低速剥離力が３．０ｇｆ／５０ｍｍ未満であり、湾曲部への追従性が不良であることが確認された。 On the other hand, in 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. In Comparative Example 2, since an unstretched polypropylene film, which is a polyolefin film, was used, poor appearance was confirmed. In 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.
　ここに開示される粘着シートは、液晶ディスプレイパネル、プラズマディスプレイパネル（ＰＤＰ）、有機エレクトロルミネッセンス（ＥＬ）ディスプレイ等の構成要素として用いられる光学部材、光学部材を含む表示装置などの製造時、搬送時等に該光学部材を保護するための表面保護フィルムとして好適である。 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.
　１：粘着シート（表面保護フィルム）
　２：重り
　３：固定台
　Ｌ：垂直下垂距離 1: Adhesive sheet (surface protective film)
2: Weight 3: Fixed base L: Vertical drop distance

Claims (6)

  1. 　基材フィルムの片面又は両面に粘着剤組成物から形成された粘着剤層を有する粘着シートにおいて、
    　前記基材フィルムが、非ポリオレフィン系フィルムであり、
    　前記粘着シートを幅５０ｍｍ、長さ１００ｍｍに切断し、長さ方向に５０ｍｍはみ出るように、水平な台に固定したときの、垂直下垂距離Ｌが、３０ｍｍ以上であり、
    　前記粘着剤層表面をガラスに貼り合せ、９０度方向に剥離速度１ｍｍ／ｍｉｎで引っ張った際の剥離力が、３．０ｇｆ／５０ｍｍ以上であることを特徴とする粘着シート。     In the pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition on one side or both sides of the base film,
    The base film is a non-polyolefin film,
    When the pressure-sensitive adhesive sheet is cut to 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 vertical droop distance L is 30 mm or more,
    A pressure-sensitive adhesive sheet having a peeling force of 3.0 gf / 50 mm or more when the pressure-sensitive adhesive layer surface is bonded to glass and pulled in a 90 ° direction at a peeling speed of 1 mm / min.
  2. 　前記粘着剤層が、アクリル系粘着剤、ウレタン系粘着剤、及び、シリコーン系粘着剤から選択される少なくとも１種を含有する粘着剤組成物から形成されることを特徴とする請求項１に記載の粘着シート。 The pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing at least one selected from an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive. Adhesive sheet.
  3. 　前記非ポリオレフィン系フィルムの引張弾性率が、１．５×１０９Ｐａ未満であることを特徴とする請求項１又は２に粘着シート。 The pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the non-polyolefin film has a tensile elastic modulus of less than 1.5 x 10 9 Pa.
  4. 　前記非ポリオレフィン系フィルムが、ポリエステルフィルムであることを特徴とする請求項１～３のいずれかに記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the non-polyolefin film is a polyester film.
  5. 　請求項１～４のいずれかに記載の粘着シートにより保護されることを特徴とする光学部材。 An optical member protected by the adhesive sheet according to any one of claims 1 to 4.
  6. 　請求項１～４のいずれかに記載の粘着シートにより保護されることを特徴とする表示装置。 A display device protected by the adhesive sheet according to any one of claims 1 to 4.
PCT/JP2019/002924 2018-02-09 2019-01-29 Adhesive sheet, optical member, and display device WO2019155939A1 (en)

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JPH06346032A (en) * 1993-06-11 1994-12-20 Sekisui Chem Co Ltd Double-side tacky tape
JPH08302304A (en) * 1995-05-15 1996-11-19 Sekisui Chem Co Ltd Plasticizer-resistant, pressure-sensitive adhesive double coated tape
JP2002003799A (en) * 2000-06-27 2002-01-09 Nitto Denko Corp Adhesive sheets
JP2009074060A (en) * 2007-08-24 2009-04-09 Nitto Denko Corp Double face self-adhesive sheet for fixation of hard disk drive component and hard disk drive
JP2012131976A (en) * 2010-11-30 2012-07-12 Nitto Denko Corp Surface protection sheet
JP2013020726A (en) * 2011-07-07 2013-01-31 Nitto Denko Corp Coating material for rectangular copper wire, coated rectangular copper wire and electrical apparatus
JP2014198830A (en) * 2013-03-29 2014-10-23 日東電工株式会社 Adhesive tape for electrochemical device
JP2018159054A (en) * 2017-03-22 2018-10-11 日東電工株式会社 Surface protective film

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06346032A (en) * 1993-06-11 1994-12-20 Sekisui Chem Co Ltd Double-side tacky tape
JPH08302304A (en) * 1995-05-15 1996-11-19 Sekisui Chem Co Ltd Plasticizer-resistant, pressure-sensitive adhesive double coated tape
JP2002003799A (en) * 2000-06-27 2002-01-09 Nitto Denko Corp Adhesive sheets
JP2009074060A (en) * 2007-08-24 2009-04-09 Nitto Denko Corp Double face self-adhesive sheet for fixation of hard disk drive component and hard disk drive
JP2012131976A (en) * 2010-11-30 2012-07-12 Nitto Denko Corp Surface protection sheet
JP2013020726A (en) * 2011-07-07 2013-01-31 Nitto Denko Corp Coating material for rectangular copper wire, coated rectangular copper wire and electrical apparatus
JP2014198830A (en) * 2013-03-29 2014-10-23 日東電工株式会社 Adhesive tape for electrochemical device
JP2018159054A (en) * 2017-03-22 2018-10-11 日東電工株式会社 Surface protective film

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