WO2024106156A1 - Laminate - Google Patents

Laminate Download PDF

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Publication number
WO2024106156A1
WO2024106156A1 PCT/JP2023/038599 JP2023038599W WO2024106156A1 WO 2024106156 A1 WO2024106156 A1 WO 2024106156A1 JP 2023038599 W JP2023038599 W JP 2023038599W WO 2024106156 A1 WO2024106156 A1 WO 2024106156A1
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WIPO (PCT)
Prior art keywords
weight
adherend
acrylate
film
meth
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Application number
PCT/JP2023/038599
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French (fr)
Japanese (ja)
Inventor
和也 浦上
圭太 小川
尚樹 橋本
貴之 足立
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日東電工株式会社
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Publication of WO2024106156A1 publication Critical patent/WO2024106156A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a laminate.
  • a surface protection film is provided on the surface of an optical component for the purposes of surface protection and impact resistance.
  • Typical surface protection films include those that are temporarily attached during the assembly, processing, transportation, etc. of a device before use and are peeled off again before the device is used (those used as process materials), and those that remain attached to the device surface even when the device is in use (those intended for permanent adhesion) (see, for example, Patent Document 1).
  • Surface protection films used as processing materials and surface protection films intended for permanent adhesion both have an adhesive layer on the main surface of the film substrate, and are attached to the surface of the adherend to be protected via this adhesive layer (see, for example, Patent Document 2).
  • Laminates that have a laminated structure in which an optical component or the like is used as an adherend and a pressure-sensitive adhesive layer of a surface protection film is bonded to the adherend have traditionally had the following problems:
  • Patent No. 3518677 Japanese Patent No. 6249617
  • the object of the present invention is to provide a laminate including a surface protection film and an adherend that is unlikely to leave traces of deformation due to deformation caused by external forces, has an appropriate initial peel strength of the surface protection film from the adherend, and exhibits little change over time in the peel strength of the surface protection film from the adherend.
  • the arithmetic mean surface roughness Ra may be 0.1 ⁇ m or less.
  • the creep recovery value may be 99% or more.
  • the shear modulus G may be 30.0 N/50 mm3 or less .
  • the present invention can provide a laminate including a surface protective film and an adherend that is less likely to leave traces of deformation due to deformation caused by external forces, has an appropriate initial peel strength of the surface protective film from the adherend, and exhibits little change over time in the peel strength of the surface protective film from the adherend.
  • weight Whenever the term “weight” appears in this specification, it may be read as “mass,” which is the commonly used SI unit for indicating weight.
  • (meth)acrylic means “acrylic and/or methacrylic
  • the term “(meth)acrylate” means “acrylate and/or methacrylate
  • the term “(meth)allyl” means “allyl and/or methallyl”
  • the term “(meth)acrolein” means "acrolein and/or methacrolein”.
  • the laminate according to an embodiment of the present invention includes a surface protection film and an adherend.
  • the surface protection film has a substrate and an adhesive layer.
  • the adhesive layer and the adherend are directly laminated together.
  • FIG. 1 shows one embodiment of the laminate of the present invention, where the laminate 1000 includes a surface protective film 100 and an adherend 200, and the surface protective film 100 has a substrate 10 and an adhesive layer 20. The adhesive layer 20 and the adherend 200 are directly laminated together.
  • the laminate according to the embodiment of the present invention may contain any other appropriate layers as long as the effects of the present invention are not impaired, so long as the laminate contains a surface protective film and an adherend.
  • Examples of such other layers include glass, a display, an imaging device, a lens, and a (half) mirror.
  • the total thickness of the laminate according to the embodiment of the present invention can be set appropriately depending on the type of adherend and the types of other layers that may be included.
  • the total thickness of the laminate according to the embodiment of the present invention is preferably 10 ⁇ m to 1000 ⁇ m, more preferably 25 ⁇ m to 800 ⁇ m, even more preferably 40 ⁇ m to 600 ⁇ m, and particularly preferably 50 ⁇ m to 500 ⁇ m.
  • the water contact angle of the surface of the adherend on the surface protection film side is preferably 85° or more, more preferably 85° to 110°, even more preferably 85° to 105°, even more preferably 90° to 100°, particularly preferably 95° to 100°, and most preferably 95° to 99°. If the water contact angle is within the above range, the effects of the present invention can be more effectively achieved.
  • the surface protection film is likely to adhere excessively to the adherend, and for example, the initial peeling force of the surface protection film from the adherend may become too high, making it impossible to peel the surface protection film from the adherend, or the peeling force of the surface protection film from the adherend may increase too much over time, making it impossible to peel the surface protection film from the adherend.
  • the surface protection film will not adhere too closely to the adherend, and for example, the initial peel strength of the surface protection film from the adherend will be too low, which may cause the surface protection film to lift off from the adherend, or when peeling off a release liner provided on the side of the adherend opposite the surface protection film (i.e., the release liner in a laminated structure of release liner/adherend/surface protection film), peeling will occur at the interface between the surface protection film and the adherend rather than at the interface between the adherend and the release liner, resulting in poor peeling (peeling at an unintended location).
  • the arithmetic mean surface roughness Ra of the surface of the adherend on the surface protection film side is preferably 0.6 ⁇ m or less, more preferably 0.35 ⁇ m or less, even more preferably 0.2 ⁇ m or less, particularly preferably 0.1 ⁇ m or less, and most preferably 0.08 ⁇ m or less.
  • the lower limit of the arithmetic mean surface roughness Ra is preferably as small as possible, and is preferably 0 ⁇ m or more. If the arithmetic mean surface roughness Ra is within the above range, the effect of the present invention can be more effectively achieved.
  • the arithmetic mean surface roughness Ra is too large outside the above range, for example, if the thickness of the adhesive layer of the surface protection film is large, the peeling force of the surface protection film from the adherend increases too much over time, and it may become impossible to peel the surface protection film from the adherend.
  • the creep recovery value of the adhesive layer of the surface protection film is preferably 96% or more, more preferably 97% or more, even more preferably 98% or more, and particularly preferably 99% or more. If the creep recovery value is within the above range, the effects of the present invention can be more effectively achieved. If the creep recovery value is too small outside the above range, there is a risk that deformation marks due to deformation caused by external forces will be more likely to remain.
  • the shear modulus G of the surface protective film is preferably 39.0 N/50 mm 3 or less, more preferably 27.0 N/50 mm 3 to 39.0 N/50 mm 3 , even more preferably 27.5 N/50 mm 3 to 38.5 N/50 mm 3 , and particularly preferably 28.0 N/50 mm 3 to 38.0 N/50 mm 3. If the shear modulus G is within the above range, the effects of the present invention can be more effectively achieved. If the shear modulus G is outside the above range, there is a risk that deformation marks due to deformation caused by external force will be easily left.
  • the thickness of the adhesive layer of the surface protection film is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, even more preferably 10 ⁇ m or more, particularly preferably 15 ⁇ m or more, and most preferably 18 ⁇ m or more.
  • the upper limit of the thickness of the adhesive layer is preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, even more preferably 80 ⁇ m or less, particularly preferably 50 ⁇ m or less, and most preferably 30 ⁇ m or less. If the thickness of the adhesive layer is within the above range, the effects of the present invention can be more effectively achieved.
  • the thickness of the adhesive layer is too small outside the above range, there is a risk that deformation marks due to deformation caused by external forces will be easily left. If the thickness of the adhesive layer is too large outside the above range, there is a risk that it will not be possible to apply it to thin devices, such as when the adherend is an optical member.
  • the surface protection film has a substrate and a pressure-sensitive adhesive layer.
  • One embodiment of the surface protection film is made of a substrate and a pressure-sensitive adhesive layer (for example, as shown in FIG. 1, a surface protection film 100 is made of a substrate 10 and a pressure-sensitive adhesive layer 20).
  • the surface protection film may have any other appropriate layers other than the substrate and the adhesive layer, as long as the effects of the present invention are not impaired.
  • Such other layers include, for example, an easy-adhesion layer, an easy-slip layer, an anti-blocking layer, an antistatic layer, an anti-reflection layer, an anti-oligomer layer, and a release liner provided on the surface of the adhesive layer opposite the substrate.
  • the components of the surface protection film may contain any appropriate additives as long as they do not impair the effects of the present invention.
  • additives include antioxidants, UV absorbers, light stabilizers, nucleating agents, fillers, pigments, surfactants, and antistatic agents.
  • a release liner may be provided on the side of the adhesive layer opposite the substrate for protection etc. until it is laminated with the adherend.
  • release liners include release liners in which the surface of a substrate (liner substrate) such as paper or plastic film is silicone-treated, and release liners in which the surface of a substrate (liner substrate) such as paper or plastic film is laminated with a polyolefin resin.
  • plastic films that can be used as liner substrates include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene-vinyl acetate copolymer film.
  • the thickness of the release liner is preferably 1 ⁇ m to 500 ⁇ m, more preferably 3 ⁇ m to 450 ⁇ m, even more preferably 5 ⁇ m to 400 ⁇ m, and particularly preferably 10 ⁇ m to 300 ⁇ m.
  • the substrate may be a substrate made of one layer, or a substrate made of a laminated structure of two or more layers.
  • the thickness of the substrate may be any appropriate thickness as long as it does not impair the effects of the present invention.
  • the thickness of the substrate is preferably 5 ⁇ m to 1000 ⁇ m, more preferably 10 ⁇ m to 800 ⁇ m, even more preferably 20 ⁇ m to 600 ⁇ m, and particularly preferably 30 ⁇ m to 400 ⁇ m.
  • any suitable material may be used as the material for the substrate, provided that the effect of the present invention is not impaired.
  • a material is preferably plastic.
  • any suitable plastic may be used as the plastic as long as it does not impair the effects of the present invention.
  • a preferable example of such a plastic is a thermoplastic resin.
  • thermoplastic resins include polyester, acrylic resins, urethane resins, polycarbonate, triacetyl cellulose (TAC), polyolefins (olefin homopolymers, copolymers of olefins and other monomers), polyamides (nylons), wholly aromatic polyamides (aramids), polyimides (PI), polyvinyl chloride (PVC), polyvinyl acetate, and cyclic olefin polymers.
  • TAC triacetyl cellulose
  • polyolefins olefin homopolymers, copolymers of olefins and other monomers
  • polyamides nylons
  • Armids wholly aromatic polyamides
  • PI polyimides
  • PVC polyvinyl chloride
  • PV acetate polyvinyl acetate
  • cyclic olefin polymers examples include polyester, acrylic resins, urethane resins, polycarbonate, triacetyl cellulose (TAC),
  • polyester is preferred in that it can better bring out the effects of the present invention.
  • polyester include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT), and polyethylene terephthalate (PET) is preferred in that it can better bring out the effects of the present invention.
  • the pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer consisting of a single layer, or may be a pressure-sensitive adhesive layer consisting of a laminated structure of two or more layers.
  • the thickness of the adhesive layer is as described above.
  • the adhesive constituting the adhesive layer is preferably at least one type selected from the group consisting of acrylic adhesives, urethane adhesives, and silicone adhesives.
  • the adhesive layer is more preferably composed of an acrylic adhesive.
  • the acrylic adhesive is formed from an acrylic adhesive composition.
  • an acrylic adhesive can be defined as something formed from an acrylic adhesive composition. This is because an acrylic adhesive becomes an acrylic adhesive when an acrylic adhesive composition undergoes a crosslinking reaction due to heating or exposure to ultraviolet light, making it impossible to directly identify an acrylic adhesive by its structure, and there are circumstances that make it impractical to do so ("impossible/impractical circumstances"). Therefore, the definition of "something formed from an acrylic adhesive composition" appropriately identifies an acrylic adhesive as a "thing.”
  • the adhesive layer may be formed by any suitable method. Examples of such methods include a method in which an adhesive composition that forms the adhesive constituting the adhesive layer is applied to any suitable substrate, and heated or dried as necessary, and cured as necessary to form an adhesive layer on the substrate; and a method in which an adhesive composition that forms the adhesive constituting the adhesive layer is applied to a film such as any suitable release liner, and heated or dried as necessary, and cured as necessary to form an adhesive layer on the film, and an adhesive layer is formed on the substrate by laminating and transferring any suitable substrate onto the adhesive layer.
  • Any appropriate means may be used to apply the acrylic adhesive composition as long as it does not impair the effects of the present invention.
  • application means include roll coating, gravure roll coating, reverse roll coating, kiss roll coating, dip roll coating, bar coating, roll brush coating, spray coating, knife coating, air knife coating, comma coating, direct coating, and die coating.
  • heating or drying the acrylic adhesive composition may be any appropriate means as long as it does not impair the effects of the present invention.
  • Such heating or drying means include, for example, heating to 60°C to 180°C, or performing an aging treatment at a temperature around room temperature.
  • Any suitable means may be used to cure the acrylic adhesive composition as long as it does not impair the effects of the present invention.
  • curing means include heat, ultraviolet radiation, laser radiation, alpha radiation, beta radiation, gamma radiation, X-ray radiation, and electron beam radiation.
  • the acrylic adhesive composition preferably contains an acrylic polymer, which can further enhance the effects of the present invention.
  • the acrylic polymer may be referred to as a so-called base polymer in the field of acrylic pressure-sensitive adhesives.
  • the acrylic polymer may be one type only, or two or more types may be used.
  • a preferred embodiment of the adhesive layer is one in which the adhesive layer is composed of an acrylic adhesive formed from an acrylic adhesive composition, and the acrylic adhesive composition contains an acrylic polymer as a base polymer.
  • the content of the acrylic polymer in the acrylic adhesive composition is preferably 60% by weight to 99.9% by weight, more preferably 65% by weight to 99.9% by weight, even more preferably 70% by weight to 99.9% by weight, particularly preferably 75% by weight to 99.9% by weight, and most preferably 80% by weight to 99.9% by weight, calculated as solid content.
  • Any suitable acrylic polymer may be used as the acrylic polymer as long as it does not impair the effects of the present invention.
  • the weight average molecular weight of the acrylic polymer is preferably 300,000 to 2,000,000, more preferably 350,000 to 1,500,000, even more preferably 400,000 to 1,000,000, and particularly preferably 500,000 to 1,000,000, in order to better express the effects of the present invention. If the weight average molecular weight is too low, there is a tendency for a large amount of low molecular weight components to be included, which may cause plastic deformation of the low molecular weight components, and there is a risk that deformation marks due to deformation caused by external forces may be easily left behind.
  • a preferred embodiment of the acrylic polymer is an acrylic polymer prepared by solution polymerization using a polymerization initiator.
  • a method of polymerization using a polymerization initiator any appropriate method, such as a conventionally known method, may be adopted as long as it does not impair the effects of the present invention.
  • the acrylic polymer is obtained by polymerizing the monomer component (M).
  • the monomer component (M) does not include the crosslinking agent, which may be contained in the acrylic adhesive composition and will be described later.
  • any suitable additive may be used as long as it does not impair the effects of the present invention.
  • Acrylic polymers can be defined as those obtained by polymerizing monomer component (M) in this way. This is because acrylic polymers become acrylic polymers through the polymerization reaction of monomer component (M), and because it is impossible and virtually impractical to directly identify acrylic polymers by their structure ("impossible/impractical circumstances") exist, and so acrylic polymers are appropriately defined as "products" by the definition that they are "obtained by polymerizing monomer component (M)."
  • the acrylic polymer preferably has a glass transition temperature Tg of 0°C or lower, more preferably -10°C or lower, even more preferably -15°C or lower, particularly preferably -20°C or lower, and most preferably -25°C or lower, so that the effects of the present invention can be more effectively expressed.
  • the lower limit of the glass transition temperature Tg is preferably -100°C or higher, more preferably -90°C or higher, and even more preferably -80°C or higher.
  • the glass transition temperature Tg of an acrylic polymer refers to a value calculated from the Fox formula based on the glass transition temperature Tg of a homopolymer of each monomer constituting the acrylic polymer and the weight fraction (copolymerization ratio based on weight) of the monomer.
  • Tg is the glass transition temperature (unit: K) of the copolymer
  • Wi is the weight fraction of monomer i in the copolymer (copolymerization ratio by weight)
  • Tgi is the glass transition temperature (unit: K) of the homopolymer of monomer i.
  • the glass transition temperature Tg of the homopolymer is to be a value listed in publicly available documents.
  • the glass transition temperature Tg of the homopolymer specifically, for example, the following values can be used.
  • the monomer component (M) preferably contains an alkyl (meth)acrylate (a) and a polar group-containing monomer (b).
  • the alkyl (meth)acrylate (a) may be of only one type or of two or more types.
  • the polar group-containing monomer (b) may be of only one type or of two or more types.
  • alkyl group in the ester portion of alkyl (meth)acrylate (a) does not include alkyl groups containing a hydroxyl group or alkyl groups containing a polar group other than a hydroxyl group. Therefore, alkyl (meth)acrylate (a) is clearly distinguished from polar group-containing monomer (b).
  • the content of alkyl (meth)acrylate (a) in monomer component (M) is preferably 40% to 99.999% by weight, in order to better demonstrate the effects of the present invention.
  • the polar group-containing monomer (b) contained in the monomer component (M) is an embodiment that contains a hydroxyl group-containing monomer (b1) but does not contain a monomer (b2) having a polar group other than a hydroxyl group, as described below
  • the content of the alkyl (meth)acrylate (a) in the monomer component (M) is more preferably 60% by weight to 99.999% by weight, even more preferably 80% by weight to 99.99% by weight, even more preferably 85% by weight to 99.9% by weight, particularly preferably 90% by weight to 99.5% by weight, and most preferably 95% by weight to 99% by weight, in order to further exhibit the effects of the present invention.
  • the content of the alkyl (meth)acrylate (a) in the monomer component (M) is more preferably 43% to 90% by weight, even more preferably 46% to 80% by weight, particularly preferably 48% to 70% by weight, and most preferably 50% to 60% by weight, in order to further exert the effects of the present invention.
  • the alkyl group of the ester portion is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 18 carbon atoms, even more preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably an alkyl group having 1 to 14 carbon atoms, and most preferably an alkyl group having 1 to 12 carbon atoms, in order to further exert the effects of the present invention.
  • the alkyl group of the ester portion is preferably a chain alkyl group, since this can better exert the effects of the present invention.
  • chain alkyl group includes both linear and branched chains.
  • alkyl (meth)acrylate (a) examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)
  • the alkyl (meth)acrylate (a) contains an alkyl (meth)acrylate (a1) whose homopolymer has a glass transition temperature Tg in the range of -80°C to -60°C.
  • An example of such an alkyl (meth)acrylate (a1) is 2-ethylhexyl acrylate (2EHA) (whose homopolymer has a glass transition temperature Tg of -70°C).
  • Tg of a homopolymer of the alkyl (meth)acrylate (a1) for example, the following values can be used specifically.
  • the content of alkyl (meth)acrylate (a1) in the total amount of alkyl (meth)acrylate (a) is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, even more preferably 80% by weight to 100% by weight, particularly preferably 90% by weight to 100% by weight, and most preferably 95% by weight to 100% by weight, in order to further exert the effects of the present invention.
  • the alkyl (meth)acrylate (a1) whose homopolymer has a glass transition temperature Tg in the range of -80°C to -60°C can affect the adhesive properties of the acrylic polymer in terms of the aspect of manifesting the effects of the present invention.
  • alkyl (meth)acrylate (a1) whose homopolymer has a glass transition temperature Tg in the range of -80°C to -60°C, preferably in the above content ratio the effects of the present invention can be more effectively manifested.
  • the alkyl (meth)acrylate (a) may contain an alkyl (meth)acrylate other than the alkyl (meth)acrylate (a1).
  • the content of the alkyl (meth)acrylate other than the alkyl (meth)acrylate (a1) in the total amount of the alkyl (meth)acrylate (a) is preferably 0% by weight to 50% by weight, more preferably 0% by weight to 30% by weight, even more preferably 0% by weight to 20% by weight, particularly preferably 0% by weight to 10% by weight, and most preferably 0% by weight to 5% by weight, in order to further exert the effects of the present invention.
  • the content of the polar group-containing monomer (b) in the monomer component (M) is preferably 1% by weight to 60% by weight, more preferably 5% by weight to 60% by weight, even more preferably 10% by weight to 60% by weight, particularly preferably 15% by weight to 60% by weight, and most preferably 20% by weight to 60% by weight, in order to further exert the effects of the present invention.
  • any appropriate monomer having a polar group may be used as the polar group-containing monomer (b) as long as it does not impair the effects of the present invention.
  • Examples of such polar group-containing monomer (b) include embodiment (I) that contains hydroxyl group-containing monomer (b1) and embodiment (II) that does not contain hydroxyl group-containing monomer (b1). Note that the "hydroxyl group” referred to here does not include the -OH group possessed by a carboxyl group (-COOH).
  • the polar group-containing monomer (b) may be appropriately selected from the above embodiments within the range in which the glass transition temperature Tg of the acrylic polymer can be adjusted to the above-mentioned preferred range.
  • the hydroxyl group-containing monomer (b1) may be of only one type or of two or more types.
  • the monomer (b2) having a polar group other than a hydroxyl group may be of only one type or of two or more types.
  • hydroxyl group-containing monomer (b1) examples include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; polypropylene glycol mono(meth)acrylate; and N-hydroxyethyl (meth)acrylamide.
  • the hydroxyl-containing monomer (b1) has a glass transition temperature Tg of its homopolymer of preferably -60°C to -10°C, more preferably -55°C to -10°C, even more preferably -45°C to -10°C, particularly preferably -35°C to -10°C, and most preferably -25°C to -10°C.
  • the glass transition temperature Tg of the homopolymer of the hydroxyl-containing monomer (b1) can affect the adhesive properties, etc., of the acrylic polymer.
  • the effects of the present invention can be further exerted.
  • the glass transition temperature Tg of the homopolymer of the hydroxyl group-containing monomer (b1) may be determined from the same explanation as for the glass transition temperature Tg of the homopolymer of the alkyl (meth)acrylate (a1).
  • HOA 2-hydroxyethyl acrylate
  • the content of the hydroxyl group-containing monomer (b1) in the polar group-containing monomer (b) is preferably 1% by weight to 100% by weight, more preferably 10% by weight to 100% by weight, even more preferably 50% by weight to 100% by weight, even more preferably 70% by weight to 100% by weight, particularly preferably 90% by weight to 100% by weight, and most preferably 95% by weight to 100% by weight, in order to further exert the effects of the present invention.
  • the polar group-containing monomer (b) may contain a monomer (b2) having a polar group other than a hydroxyl group.
  • the content of the monomer (b2) having a polar group other than a hydroxyl group in the polar group-containing monomer (b) is preferably 0% to 99% by weight, more preferably 0% to 90% by weight, even more preferably 0% to 50% by weight, even more preferably 0% to 30% by weight, particularly preferably 0% to 10% by weight, and most preferably 0% to 5% by weight, in order to further exhibit the effects of the present invention.
  • the content of the hydroxyl group-containing monomer (b1) in the monomer component (M) is preferably 0.001% by weight to 40% by weight, more preferably 0.01% by weight to 20% by weight, even more preferably 0.1% by weight to 15% by weight, particularly preferably 0.5% by weight to 10% by weight, and most preferably 1% by weight to 5% by weight, in order to further exert the effects of the present invention.
  • Examples of monomers (b2) having a polar group other than a hydroxyl group include carboxyl group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, cyano group-containing monomers, acid anhydride group-containing monomers, vinyl esters, heterocycle-containing vinyl monomers, aromatic vinyl compounds, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, isocyanate group-containing monomers, (meth)acrylic acid esters having aromatic hydrocarbon groups, aromatic vinyl compounds, olefins and dienes, vinyl ethers, (meth)acryloylmorpholine, vinyl ethers, and halogen group-containing monomers.
  • carboxy group-containing monomers examples include acrylic acid (AA), methacrylic acid (MAA), carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • An example of a sulfonic acid group-containing monomer is sodium vinyl sulfonate.
  • a phosphate group-containing monomer is 2-hydroxyethyl acryloyl phosphate.
  • Cyano group-containing monomers include, for example, acrylonitrile and methacrylonitrile.
  • Examples of monomers containing an acid anhydride group include maleic anhydride and itaconic anhydride.
  • heterocycle-containing vinyl monomers examples include N-vinyl-2-pyrrolidone, (meth)acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, and vinyloxazole.
  • aromatic vinyl compounds examples include styrene and vinyltoluene.
  • amide group-containing monomers examples include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, and N-hydroxyethyl(meth)acrylamide.
  • imide group-containing monomers examples include cyclohexylmaleimide and isopropylmaleimide.
  • amino group-containing monomers examples include aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and t-butylaminoethyl (meth)acrylate.
  • epoxy group-containing monomers examples include glycidyl (meth)acrylate and methyl glycidyl (meth)acrylate.
  • An example of an isocyanate group-containing monomer is 2-methacryloyloxyethyl isocyanate.
  • Examples of (meth)acrylic acid esters having an aromatic hydrocarbon group include phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate.
  • aromatic vinyl compounds examples include styrene and vinyltoluene.
  • olefins and dienes examples include ethylene, butadiene, isoprene, and isobutylene.
  • vinyl ethers examples include vinyl alkyl ethers.
  • halogen-containing monomer is vinyl chloride.
  • the glass transition temperature Tg of the homopolymer of the monomer (b2) having a polar group other than a hydroxyl group is preferably 0°C to 130°C, more preferably 10°C to 120°C, and even more preferably 20°C to 110°C.
  • the glass transition temperature Tg of the homopolymer of the monomer (b2) having a polar group other than a hydroxyl group may be determined from the same explanation as for the glass transition temperature Tg of the homopolymer of the alkyl (meth)acrylate (a1).
  • One embodiment of the monomer (b2) having a polar group other than a hydroxyl group includes a monomer (b2-1) having a polar group other than a hydroxyl group, the glass transition temperature Tg of which homopolymer is 0° C. to 60° C., and a monomer (b2-2) having a polar group other than a hydroxyl group, the glass transition temperature Tg of which homopolymer is 70° C. to 130° C.
  • the content of the monomer (b2-1) having a polar group other than a hydroxyl group in the monomer (b2) having a polar group other than a hydroxyl group is preferably 50% by weight to 99% by weight, more preferably 70% by weight to 99% by weight, even more preferably 80% by weight to 99% by weight, and particularly preferably 90% by weight to 99% by weight, in terms of being able to further exhibit the effects of the present invention.
  • the content of the monomer (b2-2) having a polar group other than a hydroxyl group in the monomer (b2) having a polar group other than a hydroxyl group is preferably 1% by weight to 50% by weight, more preferably 1% by weight to 30% by weight, even more preferably 1% by weight to 20% by weight, and particularly preferably 1% by weight to 10% by weight, in order to further exhibit the effects of the present invention.
  • the total content of the monomer (b2-1) having a polar group other than a hydroxyl group and the monomer (b2-2) having a polar group other than a hydroxyl group in the monomer (b2) having a polar group other than a hydroxyl group is preferably 60% by weight to 100% by weight, more preferably 80% by weight to 100% by weight, even more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight, and most preferably 98% by weight to 100% by weight.
  • the glass transition temperature Tg of the monomer (b2-1) having a polar group other than a hydroxyl group is preferably 10°C to 50°C, and more preferably 20°C to 40°C.
  • the glass transition temperature Tg of the monomer (b2-2) having a polar group other than a hydroxyl group is preferably 80°C to 120°C, and more preferably 90°C to 110°C.
  • the polar group-containing monomer (b) is embodiment (II) that does not contain a hydroxyl group-containing monomer (b1), i.e., when the monomer (b2) having a polar group other than a hydroxyl group is essentially contained
  • the content of the monomer (b2) having a polar group other than a hydroxyl group in the monomer component (M) is preferably 10% by weight to 57% by weight, more preferably 20% by weight to 54% by weight, even more preferably 30% by weight to 52% by weight, and particularly preferably 40% by weight to 50% by weight, in order to further exert the effects of the present invention.
  • the monomer component (M) preferably contains an alkyl (meth)acrylate (a) and a polar group-containing monomer (b), the content of the alkyl (meth)acrylate (a) in the monomer component (M) is 43% to 90% by weight, the alkyl (meth)acrylate (a) is an alkyl (meth)acrylate (a1) whose homopolymer has a glass transition temperature Tg in the range of -80°C to -60°C, the polar group-containing monomer (b) does not contain a hydroxyl group-containing monomer (b1) but essentially contains a monomer (b2) having a polar group other than a hydroxyl group, the hydroxyl group-containing monomer (b2) has a homopolymer glass transition temperature Tg in the range of 0°C to 130°C, and the content of the polar group-containing monomer (b2) in the monomer component (M) is 10% to 57% by weight.
  • the monomer component (M) preferably contains an alkyl (meth)acrylate (a) and a polar group-containing monomer (b),
  • the content of the alkyl (meth)acrylate (a) in the monomer component (M) is preferably 60% by weight to 99.999% by weight, more preferably 80% by weight to 99.99% by weight, even more preferably 85% by weight to 99.9% by weight, particularly preferably 90% by weight to 99.5% by weight, and most preferably 95% by weight to 99% by weight
  • the alkyl(meth)acrylate (a) preferably essentially contains an alkyl(meth)acrylate (a1) having a glass transition temperature Tg of its homopolymer in the range of ⁇ 80° C.
  • the content of the alkyl (meth)acrylate (a1) in the total amount of the alkyl (meth)acrylate (a) is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, even more preferably 80% by weight to 100% by weight, particularly preferably 90% by weight to 100% by weight, and most preferably 95% by weight to 100% by weight;
  • the content of the polar group-containing monomer (b) in the monomer component (M) is preferably 0.001% by weight to 40% by weight, more preferably 0.01% by weight to 20% by weight, even more preferably 0.1% by weight to 15% by weight, particularly preferably 0.5% by weight to 10% by weight, and most preferably 1% by weight to 5% by weight;
  • the polar group-containing monomer (b) preferably essentially contains a hydroxyl group-containing monomer (b1);
  • the hydroxyl group-containing monomer (b1) preferably has a glass transition temperature Tg of its
  • the content of the hydroxyl group-containing monomer (b1) in the polar group-containing monomer (b) is preferably 1% by weight to 100% by weight, more preferably 10% by weight to 100% by weight, even more preferably 50% by weight to 100% by weight, still more preferably 70% by weight to 100% by weight, particularly preferably 90% by weight to 100% by weight, and most preferably 95% by weight to 100% by weight;
  • the content of the polar group-containing monomer (b1) in the monomer component (M) is preferably 0.001% by weight to 40% by weight, more preferably 0.01% by weight to 20% by weight, even more preferably 0.1% by weight to 15% by weight, particularly preferably 0.5% by weight to 10% by weight, and most preferably 1% by weight to 5% by weight.
  • the monomer component (M) may contain other monomers (c) that do not fall into either the alkyl (meth)acrylate (a) or the polar group-containing monomer (b).
  • the other monomers (c) can be used for purposes such as adjusting the glass transition temperature Tg of the acrylic polymer and adjusting the adhesive performance.
  • the other monomers may be of only one type or of two or more types.
  • the content of other monomers (c) in monomer component (M) is preferably 20% by weight or less, more preferably 10% by weight or less, even more preferably 5% by weight or less, particularly preferably 3% by weight or less, and most preferably 1% by weight or less.
  • the acrylic polymer is obtained by polymerizing the monomer component (M).
  • a preferred embodiment of the acrylic polymer is an acrylic polymer prepared by solution polymerization using a polymerization initiator.
  • polymerization initiator Any appropriate polymerization initiator may be used depending on the type of polymerization reaction.
  • the polymerization initiator may be of only one type or of two or more types.
  • a typical example of a polymerization initiator is a thermal polymerization initiator.
  • the thermal polymerization initiator may be preferably used when obtaining an acrylic polymer by solution polymerization.
  • a thermal polymerization initiator examples include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis(2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propionate], and 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propionate].
  • AIBN 2,2'-azobisisobutyronitrile
  • 2,2'-azobis-2-methylbutyronitrile 2,2'-azobis(2-methylpropionic acid) dimethyl
  • 4,4'-azobis-4-cyanovaleric acid 4,4
  • azo initiators such as 2,2'-azobis(2-methylpropionamidine)dihydrochloride, 2,2'-azobis(N,N'-dimethyleneisobutylamidine), and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.); persulfates such as potassium persulfate and ammonium persulfate, and di(2-ethylhexyl)peroxydicarbonate.
  • the amount of the thermal polymerization initiator used may be set to any appropriate amount as long as it does not impair the effects of the present invention.
  • the amount of the thermal polymerization initiator used is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight, even more preferably 0.007 to 3 parts by weight, and particularly preferably 0.01 to 1 part by weight, relative to 100 parts by weight of the monomer component (M), in order to further exert the effects of the present invention.
  • Any suitable solvent may be used when obtaining an acrylic polymer by solution polymerization, as long as it does not impair the effects of the present invention.
  • the acrylic pressure-sensitive adhesive composition may contain a crosslinking agent.
  • the crosslinking agent may be one type only, or two or more types.
  • crosslinking agents examples include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, silicone-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, silane-based crosslinking agents, alkyl etherified melamine-based crosslinking agents, metal chelate-based crosslinking agents, and peroxides.
  • at least one type (component c) selected from the group consisting of isocyanate-based crosslinking agents, epoxy-based crosslinking agents, and peroxides is preferred.
  • isocyanate-based crosslinking agent a compound having two or more isocyanate groups (including isocyanate-regenerating polar groups in which the isocyanate group is temporarily protected by a blocking agent or oligomerization) in one molecule can be used.
  • isocyanate-based crosslinking agents include aromatic isocyanates such as tolylene diisocyanate and xylylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and aliphatic isocyanates such as hexamethylene diisocyanate.
  • isocyanate-based crosslinking agents include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate; aromatic diisocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and polymethylene polyphenyl isocyanate; trimethylolpropane/tolylene diisocyanate trimer adduct (e.g., manufactured by Tosoh Corporation, product name: Coronate L), trimethylolpropane/hexamethylene diisocyanate trimer adduct (e.g., manufactured by Tosoh Corporation, product name: Coronate HL), and isocyanurate of hexamethylene diis
  • epoxy-based crosslinking agent a multifunctional epoxy compound having two or more epoxy groups in one molecule can be used.
  • epoxy crosslinking agents include N,N,N',N'-tetraglycidyl-m-xylylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidy
  • peroxides examples include dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl hydroperoxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxine)hexyne-3, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-mono(t-butylperoxy)-hexane, ⁇ , ⁇ '-bis(t-butylperoxy-m-isopropyl)benzene, di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxy
  • the content of the crosslinking agent in the acrylic adhesive composition may be any appropriate content within the range that does not impair the effects of the present invention.
  • a content is preferably 0.05 parts by weight to 20 parts by weight, more preferably 0.1 parts by weight to 18 parts by weight, even more preferably 0.5 parts by weight to 15 parts by weight, and particularly preferably 0.5 parts by weight to 10 parts by weight, relative to the solid content (100 parts by weight) of the acrylic polymer, in order to further exert the effects of the present invention.
  • the acrylic pressure-sensitive adhesive composition may contain a polyfunctional alcohol. By using the polyfunctional alcohol, it is possible to impart appropriate softness to the acrylic pressure-sensitive adhesive.
  • the polyfunctional alcohol may be one type only, or two or more types.
  • the number of functional groups of the polyfunctional alcohol is preferably 2 or more, more preferably 3 to 6, even more preferably 3 to 5, particularly preferably 3 to 4, and most preferably 3, in order to better demonstrate the effects of the present invention.
  • polyfunctional alcohols examples include polyether polyols and polyester polyols.
  • polyether polyols examples include polypropylene glycol (bifunctional), diol (bifunctional) with propylene oxide added to bisphenol A, triol (trifunctional) with propylene oxide added to glycerin, triol (trifunctional) with propylene oxide added to trimethylolpropane, tetraol (tetrafunctional) with propylene oxide added to the active hydrogen of ethylenediamine, polyol (multifunctional) with propylene oxide added to sorbitol or sucrose, triol (trifunctional) with propylene oxide and ethylene oxide added to glycerin, the ends of which are blocked with ethylene oxide, and tetraol (trifunctional) with propylene oxide and ethylene oxide added to the active hydrogen of ethylenediamine, the ends of which are blocked with ethylene oxide.
  • polyols examples include tetraols (4 functional), polypropylene polyethylene glycols (2 functional) in which the terminals are blocked with ethylene oxide, diols (2 functional) in which propylene oxide and ethylene oxide are added to bisphenol A and the terminals are blocked with ethylene oxide, triols (3 functional) in which ethylene oxide is added to trimethylolpropane, polypropylene polyethylene glycols (2 functional) in which ethylene oxide and propylene oxide are randomly added, triols (3 functional) in which propylene oxide and ethylene oxide are added to glycerin and the terminals are blocked with ethylene oxide and propylene oxide, and flame retardant polyols (2 functional).
  • polyether polyols include, for example, ADEKA Polyols from ADEKA Corporation (e.g., P series, BPX series, G series, T series, EDP series, SP series, SC series, R series, RD series, AM series, BM series, CM series, EM series, GM series, PR series, GR series, flame-retardant polyols, etc.), and polyols from Sanyo Chemical Industries, Ltd.
  • ADEKA Polyols from ADEKA Corporation (e.g., P series, BPX series, G series, T series, EDP series, SP series, SC series, R series, RD series, AM series, BM series, CM series, EM series, GM series, PR series, GR series, flame-retardant polyols, etc.), and polyols from Sanyo Chemical Industries, Ltd.
  • triol (trifunctional) obtained by adding propylene oxide to glycerin triol (trifunctional) obtained by adding propylene oxide to trimethylolpropane, triol (trifunctional) obtained by adding propylene oxide and ethylene oxide to glycerin, the ends of which are blocked with ethylene oxide, triol (trifunctional) obtained by adding ethylene oxide to trimethylolpropane, triol (trifunctional) obtained by adding propylene oxide and ethylene oxide to glycerin, the ends of which are blocked with ethylene oxide
  • a triol (trifunctional) in which propylene oxide is added randomly to glycerin more preferably a triol (trifunctional) in which propylene oxide is added to glycerin, a triol (trifunctional) in which propylene oxide and ethylene oxide are added to glycerin and the ends are blocked with ethylene oxide, a triol (trifunctional) in which propylene oxide in which propylene oxide
  • the polyester polyol may be, for example, a polyester polyol obtained by reacting an acid component with a glycol component.
  • the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid.
  • glycol component examples include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, and butylethylpentanediol.
  • polyol component examples include glycerin, trimethylolpropane, and pentaerythritol.
  • polyester polyol (a1) include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly( ⁇ -methyl- ⁇ -valerolactone), and polyvalerolactone.
  • polyester polyols include, for example, ADEKA New Ace from ADEKA Corporation (e.g., F18-62, F7-67, Y9-10, Y4-5, Y52-13, Y52-21, V14-90, YG-108, F1212-29, #50, Y65-55, YT-101, YT-651, NS-2400, etc.).
  • the number average molecular weight of the polyfunctional alcohol is preferably 50 to 10,000, more preferably 60 to 5,000, in order to better demonstrate the effects of the present invention.
  • the content of the polyfunctional alcohol in the acrylic adhesive composition may be any appropriate content within the range that does not impair the effects of the present invention.
  • a content is preferably 0.0001 parts by weight to 20 parts by weight, more preferably 0.001 parts by weight to 15 parts by weight, even more preferably 0.01 parts by weight to 10 parts by weight, and particularly preferably 0.1 parts by weight to 5 parts by weight, relative to the solid content (100 parts by weight) of the acrylic polymer, in order to further exert the effects of the present invention.
  • the acrylic adhesive composition may contain any other suitable components within the scope that does not impair the effect of the present invention.Such other components include, for example, polymer components other than acrylic polymers, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifier resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), antiaging agents, inorganic fillers, organic fillers, metal powders, colorants (pigments, dyes, etc.), foil-like materials, ultraviolet absorbers, antioxidants, light stabilizers, nucleating agents, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, etc.
  • tackifier resins Rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.
  • antiaging agents inorganic fill
  • Substrate ⁇ As long as the adherend has a water contact angle and an arithmetic mean surface roughness Ra of the surface on which the surface protective film is laminated within the above-mentioned preferred ranges, the effect of the present invention is not impaired. Any suitable adherend may be employed.
  • the water contact angle of the surface of the adherend on the surface protection film side is preferably 85° or more, more preferably 85° to 110°, even more preferably 85° to 105°, particularly preferably 90° to 100°, and most preferably 91° to 100°. If the water contact angle is within the above range, the effects of the present invention can be more effectively achieved.
  • the surface protection film is likely to adhere excessively to the adherend, and, for example, the initial peeling force of the surface protection film from the adherend may become too high, making it impossible to peel the surface protection film from the adherend, or the peeling force of the surface protection film from the adherend may increase too much over time, making it impossible to peel the surface protection film from the adherend.
  • the surface protection film will not adhere too closely to the adherend, and for example, the initial peel strength of the surface protection film from the adherend will be too low, which may cause the surface protection film to lift off the adherend or cause poor peeling when peeling off a release liner that may be provided on the outermost surface of the surface protection film.
  • the arithmetic mean surface roughness Ra of the surface of the adherend on the surface protection film side is preferably 0.6 ⁇ m or less, more preferably 0.35 ⁇ m or less, even more preferably 0.2 ⁇ m or less, particularly preferably 0.1 ⁇ m or less, and most preferably 0.08 ⁇ m or less.
  • the lower limit of the arithmetic mean surface roughness Ra is preferably as small as possible, and is preferably 0 ⁇ m or more. If the arithmetic mean surface roughness Ra is within the above range, the effect of the present invention can be more effectively achieved.
  • the arithmetic mean surface roughness Ra is too large outside the above range, for example, when the thickness of the adhesive layer of the surface protection film is large, the peeling force of the surface protection film from the adherend increases too much over time, and it may become impossible to peel the surface protection film from the adherend.
  • the adherend is typically an optical member. Any suitable optical member may be used as the optical member as long as it does not impair the effects of the present invention. Examples of such optical members include members having any suitable layer on any suitable substrate. Specific examples of optical members include polarizing plates, retardation plates, displays, imaging devices, lenses, and (half) mirrors.
  • the adherend may be selected so that the water contact angle and the arithmetic mean surface roughness Ra of the surface on which the surface protective film is laminated are within the above-mentioned preferred ranges, and any appropriate material may be used for the surface.
  • any appropriate material may be used for the surface.
  • a representative example of such a material is a resin
  • the adherend is preferably a member having any appropriate resin layer.
  • the thickness of the adherend may be any appropriate thickness depending on the type of adherend. Typically, the thickness of the adherend is preferably 5 ⁇ m to 950 ⁇ m, more preferably 20 ⁇ m to 750 ⁇ m, even more preferably 30 ⁇ m to 550 ⁇ m, and particularly preferably 40 ⁇ m to 450 ⁇ m.
  • Measurement device Contact angle measuring device DropMaster DM700 (manufactured by Kyowa Interface Science Co., Ltd.) Measurement atmosphere: 23°C, 50% RH Measurement liquid: distilled water Measurement time: 500 ms after droplets
  • arithmetic mean surface roughness Ra The arithmetic mean surface roughness Ra of the surface of the adherend on the surface protective film side (the side on which the surface protective film was laminated) was measured. Specifically, the measurement was performed under the following conditions.
  • Measuring device High-precision micro-shape measuring device SURFCORDER ET4000A (manufactured by Kosaka Laboratory) Stylus of detection part: Tip curvature radius 0.5 ⁇ m, apex angle 60 degrees, material diamond Reference length (cutoff value ⁇ c of roughness curve): 0.8 mm Evaluation length (reference length): 12 mm Stylus feed speed: 1 mm/s Vertical magnification: 20,000 times Horizontal magnification: 10 times
  • a test piece 1000 was placed on the upper surface of a test plate 2000 having a recess of 25 mm length, 25 mm width and 1 mm depth formed on the upper surface.
  • the laminate (adherend with surface protective film) obtained in the Examples and Comparative Examples was cut to a length of 60 mm and a width of 60 mm.
  • This state was maintained for 1.0 second, and then the rod was removed from the laminate 1000.
  • this state was confirmed whether or not a pressing mark remained on the laminate 1000. (evaluation) None ( ⁇ ): No indentation remains. Yes ( ⁇ ): Indentations remain.
  • the initial peel force (A) is preferably 0.025 N/25 mm or more and less than 0.100 N/25 mm, more preferably 0.030 N/25 mm or more and less than 0.090 N/25 mm, even more preferably 0.035 N/25 mm or more and less than 0.085 N/25 mm, even more preferably 0.040 N/25 mm or more and less than 0.085 N/25 mm, even more preferably 0.040 N/25 mm or more and less than 0.080 N/25 mm, particularly preferably 0.040 N/25 mm or more and less than 0.075 N/25 mm, and most preferably 0.040 N/25 mm or more and less than 0.070 N/25 mm.
  • the evaluation criteria were as follows. (Evaluation criteria) ⁇ : 0.040N/25mm or more and less than 0.085N/25mm ⁇ : 0.030N/25mm or more and less than 0.040N/25mm or 0.085N/25mm or more and less than 0.090N/25mm ⁇ : 0.025N/25mm or more and less than 0.030N/25mm or 0.090N/25mm or more and less than 0.100N/25mm ⁇ : Less than 0.025N/25mm or 0.100N/25mm or more
  • the laminates (adherends with surface protective films) obtained in the examples and comparative examples were stored in an environment at a temperature of 60°C for 72 hours, and then allowed to stand for 30 minutes in an environment at a temperature of 23°C and a relative humidity of 50%, and then a peel test was carried out in the same environment at a peel angle of 180° and a tensile speed of 300 mm/min to measure the 180° peel strength, which was recorded as the peel strength after storage at 60°C for 72 hours.
  • the peel force (B) after storage at 60°C for 72 hours is preferably 0.030 N/25 mm or more and less than 0.115 N/25 mm, more preferably 0.040 N/25 mm or more and less than 0.105 N/25 mm, even more preferably 0.040 N/25 mm or more and less than 0.100 N/25 mm, still more preferably 0.045 N/25 mm or more and less than 0.095 N/25 mm, still more preferably 0.050 N/25 mm or more and less than 0.095 N/25 mm, particularly preferably 0.055 N/25 mm or more and less than 0.095 N/25 mm, and most preferably 0.055 N/25 mm or more and less than 0.092 N/25 mm.
  • the evaluation criteria were as follows. (Evaluation criteria) ⁇ : 0.055N/25mm or more and less than 0.095N/25mm ⁇ : 0.040N/25mm or more and less than 0.055N/25mm or 0.095N/25mm or more and less than 0.100N/25mm ⁇ : 0.030N/25mm or more and less than 0.040N/25mm or 0.100N/25mm or more and less than 0.115N/25mm ⁇ : Less than 0.030N/25mm or 0.115N/25mm or more
  • this peel force change (B) - (A) is, the more preferable, and is preferably less than 0.045 N/25 mm, more preferably less than 0.042 N/25 mm, even more preferably less than 0.040 N/25 mm, even more preferably less than 0.037 N/25 mm, even more preferably less than 0.035 N/25 mm, particularly preferably less than 0.032 N/25 mm, and most preferably less than 0.030 N/25 mm.
  • the evaluation criteria were as follows.
  • ⁇ Creep recovery value of adhesive layer Only the pressure-sensitive adhesive layer was taken out from the laminate, laminated to a thickness of about 1 mm, and punched out to a diameter of 8 mm to prepare a cylindrical pellet, which was used as a measurement sample. Using a dynamic viscoelasticity measuring device (TA Instruments, DHR2), the obtained measurement sample was fixed to a jig with a ⁇ 8 mm parallel plate. At 25°C, the deformation strain (%) after applying a deformation stress of 5 KPa and holding for 300 seconds was defined as A value, and the deformation strain (%) after further reducing the deformation stress to 0 and holding for 300 seconds was defined as B value. The value calculated by [ ⁇ (A value-B value)/A value ⁇ 100] was defined as the creep recovery value.
  • ⁇ Shear modulus> The surface protection film used in the laminate obtained in the examples and comparative examples was cut to 5 mm (TD) x 50 mm (MD), and the adhesive layer of the surface protection film was attached to an acrylic plate (manufactured by Mitsubishi Chemical, product name "Acrylite L") as an adherend so that the contact area was 5 mm x 10 mm. After that, it was left to stand for 30 minutes in an environment of 23 ° C.
  • a precision universal testing machine manufactured by Shimadzu Corporation, AUTOGRAPH AG-X plus was used to measure the shear stress in the shear direction at a tensile speed of 0.06 mm / min, and a shear strain (horizontal axis) - shear stress (vertical axis) curve was obtained.
  • the shear modulus G was calculated from the following formula as the slope from a shear strain of 0.05 mm to 0.2 mm.
  • the liquid temperature was kept at around 65°C and a polymerization reaction was carried out for 6 hours to produce a solution of acrylic polymer (1) (concentration 40% by weight).
  • the weight average molecular weight of the acrylic polymer (1) was 540,000.
  • the liquid temperature was kept at around 63°C and a polymerization reaction was carried out for 6 hours. Thereafter, the temperature of the contents of the vessel was raised to 80°C and aged for 3.5 hours to produce a solution of acrylic polymer (2) (concentration 40% by weight).
  • the weight average molecular weight of the acrylic polymer (2) was 650,000.
  • Production of Surface Protective Film (1) The acrylic pressure-sensitive adhesive composition (1) obtained in Production Example 6 was applied to the corona surface of a biaxially stretched polyester film ("T100C38" manufactured by Mitsubishi Chemical, thickness 38 ⁇ m) and heated at 130° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 21 ⁇ m.
  • the release-treated surface of a release liner (a polyester film having a thickness of 25 ⁇ m and one side of which was treated with silicone release) was bonded to the surface of the pressure-sensitive adhesive layer to produce a surface protective film (1) with a release liner.
  • Production of Surface Protective Film (2) The acrylic pressure-sensitive adhesive composition (2) obtained in Production Example 7 was applied to the corona surface of a biaxially stretched polyester film ("T100C38" manufactured by Mitsubishi Chemical, thickness 38 ⁇ m) and heated at 130° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 21 ⁇ m.
  • the release-treated surface of a release liner (a polyester film having a thickness of 25 ⁇ m and one side of which was treated with silicone release) was bonded to the surface of the pressure-sensitive adhesive layer to produce a surface protective film (2) with a release liner.
  • Production of Surface Protective Film (3) The acrylic pressure-sensitive adhesive composition (3) obtained in Production Example 8 was applied to the corona surface of a biaxially stretched polyester film ("T100C38" manufactured by Mitsubishi Chemical, thickness 38 ⁇ m) and heated at 130° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 10 ⁇ m.
  • the release-treated surface of a release liner (a polyester film having a thickness of 25 ⁇ m and one side of which was treated with silicone release) was bonded to the surface of the pressure-sensitive adhesive layer to produce a surface protective film (3) with a release liner.
  • Production of Surface Protective Film (4) The acrylic pressure-sensitive adhesive composition (4) obtained in Production Example 9 was applied to the corona surface of a biaxially stretched polyester film ("T100C38" manufactured by Mitsubishi Chemical, thickness 38 ⁇ m) and heated at 130° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 10 ⁇ m.
  • the release-treated surface of a release liner (a polyester film having a thickness of 25 ⁇ m and one side of which was treated with silicone release) was bonded to the surface of the pressure-sensitive adhesive layer to produce a surface protective film (4) with a release liner.
  • Production of Surface Protective Film (5) The acrylic pressure-sensitive adhesive composition (5) obtained in Production Example 10 was applied to the corona surface of a biaxially stretched polyester film ("T100C38" manufactured by Mitsubishi Chemical, thickness 38 ⁇ m) and heated at 130° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 10 ⁇ m.
  • the release-treated surface of a release liner (a polyester film having a thickness of 25 ⁇ m and one side of which was treated with silicone release) was bonded to the surface of the pressure-sensitive adhesive layer to produce a surface protective film (5) with a release liner.
  • Production of Coating Solution (4) [0223] The same procedure as in Production Example 16 was repeated, except that the amount of a leveling agent (manufactured by DIC Corporation, product name "GRANDIC PC4100", solid content 10%) used was changed from 0.1 part by weight to 0.01 part by weight, to produce a coating solution (4).
  • a leveling agent manufactured by DIC Corporation, product name "GRANDIC PC4100", solid content 10%
  • Production of Coating Solution (5) [0213] The same procedure as in Production Example 16 was repeated, except that the amount of a leveling agent (manufactured by DIC Corporation, product name "GRANDIC PC4100", solid content 10%) used was changed from 0.1 part by weight to 0.05 part by weight, to produce a coating solution (5).
  • a leveling agent manufactured by DIC Corporation, product name "GRANDIC PC4100", solid content 10%
  • Production of Coating Solution (6) [0213] The same procedure as in Production Example 16 was carried out, except that the amount of a leveling agent (manufactured by DIC Corporation, product name "GRANDIC PC4100", solid content 10%) used was changed from 0.1 part by weight to 0.15 part by weight, to produce a coating solution (6).
  • a leveling agent manufactured by DIC Corporation, product name "GRANDIC PC4100", solid content 10%
  • Example 1 Production of laminate (1) A surface protection film (1) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (1) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (1). The results are shown in Table 1.
  • Example 2 Production of laminate (2) A surface protection film (2) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (1) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (2).
  • the results are shown in Table 1.
  • Example 3 Production of laminate (3) A surface protection film (3) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (1) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (3).
  • the results are shown in Table 1.
  • Example 4 Production of laminate (4) A surface protection film (4) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (1) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (4).
  • the results are shown in Table 1.
  • Example 5 Production of laminate (5) A surface protection film (1) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (2) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (5).
  • the results are shown in Table 1.
  • Example 6 Production of laminate (6) A surface protection film (4) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (2) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (6).
  • the results are shown in Table 1.
  • Example 7 Production of laminate (7) A surface protection film (1) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (3) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (7).
  • the results are shown in Table 1.
  • Example 8 Production of laminate (8) A surface protection film (4) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (3) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (8).
  • the results are shown in Table 1.
  • Example 9 Production of laminate (9) A surface protection film (1) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (6) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (9). The results are shown in Table 1.
  • Example 10 Production of laminate (10) A surface protective film (1) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (7) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (10). The results are shown in Table 1.
  • Example 11 Production of laminate (11) A surface protective film (1) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (8) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (11). The results are shown in Table 1.
  • Comparative Example 1 Production of Laminate (C1) A surface protective film (5) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (1) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (C1). The results are shown in Table 1.
  • the laminate of the present invention can be used for any suitable application.
  • the laminate of the present invention is used in the fields of optical components and electronic components.

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

A laminate comprising a surface-protective film and an adherend is provided in which a deformation mark due to a deformation caused by external force is less apt to remain and the surface-protective film has an adequate initial peel force in peeling from the adherend and changes little with the lapse of time in the peel force in peeling from the adherend.　The laminate according to an embodiment of the present invention comprises a surface-protective film and an adherend, wherein the surface-protective film comprises a substrate and a pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer having been directly laminated to the adherend. The surface-protective-film-side surface of the adherend has a contact angel with water of 85° or greater. The surface-protective-film-side surface of the adherend has an arithmetic average surface roughness Ra of 0.6 μm or less. The laminate satisfies (i) the pressure-sensitive adhesive layer has a creep recovery value of 96% or higher and/or (ii) the surface-protective film has a coefficient G of shear modulus of 39.0 N/50 mm3 or less.

Description

積層体Laminate
　本発明は、積層体に関する。 The present invention relates to a laminate.
　光学部材の表面には、表面保護や耐衝撃性付与等を目的として、表面保護フィルムが設けられる。表面保護フィルムとしては、代表的には、デバイスの組み立て、加工、輸送等の使用前の状態において一時的に仮着され、デバイスの使用前に再剥離されるもの（工程材として用いられるもの）、デバイスの使用時にもデバイス表面に貼着したままの状態で使用されるもの（永久接着を目的としたもの）がある（例えば、特許文献１参照）。 A surface protection film is provided on the surface of an optical component for the purposes of surface protection and impact resistance. Typical surface protection films include those that are temporarily attached during the assembly, processing, transportation, etc. of a device before use and are peeled off again before the device is used (those used as process materials), and those that remain attached to the device surface even when the device is in use (those intended for permanent adhesion) (see, for example, Patent Document 1).
　工程材として用いられる表面保護フィルムおよび永久接着を目的とした表面保護フィルムは、いずれも、フィルム基材の主面に粘着剤層を備え、この粘着剤層を介して、保護対象である被着体の表面に貼り合わせられる（例えば、特許文献２参照）。 Surface protection films used as processing materials and surface protection films intended for permanent adhesion both have an adhesive layer on the main surface of the film substrate, and are attached to the surface of the adherend to be protected via this adhesive layer (see, for example, Patent Document 2).
　光学部材などを被着体とし、この被着体に表面保護フィルムの粘着剤層が貼り合わせられた積層構造を有する積層体は、従来、次のような問題がある。 Laminates that have a laminated structure in which an optical component or the like is used as an adherend and a pressure-sensitive adhesive layer of a surface protection film is bonded to the adherend have traditionally had the following problems:
　上記のような積層体の取り扱い時の外力による変形により変形跡が残ってしまうと、不良品となってしまうおそれがあり、歩留まりが低下してしまうおそれがある。 If deformation marks remain due to external forces during handling of the laminate as described above, the product may become defective and the yield may decrease.
　上記のような積層体において、被着体からの表面保護フィルムの初期剥離力が低すぎると、被着体からの表面保護フィルムの浮きが生じるおそれや、被着体の表面保護フィルムと反対側に設けられたはく離ライナー（すなわち、はく離ライナー／被着体／表面保護フィルムの積層構成における該はく離ライナー）をはく離する際に、被着体とはく離ライナーの界面でのはく離よりも表面保護フィルムと被着体の界面でのはく離が起こってしまうというはく離不良（意図しない箇所のはく離）が生じるおそれがある。 In the above-mentioned laminate, if the initial peel strength of the surface protective film from the adherend is too low, there is a risk that the surface protective film will lift off the adherend, or that when peeling the release liner provided on the side of the adherend opposite the surface protective film (i.e., the release liner in a laminate structure of release liner/adherend/surface protective film), peeling will occur at the interface between the surface protective film and the adherend rather than at the interface between the adherend and the release liner, resulting in poor peeling (peel at an unintended location).
　上記のような積層体において、被着体からの表面保護フィルムの初期剥離力が高すぎると、被着体から表面保護フィルムを剥離できなくなるおそれがある。 In the above-mentioned laminate, if the initial peel strength of the surface protection film from the adherend is too high, it may not be possible to peel the surface protection film from the adherend.
　上記のような積層体において、被着体からの表面保護フィルムの剥離力が経時で大きく上昇すると、被着体から表面保護フィルムを剥離できなくなるおそれがある。 In the above-mentioned laminate, if the peel strength of the surface protection film from the adherend increases significantly over time, it may become impossible to peel the surface protection film from the adherend.
特許第３５１８６７７号公報Patent No. 3518677 特許第６２４９６１７号公報Japanese Patent No. 6249617
　本発明の課題は、外力による変形による変形跡が残りにくく、被着体からの表面保護フィルムの初期剥離力が適度であり、被着体からの表面保護フィルムの剥離力の経時変化が小さい、表面保護フィルムと被着体を含む積層体を提供することにある。 The object of the present invention is to provide a laminate including a surface protection film and an adherend that is unlikely to leave traces of deformation due to deformation caused by external forces, has an appropriate initial peel strength of the surface protection film from the adherend, and exhibits little change over time in the peel strength of the surface protection film from the adherend.
　［１］本発明の一つの実施形態による積層体は、表面保護フィルムと被着体を含む積層体であって、該表面保護フィルムは、基材と粘着剤層を有し、該粘着剤層と該被着体が直接積層されてなり、該被着体の該表面保護フィルム側の表面の水接触角が８５°以上であり、該被着体の該表面保護フィルム側の表面の算術平均表面粗さＲａが０．６μｍ以下であり、該粘着剤層のクリープリカバリー値が９６％以上である。
　［２］本発明の別の一つの実施形態による積層体は、表面保護フィルムと被着体を含む積層体であって、該表面保護フィルムは、基材と粘着剤層を有し、該粘着剤層と該被着体が直接積層されてなり、該被着体の該表面保護フィルム側の表面の水接触角が８５°以上であり、該被着体の該表面保護フィルム側の表面の算術平均表面粗さＲａが０．６μｍ以下であり、該表面保護フィルムのせん断弾性係数Ｇが３９．０Ｎ／５０ｍｍ3以下である。
　［３］上記［１］または［２］に記載の積層体において、上記水接触角が８５°～１０５°であってもよい。
　［４］上記［１］から［３］までのいずれかに記載の積層体において、上記算術平均表面粗さＲａが０．１μｍ以下であってもよい。
　［５］上記［１］、［３］、または［４］に記載の積層体において、上記クリープリカバリー値が９９％以上であってもよい。
　［６］上記［２］から［４］までのいずれかに記載の積層体において、上記せん断弾性係数Ｇが３０．０Ｎ／５０ｍｍ3以下であってもよい。 [1] A laminate according to one embodiment of the present invention is a laminate including a surface protection film and an adherend, the surface protection film having a substrate and a pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer and the adherend being directly laminated together, the water contact angle of the surface of the adherend facing the surface protection film being 85° or more, the arithmetic mean surface roughness Ra of the surface of the adherend facing the surface protection film being 0.6 μm or less, and the creep recovery value of the pressure-sensitive adhesive layer being 96% or more.
[2] A laminate according to another embodiment of the present invention is a laminate including a surface protection film and an adherend, the surface protection film having a substrate and a pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer and the adherend being directly laminated together, the water contact angle of the surface of the adherend facing the surface protection film being 85° or more, the arithmetic mean surface roughness Ra of the surface of the adherend facing the surface protection film being 0.6 μm or less, and the shear modulus of elasticity G of the surface protection film being 39.0 N/50 mm3 or less.
[3] In the laminate according to the above [1] or [2], the water contact angle may be 85° to 105°.
[4] In the laminate according to any one of the above [1] to [3], the arithmetic mean surface roughness Ra may be 0.1 μm or less.
[5] In the laminate according to the above [1], [3], or [4], the creep recovery value may be 99% or more.
[6] In the laminate according to any one of [2] to [4] above, the shear modulus G may be 30.0 N/50 mm3 or less .
　本発明によれば、外力による変形による変形跡が残りにくく、被着体からの表面保護フィルムの初期剥離力が適度であり、被着体からの表面保護フィルムの剥離力の経時変化が小さい、表面保護フィルムと被着体を含む積層体を提供することができる。 The present invention can provide a laminate including a surface protective film and an adherend that is less likely to leave traces of deformation due to deformation caused by external forces, has an appropriate initial peel strength of the surface protective film from the adherend, and exhibits little change over time in the peel strength of the surface protective film from the adherend.
本発明の積層体の一つの実施形態を示す概略断面図である。1 is a schematic cross-sectional view showing one embodiment of a laminate of the present invention. 積層体の変形を評価する方法を説明する概略説明図である。FIG. 2 is a schematic diagram illustrating a method for evaluating deformation of a laminate.
　本明細書中で「重量」との表現がある場合は、重さを示すＳＩ系単位として慣用されている「質量」と読み替えてもよい。 Whenever the term "weight" appears in this specification, it may be read as "mass," which is the commonly used SI unit for indicating weight.
　本明細書中で「（メタ）アクリル」との表現がある場合は、「アクリルおよび／またはメタクリル」を意味し、「（メタ）アクリレート」との表現がある場合は、「アクリレートおよび／またはメタクリレート」を意味し、「（メタ）アリル」との表現がある場合は、「アリルおよび／またはメタリル」を意味し、「（メタ）アクロレイン」との表現がある場合は、「アクロレインおよび／またはメタクロレイン」を意味する。 In this specification, the term "(meth)acrylic" means "acrylic and/or methacrylic", the term "(meth)acrylate" means "acrylate and/or methacrylate", the term "(meth)allyl" means "allyl and/or methallyl", and the term "(meth)acrolein" means "acrolein and/or methacrolein".
　本発明の実施形態による積層体は、表面保護フィルムと被着体を含む。表面保護フィルムは、基材と粘着剤層を有する。 The laminate according to an embodiment of the present invention includes a surface protection film and an adherend. The surface protection film has a substrate and an adhesive layer.
　本発明の実施形態による積層体においては、粘着剤層と被着体が直接積層されてなる。 In the laminate according to an embodiment of the present invention, the adhesive layer and the adherend are directly laminated together.
　図１は、本発明の積層体の一つの実施形態であり、積層体１０００は、表面保護フィルム１００と被着体２００を含み、該表面保護フィルム１００は、基材１０と粘着剤層２０を有する。粘着剤層２０と被着体２００は直接積層されている。 FIG. 1 shows one embodiment of the laminate of the present invention, where the laminate 1000 includes a surface protective film 100 and an adherend 200, and the surface protective film 100 has a substrate 10 and an adhesive layer 20. The adhesive layer 20 and the adherend 200 are directly laminated together.
　本発明の実施形態による積層体は、表面保護フィルムと被着体を含んでいれば、本発明の効果を損なわない範囲で、任意の適切な他の層を含んでいてもよい。このような他の層としては、例えば、ガラス、ディスプレイ、撮像装置、レンズ、（ハーフ）ミラーが挙げられる。 The laminate according to the embodiment of the present invention may contain any other appropriate layers as long as the effects of the present invention are not impaired, so long as the laminate contains a surface protective film and an adherend. Examples of such other layers include glass, a display, an imaging device, a lens, and a (half) mirror.
　本発明の実施形態による積層体の総厚みは、被着体の種類や含み得る他の層の種類によって適宜設定し得る。代表的には、本発明の実施形態による積層体の総厚みは、好ましくは１０μｍ～１０００μｍであり、より好ましくは２５μｍ～８００μｍであり、さらに好ましくは４０μｍ～６００μｍであり、特に好ましくは５０μｍ～５００μｍである。 The total thickness of the laminate according to the embodiment of the present invention can be set appropriately depending on the type of adherend and the types of other layers that may be included. Typically, the total thickness of the laminate according to the embodiment of the present invention is preferably 10 μm to 1000 μm, more preferably 25 μm to 800 μm, even more preferably 40 μm to 600 μm, and particularly preferably 50 μm to 500 μm.
　本発明の実施形態による積層体においては、被着体の表面保護フィルム側（表面保護フィルムが積層されている側）の表面の水接触角が、好ましくは８５°以上であり、より好ましくは８５°～１１０°であり、さらに好ましくは８５°～１０５°であり、さらに好ましくは９０°～１００°であり、特に好ましくは９５°～１００°であり、最も好ましくは９５°～９９°である。上記水接触角が上記範囲内にあれば、本発明の効果がより発現し得る。上記水接触角が上記範囲を外れて小さすぎると、表面保護フィルムが被着体に過度に密着しやすくなり、例えば、被着体からの表面保護フィルムの初期剥離力が高くなって、被着体から表面保護フィルムを剥離できなくなるおそれがあり、被着体からの表面保護フィルムの剥離力が経時で大きく上昇しすぎて、被着体から表面保護フィルムを剥離できなくなるおそれがある。上記水接触角が上記範囲を外れて大きすぎると、表面保護フィルムが被着体に過度に密着しにくくなり、例えば、被着体からの表面保護フィルムの初期剥離力が低すぎることとなり、被着体からの表面保護フィルムの浮きが生じるおそれや、被着体の表面保護フィルムと反対側に設けられたはく離ライナー（すなわち、はく離ライナー／被着体／表面保護フィルムの積層構成における該はく離ライナー）をはく離する際に、被着体とはく離ライナーの界面でのはく離よりも表面保護フィルムと被着体の界面でのはく離が起こってしまうというはく離不良（意図しない箇所のはく離）が生じるおそれがある。 In the laminate according to an embodiment of the present invention, the water contact angle of the surface of the adherend on the surface protection film side (the side on which the surface protection film is laminated) is preferably 85° or more, more preferably 85° to 110°, even more preferably 85° to 105°, even more preferably 90° to 100°, particularly preferably 95° to 100°, and most preferably 95° to 99°. If the water contact angle is within the above range, the effects of the present invention can be more effectively achieved. If the water contact angle is too small outside the above range, the surface protection film is likely to adhere excessively to the adherend, and for example, the initial peeling force of the surface protection film from the adherend may become too high, making it impossible to peel the surface protection film from the adherend, or the peeling force of the surface protection film from the adherend may increase too much over time, making it impossible to peel the surface protection film from the adherend. If the water contact angle is too large outside the above range, the surface protection film will not adhere too closely to the adherend, and for example, the initial peel strength of the surface protection film from the adherend will be too low, which may cause the surface protection film to lift off from the adherend, or when peeling off a release liner provided on the side of the adherend opposite the surface protection film (i.e., the release liner in a laminated structure of release liner/adherend/surface protection film), peeling will occur at the interface between the surface protection film and the adherend rather than at the interface between the adherend and the release liner, resulting in poor peeling (peeling at an unintended location).
　本発明の実施形態による積層体においては、被着体の表面保護フィルム側（表面保護フィルムが積層されている側）の表面の算術平均表面粗さＲａが、好ましくは０．６μｍ以下であり、より好ましくは０．３５μｍ以下であり、さらに好ましくは０．２μｍ以下であり、特に好ましくは０．１μｍ以下であり、最も好ましくは０．０８μｍ以下である。上記算術平均表面粗さＲａの下限値は小さければ小さいほどよく、好ましくは０μｍ以上である。上記算術平均表面粗さＲａが上記範囲内にあれば、本発明の効果がより発現し得る。上記算術平均表面粗さＲａが上記範囲を外れて大きすぎると、例えば、表面保護フィルムが有する粘着剤層の厚みが大きい場合、被着体からの表面保護フィルムの剥離力が経時で大きく上昇しすぎて、被着体から表面保護フィルムを剥離できなくなるおそれがある。 In the laminate according to an embodiment of the present invention, the arithmetic mean surface roughness Ra of the surface of the adherend on the surface protection film side (the side on which the surface protection film is laminated) is preferably 0.6 μm or less, more preferably 0.35 μm or less, even more preferably 0.2 μm or less, particularly preferably 0.1 μm or less, and most preferably 0.08 μm or less. The lower limit of the arithmetic mean surface roughness Ra is preferably as small as possible, and is preferably 0 μm or more. If the arithmetic mean surface roughness Ra is within the above range, the effect of the present invention can be more effectively achieved. If the arithmetic mean surface roughness Ra is too large outside the above range, for example, if the thickness of the adhesive layer of the surface protection film is large, the peeling force of the surface protection film from the adherend increases too much over time, and it may become impossible to peel the surface protection film from the adherend.
　本発明の実施形態による積層体においては、表面保護フィルムが有する粘着剤層のクリープリカバリー値が、好ましくは９６％以上であり、より好ましくは９７％以上であり、さらに好ましくは９８％以上であり、特に好ましくは９９％以上である。上記クリープリカバリー値が上記範囲内にあれば、本発明の効果がより発現し得る。上記クリープリカバリー値が上記範囲を外れて小さすぎると、外力による変形による変形跡が残りやすくなるおそれがある。 In the laminate according to an embodiment of the present invention, the creep recovery value of the adhesive layer of the surface protection film is preferably 96% or more, more preferably 97% or more, even more preferably 98% or more, and particularly preferably 99% or more. If the creep recovery value is within the above range, the effects of the present invention can be more effectively achieved. If the creep recovery value is too small outside the above range, there is a risk that deformation marks due to deformation caused by external forces will be more likely to remain.
　本発明の実施形態による積層体においては、表面保護フィルムのせん断弾性係数Ｇが、好ましくは３９．０Ｎ／５０ｍｍ3以下であり、より好ましくは２７．０Ｎ／５０ｍｍ3～３９．０Ｎ／５０ｍｍ3であり、さらに好ましくは２７．５Ｎ／５０ｍｍ3～３８．５Ｎ／５０ｍｍ3であり、特に好ましくは２８．０Ｎ／５０ｍｍ3～３８．０Ｎ／５０ｍｍ3である。上記せん断弾性係数Ｇが上記範囲内にあれば、本発明の効果がより発現し得る。上記せん断弾性係数Ｇが上記範囲を外れてると、外力による変形による変形跡が残りやすくなるおそれがある。 In the laminate according to the embodiment of the present invention, the shear modulus G of the surface protective film is preferably 39.0 N/50 mm 3 or less, more preferably 27.0 N/50 mm 3 to 39.0 N/50 mm 3 , even more preferably 27.5 N/50 mm 3 to 38.5 N/50 mm 3 , and particularly preferably 28.0 N/50 mm 3 to 38.0 N/50 mm 3. If the shear modulus G is within the above range, the effects of the present invention can be more effectively achieved. If the shear modulus G is outside the above range, there is a risk that deformation marks due to deformation caused by external force will be easily left.
　本発明の実施形態による積層体においては、表面保護フィルムが有する粘着剤層の厚みが、好ましくは１μｍ以上であり、より好ましくは５μｍ以上であり、さらに好ましくは１０μｍ以上であり、特に好ましくは１５μｍ以上であり、最も好ましくは１８μｍ以上である。上記粘着剤層の厚みの上限値は、好ましくは１５０μｍ以下であり、より好ましくは１００μｍ以下であり、さらに好ましくは８０μｍ以下であり、特に好ましくは５０μｍ以下であり、最も好ましくは３０μｍ以下である。上記粘着剤層の厚みが上記範囲内にあれば、本発明の効果がより発現し得る。上記粘着剤層の厚みが上記範囲を外れて小さすぎると、外力による変形による変形跡が残りやすくなるおそれがある。上記粘着剤層の厚みが上記範囲を外れて大きすぎると、被着体が光学部材である場合など、薄型デバイスへの適用ができなくなるおそれがある。 In the laminate according to an embodiment of the present invention, the thickness of the adhesive layer of the surface protection film is preferably 1 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, particularly preferably 15 μm or more, and most preferably 18 μm or more. The upper limit of the thickness of the adhesive layer is preferably 150 μm or less, more preferably 100 μm or less, even more preferably 80 μm or less, particularly preferably 50 μm or less, and most preferably 30 μm or less. If the thickness of the adhesive layer is within the above range, the effects of the present invention can be more effectively achieved. If the thickness of the adhesive layer is too small outside the above range, there is a risk that deformation marks due to deformation caused by external forces will be easily left. If the thickness of the adhesive layer is too large outside the above range, there is a risk that it will not be possible to apply it to thin devices, such as when the adherend is an optical member.
≪≪１．表面保護フィルム≫≫
　表面保護フィルムは、基材と粘着剤層を有する。表面保護フィルムの一つの実施形態は、基材と粘着剤層とからなる（例えば、図１に示すように、表面保護フィルム１００が、基材１０と粘着剤層２０とからなる）。 ≪≪1. Surface protection film≫≫
The surface protection film has a substrate and a pressure-sensitive adhesive layer. One embodiment of the surface protection film is made of a substrate and a pressure-sensitive adhesive layer (for example, as shown in FIG. 1, a surface protection film 100 is made of a substrate 10 and a pressure-sensitive adhesive layer 20).
　表面保護フィルムは、本発明の効果を損なわない範囲で、基材と粘着剤層以外の任意の適切な他の層を有していてもよい。 The surface protection film may have any other appropriate layers other than the substrate and the adhesive layer, as long as the effects of the present invention are not impaired.
　このような他の層としては、例えば、易接着層、易滑層、ブロッキング防止層、帯電防止層、反射防止層、オリゴマー防止層、粘着剤層の基材と反対側の表面に設けるはく離ライナーが挙げられる。 Such other layers include, for example, an easy-adhesion layer, an easy-slip layer, an anti-blocking layer, an antistatic layer, an anti-reflection layer, an anti-oligomer layer, and a release liner provided on the surface of the adhesive layer opposite the substrate.
　表面保護フィルムの構成要素（基材、粘着剤層、必要に応じて他の層など）は、本発明の効果を損なわない範囲で、任意の適切な添加剤を含んでいてもよい。このような添加剤としては、例えば、酸化防止剤、紫外線吸収剤、光安定剤、造核剤、充填剤、顔料、界面活性剤、帯電防止剤が挙げられる。 The components of the surface protection film (substrate, adhesive layer, other layers as necessary, etc.) may contain any appropriate additives as long as they do not impair the effects of the present invention. Examples of such additives include antioxidants, UV absorbers, light stabilizers, nucleating agents, fillers, pigments, surfactants, and antistatic agents.
　粘着剤層の基材と反対側には、被着体と積層するまでの間、保護等のために、必要に応じて、はく離ライナーが設けられていてもよい。 If necessary, a release liner may be provided on the side of the adhesive layer opposite the substrate for protection etc. until it is laminated with the adherend.
　はく離ライナーとしては、例えば、紙やプラスチックフィルム等の基材（ライナー基材）の表面がシリコーン処理されたはく離ライナー、紙やプラスチックフィルム等の基材（ライナー基材）の表面がポリオレフィン系樹脂によりラミネートされたはく離ライナーなどが挙げられる。ライナー基材としてのプラスチックフィルムとしては、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、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、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。 Examples of release liners include release liners in which the surface of a substrate (liner substrate) such as paper or plastic film is silicone-treated, and release liners in which the surface of a substrate (liner substrate) such as paper or plastic film is laminated with a polyolefin resin. Examples of plastic films that can be used as liner substrates include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene-vinyl acetate copolymer film.
　はく離ライナーの厚みは、好ましくは１μｍ～５００μｍであり、より好ましくは３μｍ～４５０μｍであり、さらに好ましくは５μｍ～４００μｍであり、特に好ましくは１０μｍ～３００μｍである。 The thickness of the release liner is preferably 1 μm to 500 μm, more preferably 3 μm to 450 μm, even more preferably 5 μm to 400 μm, and particularly preferably 10 μm to 300 μm.
≪１－１．基材≫
　基材は、１層からなる基材であってもよいし、２層以上の積層構造からなる基材であってもよい。 <<1-1. Substrate≫
The substrate may be a substrate made of one layer, or a substrate made of a laminated structure of two or more layers.
　基材の厚みは、本発明の効果を損なわない範囲で、任意の適切な厚みを採用し得る。本発明の効果をより発現させ得る点で、基材の厚みは、好ましくは５μｍ～１０００μｍであり、より好ましくは１０μｍ～８００μｍであり、さらに好ましくは２０μｍ～６００μｍであり、特に好ましくは３０μｍ～４００μｍである。 The thickness of the substrate may be any appropriate thickness as long as it does not impair the effects of the present invention. In order to maximize the effects of the present invention, the thickness of the substrate is preferably 5 μm to 1000 μm, more preferably 10 μm to 800 μm, even more preferably 20 μm to 600 μm, and particularly preferably 30 μm to 400 μm.
　基材の材料としては、本発明の効果を損なわない範囲で、任意の適切な材料を採用し得る。本発明の効果をより発現させ得る点で、このような材料としては、好ましくは、プラスチックが挙げられる。 Any suitable material may be used as the material for the substrate, provided that the effect of the present invention is not impaired. In terms of being able to more effectively express the effect of the present invention, such a material is preferably plastic.
　プラスチックとしては、本発明の効果を損なわない範囲で、任意の適切なプラスチックを採用し得る。本発明の効果をより発現させ得る点で、このようなプラスチックとしては、好ましくは、熱可塑性樹脂が挙げられる。 Any suitable plastic may be used as the plastic as long as it does not impair the effects of the present invention. In terms of being able to more effectively express the effects of the present invention, a preferable example of such a plastic is a thermoplastic resin.
　熱可塑性樹脂としては、例えば、ポリエステル、アクリル系樹脂、ウレタン系樹脂、ポリカーボネート、トリアセチルセルロース（ＴＡＣ）、ポリオレフィン（オレフィン単独重合体、オレフィンと他のモノマーの共重合体）、ポリアミド（ナイロン）、全芳香族ポリアミド（アラミド）、ポリイミド（ＰＩ）、ポリ塩化ビニル（ＰＶＣ）、ポリ酢酸ビニル、環状オレフィン系ポリマーが挙げられる。 Examples of thermoplastic resins include polyester, acrylic resins, urethane resins, polycarbonate, triacetyl cellulose (TAC), polyolefins (olefin homopolymers, copolymers of olefins and other monomers), polyamides (nylons), wholly aromatic polyamides (aramids), polyimides (PI), polyvinyl chloride (PVC), polyvinyl acetate, and cyclic olefin polymers.
　熱可塑性樹脂としては、本発明の効果をより発現させ得る点で、ポリエステルが好ましい。ポリエステルとしては、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（ＰＢＴ）が挙げられ、本発明の効果をより発現させ得る点で、ポリエチレンテレフタレート（ＰＥＴ）が好ましい。 As the thermoplastic resin, polyester is preferred in that it can better bring out the effects of the present invention. Examples of polyester include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT), and polyethylene terephthalate (PET) is preferred in that it can better bring out the effects of the present invention.
≪１－２．粘着剤層≫
　粘着剤層は、１層からなる粘着剤層であってもよいし、２層以上の積層構造からなる粘着剤層であってもよい。 <1-2. Adhesive layer>
The pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer consisting of a single layer, or may be a pressure-sensitive adhesive layer consisting of a laminated structure of two or more layers.
　粘着剤層の厚みは、前述した通りである。 The thickness of the adhesive layer is as described above.
　粘着剤層を構成する粘着剤は、好ましくは、アクリル系粘着剤、ウレタン系粘着剤、および、シリコーン系粘着剤からなる群から選ばれる少なくとも１種である。 The adhesive constituting the adhesive layer is preferably at least one type selected from the group consisting of acrylic adhesives, urethane adhesives, and silicone adhesives.
　粘着剤層は、より好ましくは、アクリル系粘着剤から構成される。 The adhesive layer is more preferably composed of an acrylic adhesive.
　アクリル系粘着剤は、アクリル系粘着剤組成物から形成される。 The acrylic adhesive is formed from an acrylic adhesive composition.
　アクリル系粘着剤は、このように、アクリル系粘着剤組成物から形成されるものとして規定し得る。これは、アクリル系粘着剤は、アクリル系粘着剤組成物が、加熱や紫外線照射などによって架橋反応などを起こすことにより、アクリル系粘着剤となるため、アクリル系粘着剤をその構造により直接特定することが不可能であり、また、およそ実際的でないという事情（「不可能・非実際的事情」）が存在するため、「アクリル系粘着剤組成物から形成されるもの」との規定により、アクリル系粘着剤を「物」として妥当に特定したものである。 In this way, an acrylic adhesive can be defined as something formed from an acrylic adhesive composition. This is because an acrylic adhesive becomes an acrylic adhesive when an acrylic adhesive composition undergoes a crosslinking reaction due to heating or exposure to ultraviolet light, making it impossible to directly identify an acrylic adhesive by its structure, and there are circumstances that make it impractical to do so ("impossible/impractical circumstances"). Therefore, the definition of "something formed from an acrylic adhesive composition" appropriately identifies an acrylic adhesive as a "thing."
　粘着剤層は、任意の適切な方法によって形成し得る。このような方法としては、例えば、粘着剤層を構成する粘着剤を形成する粘着剤組成物を任意の適切な基材上に塗布し、必要に応じて加熱や乾燥を行い、必要に応じて硬化させて、該基材上において粘着剤層を形成する方法、粘着剤層を構成する粘着剤を形成する粘着剤組成物を任意の適切なはく離ライナーなどのフィルム上に塗布し、必要に応じて加熱や乾燥を行い、必要に応じて硬化させて、該フィルム上において粘着剤層を形成し、該粘着剤層上に任意の適切な基材を貼り合わせて転写することにより、該基材上において粘着剤層を形成する方法、が挙げられる。 The adhesive layer may be formed by any suitable method. Examples of such methods include a method in which an adhesive composition that forms the adhesive constituting the adhesive layer is applied to any suitable substrate, and heated or dried as necessary, and cured as necessary to form an adhesive layer on the substrate; and a method in which an adhesive composition that forms the adhesive constituting the adhesive layer is applied to a film such as any suitable release liner, and heated or dried as necessary, and cured as necessary to form an adhesive layer on the film, and an adhesive layer is formed on the substrate by laminating and transferring any suitable substrate onto the adhesive layer.
　アクリル系粘着剤組成物を塗布する手段としては、本発明の効果を損なわない範囲で、任意の適切な手段を採用し得る。このような塗布の手段としては、例えば、ロールコート法、グラビアロールコート法、リバースロールコート法、キスロールコート法、ディップロールコート法、バーコート法、ロールブラッシュコート法、スプレーコート法、ナイフコート法、エアーナイフコート法、コンマコート法、ダイレクトコート法、ダイコート法が挙げられる。 Any appropriate means may be used to apply the acrylic adhesive composition as long as it does not impair the effects of the present invention. Examples of such application means include roll coating, gravure roll coating, reverse roll coating, kiss roll coating, dip roll coating, bar coating, roll brush coating, spray coating, knife coating, air knife coating, comma coating, direct coating, and die coating.
　アクリル系粘着剤組成物の加熱や乾燥は、本発明の効果を損なわない範囲で、任意の適切な手段を採用し得る。このような加熱や乾燥の手段としては、例えば、６０℃～１８０℃に加熱することや、例えば、室温程度の温度で、エージング処理を行うことが挙げられる。 Any appropriate means may be used for heating or drying the acrylic adhesive composition as long as it does not impair the effects of the present invention. Such heating or drying means include, for example, heating to 60°C to 180°C, or performing an aging treatment at a temperature around room temperature.
　アクリル系粘着剤組成物の硬化は、本発明の効果を損なわない範囲で、任意の適切な手段を採用し得る。このような硬化の手段としては、例えば、熱、紫外線照射、レーザー線照射、α線照射、β線照射、γ線照射、Ｘ線照射、電子線照射が挙げられる。 Any suitable means may be used to cure the acrylic adhesive composition as long as it does not impair the effects of the present invention. Examples of such curing means include heat, ultraviolet radiation, laser radiation, alpha radiation, beta radiation, gamma radiation, X-ray radiation, and electron beam radiation.
　アクリル系粘着剤組成物は、本発明の効果をより発現させ得る点で、好ましくは、アクリル系ポリマーを含む。 The acrylic adhesive composition preferably contains an acrylic polymer, which can further enhance the effects of the present invention.
＜１－２－ａ．アクリル系ポリマー＞
　アクリル系ポリマーは、アクリル系粘着剤の分野においていわゆるベースポリマーと称され得るものである。アクリル系ポリマーは、１種のみであってもよいし、２種以上であってもよい。 <1-2-a. Acrylic polymer>
The acrylic polymer may be referred to as a so-called base polymer in the field of acrylic pressure-sensitive adhesives. The acrylic polymer may be one type only, or two or more types may be used.
　すなわち、粘着剤層の好ましい実施形態は、アクリル系粘着剤組成物から形成されるアクリル系粘着剤から構成され、該アクリル系粘着剤組成物はアクリル系ポリマーをベースポリマーとして含む実施形態である。 In other words, a preferred embodiment of the adhesive layer is one in which the adhesive layer is composed of an acrylic adhesive formed from an acrylic adhesive composition, and the acrylic adhesive composition contains an acrylic polymer as a base polymer.
　アクリル系粘着剤組成物中のアクリル系ポリマーの含有割合は、固形分換算で、好ましくは６０重量％～９９．９重量％であり、より好ましくは６５重量％～９９．９重量％であり、さらに好ましくは７０重量％～９９．９重量％であり、特に好ましくは７５重量％～９９．９重量％であり、最も好ましくは８０重量％～９９．９重量％である。 The content of the acrylic polymer in the acrylic adhesive composition is preferably 60% by weight to 99.9% by weight, more preferably 65% by weight to 99.9% by weight, even more preferably 70% by weight to 99.9% by weight, particularly preferably 75% by weight to 99.9% by weight, and most preferably 80% by weight to 99.9% by weight, calculated as solid content.
　アクリル系ポリマーとしては、本発明の効果を損なわない範囲で、任意の適切なアクリル系ポリマーを採用し得る。 Any suitable acrylic polymer may be used as the acrylic polymer as long as it does not impair the effects of the present invention.
　アクリル系ポリマーの重量平均分子量は、本発明の効果をより発現させ得る点で、好ましくは３０万～２００万であり、より好ましくは３５万～１５０万であり、さらに好ましくは４０万～１００万であり、特に好ましくは５０万～１００万である。上記重量平均分子量が低すぎると、低分子量成分が多く含まれる傾向があり、低分子量成分の塑性変形が起こり得るため、外力による変形による変形跡が残りやすくなるおそれがある。 The weight average molecular weight of the acrylic polymer is preferably 300,000 to 2,000,000, more preferably 350,000 to 1,500,000, even more preferably 400,000 to 1,000,000, and particularly preferably 500,000 to 1,000,000, in order to better express the effects of the present invention. If the weight average molecular weight is too low, there is a tendency for a large amount of low molecular weight components to be included, which may cause plastic deformation of the low molecular weight components, and there is a risk that deformation marks due to deformation caused by external forces may be easily left behind.
　アクリル系ポリマーの好ましい実施形態は、重合開始剤を用いた溶液重合で調製したアクリル系ポリマーである。重合開始剤を用いた重合の方法としては、例えば、従来公知の方法など、本発明の効果を損なわない範囲で、任意の適切な方法を採用し得る。 A preferred embodiment of the acrylic polymer is an acrylic polymer prepared by solution polymerization using a polymerization initiator. As a method of polymerization using a polymerization initiator, any appropriate method, such as a conventionally known method, may be adopted as long as it does not impair the effects of the present invention.
　アクリル系ポリマーは、モノマー成分（Ｍ）を重合して得られるものである。ここでいうモノマー成分（Ｍ）には、アクリル系粘着剤組成物中に含み得る後述する架橋剤は包含されない。アクリル系ポリマーを重合により得る際には、モノマー成分（Ｍ）、重合開始剤以外に、本発明の効果を損なわない範囲で、任意の適切な添加剤を用いてもよい。 The acrylic polymer is obtained by polymerizing the monomer component (M). The monomer component (M) does not include the crosslinking agent, which may be contained in the acrylic adhesive composition and will be described later. When obtaining the acrylic polymer by polymerization, in addition to the monomer component (M) and the polymerization initiator, any suitable additive may be used as long as it does not impair the effects of the present invention.
　アクリル系ポリマーは、このように、モノマー成分（Ｍ）を重合して得られるものとして規定し得る。これは、アクリル系ポリマーは、モノマー成分（Ｍ）が重合反応を起こすことによりアクリル系ポリマーとなり、アクリル系ポリマーをその構造により直接特定することが不可能であり、また、およそ実際的でないという事情（「不可能・非実際的事情」）が存在するため、「モノマー成分（Ｍ）を重合して得られるもの」との規定により、アクリル系ポリマーを「物」として妥当に特定したものである。 Acrylic polymers can be defined as those obtained by polymerizing monomer component (M) in this way. This is because acrylic polymers become acrylic polymers through the polymerization reaction of monomer component (M), and because it is impossible and virtually impractical to directly identify acrylic polymers by their structure ("impossible/impractical circumstances") exist, and so acrylic polymers are appropriately defined as "products" by the definition that they are "obtained by polymerizing monomer component (M)."
　アクリル系ポリマーは、本発明の効果をより発現させ得る点で、そのガラス転移温度Ｔｇが、好ましくは０℃以下であり、より好ましくは－１０℃以下であり、さらに好ましくは－１５℃以下であり、特に好ましくは－２０℃以下であり、最も好ましくは－２５℃以下である。上記ガラス転移温度Ｔｇの下限値は、好ましくは－１００℃以上であり、より好ましくは－９０℃以上であり、さらに好ましくは－８０℃以上である。アクリル系ポリマーのガラス転移温度Ｔｇを上記の特定の範囲内に調整することにより、本発明の効果をより発現させ得る。 The acrylic polymer preferably has a glass transition temperature Tg of 0°C or lower, more preferably -10°C or lower, even more preferably -15°C or lower, particularly preferably -20°C or lower, and most preferably -25°C or lower, so that the effects of the present invention can be more effectively expressed. The lower limit of the glass transition temperature Tg is preferably -100°C or higher, more preferably -90°C or higher, and even more preferably -80°C or higher. By adjusting the glass transition temperature Tg of the acrylic polymer to fall within the above specific range, the effects of the present invention can be more effectively expressed.
　ここで、アクリル系ポリマーのガラス転移温度Ｔｇとは、アクリル系ポリマーを構成する各モノマーの単独重合体（ホモポリマー）のガラス転移温度Ｔｇおよび該モノマーの重量分率（重量基準の共重合割合）に基づいて、フォックス（Ｆｏｘ）の式から求められる値をいう。Ｆｏｘの式とは、以下に示すように、共重合体のガラス転移温度Ｔｇと、該共重合体を構成するモノマーのそれぞれを単独重合したホモポリマーのガラス転移温度Ｔｇｉとの関係式である。
１／Ｔｇ＝Σ（Ｗｉ／Ｔｇｉ） Here, the glass transition temperature Tg of an acrylic polymer refers to a value calculated from the Fox formula based on the glass transition temperature Tg of a homopolymer of each monomer constituting the acrylic polymer and the weight fraction (copolymerization ratio based on weight) of the monomer. The Fox formula is a relational expression between the glass transition temperature Tg of a copolymer and the glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer, as shown below.
1/Tg=Σ(Wi/Tgi)
　上記Ｆｏｘの式において、Ｔｇは共重合体のガラス転移温度（単位：Ｋ）、Ｗｉは該共重合体におけるモノマーｉの重量分率（重量基準の共重合割合）、Ｔｇｉはモノマーｉのホモポリマーのガラス転移温度（単位：Ｋ）を表す。ホモポリマーのガラス転移温度Ｔｇとしては、公知資料に記載の値を採用するものとする。 In the above Fox formula, Tg is the glass transition temperature (unit: K) of the copolymer, Wi is the weight fraction of monomer i in the copolymer (copolymerization ratio by weight), and Tgi is the glass transition temperature (unit: K) of the homopolymer of monomer i. The glass transition temperature Tg of the homopolymer is to be a value listed in publicly available documents.
　ホモポリマーのガラス転移温度Ｔｇとして、例えば、具体的には以下の値を用い得る。
ｎ－ブチルアクリレート（ＢＡ）のホモポリマー：－５５℃
ラウリルアクリレート（ＬＡ）のホモポリマー：－２３℃
２－エチルヘキシルアクリレート（２ＥＨＡ）のホモポリマー：－７０℃
メタクリル酸メチル（ＭＭＡ）のホモポリマー：１０５℃
２－ヒドロキシエチルアクリレート（ＨＥＡ）のホモポリマー：－１５℃
４－ヒドロキシブチルアクリレート（４ＨＢＡ）のホモポリマー：－４０℃
Ｎ－ビニル－２－ピロリドン（ＮＶＰ）のホモポリマー：８０℃
酢酸ビニル（ＶＡｃ）のホモポリマー：３０℃
アクリル酸（ＡＡ）のホモポリマー：１０６℃ As the glass transition temperature Tg of the homopolymer, specifically, for example, the following values can be used.
Homopolymer of n-butyl acrylate (BA): -55°C
Homopolymer of lauryl acrylate (LA): -23°C
Homopolymer of 2-ethylhexyl acrylate (2EHA): -70°C
Homopolymer of methyl methacrylate (MMA): 105°C
Homopolymer of 2-hydroxyethyl acrylate (HEA): -15°C
Homopolymer of 4-hydroxybutyl acrylate (4HBA): -40°C
Homopolymer of N-vinyl-2-pyrrolidone (NVP): 80° C.
Homopolymer of vinyl acetate (VAc): 30°C
Homopolymer of acrylic acid (AA): 106°C
　上記で例示した以外のホモポリマーのガラス転移温度Ｔｇについては、「Ｐｏｌｙｍｅｒ　Ｈａｎｄｂｏｏｋ」（第３版、Ｊｏｈｎ　Ｗｉｌｅｙ　＆　Ｓｏｎｓ，Ｉｎｃ．，１９８９）に記載の数値を用いることができる。上記「Ｐｏｌｙｍｅｒ　Ｈａｎｄｂｏｏｋ」に複数の数値が記載されている場合は、ｃｏｎｖｅｎｔｉｏｎａｌの値を採用する。上記「Ｐｏｌｙｍｅｒ　Ｈａｎｄｂｏｏｋ」に記載のないモノマーについては、モノマー製造企業のカタログ値を採用する。上記「Ｐｏｌｙｍｅｒ　Ｈａｎｄｂｏｏｋ」に記載がなく、モノマー製造企業のカタログ値も提供されていないモノマーのホモポリマーのガラス転移温度Ｔｇとしては、特開２００７－５１２７１号公報に記載の測定方法により得られる値を用いるものとする。 For the glass transition temperature Tg of homopolymers other than those exemplified above, the values listed in "Polymer Handbook" (3rd Edition, John Wiley & Sons, Inc., 1989) can be used. If multiple values are listed in the "Polymer Handbook," the conventional values are used. For monomers not listed in the "Polymer Handbook," the catalog values of the monomer manufacturers are used. For the glass transition temperature Tg of homopolymers of monomers not listed in the "Polymer Handbook" and for which no catalog values are provided by the monomer manufacturers, the values obtained by the measurement method described in JP 2007-51271 A are used.
　モノマー成分（Ｍ）は、好ましくは、アルキル（メタ）アクリレート（ａ）と極性基含有モノマー（ｂ）を含む。アルキル（メタ）アクリレート（ａ）は、１種のみであってもよいし、２種以上であってもよい。極性基含有モノマー（ｂ）は、１種のみであってもよいし、２種以上であってもよい。 The monomer component (M) preferably contains an alkyl (meth)acrylate (a) and a polar group-containing monomer (b). The alkyl (meth)acrylate (a) may be of only one type or of two or more types. The polar group-containing monomer (b) may be of only one type or of two or more types.
　なお、アルキル（メタ）アクリレート（ａ）のエステル部分のアルキル基（以下、単に「エステル部分のアルキル基」と称することがある。）には、水酸基を含むアルキル基および水酸基以外の極性基を含むアルキル基は含まない。したがって、アルキル（メタ）アクリレート（ａ）は、極性基含有モノマー（ｂ）と明確に区別される。 The alkyl group in the ester portion of alkyl (meth)acrylate (a) (hereinafter sometimes simply referred to as "alkyl group in the ester portion") does not include alkyl groups containing a hydroxyl group or alkyl groups containing a polar group other than a hydroxyl group. Therefore, alkyl (meth)acrylate (a) is clearly distinguished from polar group-containing monomer (b).
　モノマー成分（Ｍ）中のアルキル（メタ）アクリレート（ａ）の含有割合は、本発明の効果をより発現させ得る点で、好ましくは４０重量％～９９．９９９重量％である。 The content of alkyl (meth)acrylate (a) in monomer component (M) is preferably 40% to 99.999% by weight, in order to better demonstrate the effects of the present invention.
　モノマー成分（Ｍ）が含む極性基含有モノマー（ｂ）が、後述するように、水酸基含有モノマー（ｂ１）を含み水酸基以外の極性基を有するモノマー（ｂ２）を含まない実施形態である場合は、特に、モノマー成分（Ｍ）中のアルキル（メタ）アクリレート（ａ）の含有割合は、本発明の効果をより発現させ得る点で、より好ましくは６０重量％～９９．９９９重量％であり、さらに好ましくは８０重量％～９９．９９重量％であり、さらに好ましくは８５重量％～９９．９重量％であり、特に好ましくは９０重量％～９９．５重量％であり、最も好ましくは９５重量％～９９重量％である。 In the case where the polar group-containing monomer (b) contained in the monomer component (M) is an embodiment that contains a hydroxyl group-containing monomer (b1) but does not contain a monomer (b2) having a polar group other than a hydroxyl group, as described below, the content of the alkyl (meth)acrylate (a) in the monomer component (M) is more preferably 60% by weight to 99.999% by weight, even more preferably 80% by weight to 99.99% by weight, even more preferably 85% by weight to 99.9% by weight, particularly preferably 90% by weight to 99.5% by weight, and most preferably 95% by weight to 99% by weight, in order to further exhibit the effects of the present invention.
　モノマー成分（Ｍ）が含む極性基含有モノマー（ｂ）が、後述するように、水酸基含有モノマー（ｂ１）を含まず水酸基以外の極性基を有するモノマー（ｂ２）を含む実施形態である場合は、特に、モノマー成分（Ｍ）中のアルキル（メタ）アクリレート（ａ）の含有割合は、本発明の効果をより発現させ得る点で、より好ましくは４３重量％～９０重量％であり、さらに好ましくは４６重量％～８０重量％であり、特に好ましくは４８重量％～７０重量％であり、最も好ましくは５０重量％～６０重量％である。 In the case where the polar group-containing monomer (b) contained in the monomer component (M) does not contain a hydroxyl group-containing monomer (b1) but contains a monomer (b2) having a polar group other than a hydroxyl group, as described below, the content of the alkyl (meth)acrylate (a) in the monomer component (M) is more preferably 43% to 90% by weight, even more preferably 46% to 80% by weight, particularly preferably 48% to 70% by weight, and most preferably 50% to 60% by weight, in order to further exert the effects of the present invention.
　アルキル（メタ）アクリレート（ａ）において、エステル部分のアルキル基は、本発明の効果をより発現させ得る点で、好ましくは、炭素数１～２０のアルキル基であり、より好ましくは、炭素数１～１８のアルキル基であり、さらに好ましくは、炭素数１～１６のアルキル基であり、特に好ましくは、炭素数１～１４のアルキル基であり、最も好ましくは、炭素数１～１２のアルキル基である。 In the alkyl (meth)acrylate (a), the alkyl group of the ester portion is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 18 carbon atoms, even more preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably an alkyl group having 1 to 14 carbon atoms, and most preferably an alkyl group having 1 to 12 carbon atoms, in order to further exert the effects of the present invention.
　エステル部分のアルキル基は、本発明の効果をより発現させ得る点で、好ましくは、鎖状アルキル基である。ここで鎖状とは、直鎖状および分岐鎖状を包含する意味である。 The alkyl group of the ester portion is preferably a chain alkyl group, since this can better exert the effects of the present invention. Here, chain alkyl group includes both linear and branched chains.
　アルキル（メタ）アクリレート（ａ）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、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、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、ペンタデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ヘプタデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ノナデシル（メタ）アクリレート、エイコシル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレートが挙げられる。 Examples of the alkyl (meth)acrylate (a) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.
　本発明の効果をより発現させ得る点で、アルキル（メタ）アクリレート（ａ）は、その単独重合体（ホモポリマー）のガラス転移温度Ｔｇが－８０℃～－６０℃の範囲内にあるアルキル（メタ）アクリレート（ａ１）を含むことが好ましい。このようなアルキル（メタ）アクリレート（ａ１）としては、例えば、２－エチルヘキシルアクリレート（２ＥＨＡ）（その単独重合体（ホモポリマー）のガラス転移温度Ｔｇ＝－７０℃）が挙げられる。 In order to further exert the effects of the present invention, it is preferable that the alkyl (meth)acrylate (a) contains an alkyl (meth)acrylate (a1) whose homopolymer has a glass transition temperature Tg in the range of -80°C to -60°C. An example of such an alkyl (meth)acrylate (a1) is 2-ethylhexyl acrylate (2EHA) (whose homopolymer has a glass transition temperature Tg of -70°C).
　アルキル（メタ）アクリレート（ａ１）の単独重合体（ホモポリマー）のガラス転移温度Ｔｇとして、例えば、具体的には以下の値を用い得る。
ｎ－ブチルアクリレート（ＢＡ）のホモポリマー：－５５℃
ラウリルアクリレート（ＬＡ）のホモポリマー：－２３℃
２－エチルヘキシルアクリレート（２ＥＨＡ）のホモポリマー：－７０℃ As the glass transition temperature Tg of a homopolymer of the alkyl (meth)acrylate (a1), for example, the following values can be used specifically.
Homopolymer of n-butyl acrylate (BA): -55°C
Homopolymer of lauryl acrylate (LA): -23°C
Homopolymer of 2-ethylhexyl acrylate (2EHA): -70°C
　上記で例示した以外のホモポリマーのガラス転移温度Ｔｇについては、「Ｐｏｌｙｍｅｒ　Ｈａｎｄｂｏｏｋ」（第３版、Ｊｏｈｎ　Ｗｉｌｅｙ　＆　Ｓｏｎｓ，Ｉｎｃ．，１９８９）に記載の数値を用いることができる。上記「Ｐｏｌｙｍｅｒ　Ｈａｎｄｂｏｏｋ」に複数の数値が記載されている場合は、ｃｏｎｖｅｎｔｉｏｎａｌの値を採用する。上記「Ｐｏｌｙｍｅｒ　Ｈａｎｄｂｏｏｋ」に記載のないモノマーについては、モノマー製造企業のカタログ値を採用する。上記「Ｐｏｌｙｍｅｒ　Ｈａｎｄｂｏｏｋ」に記載がなく、モノマー製造企業のカタログ値も提供されていないモノマーのホモポリマーのガラス転移温度Ｔｇとしては、特開２００７－５１２７１号公報に記載の測定方法により得られる値を用いるものとする。 For the glass transition temperature Tg of homopolymers other than those exemplified above, the values listed in "Polymer Handbook" (3rd Edition, John Wiley & Sons, Inc., 1989) can be used. If multiple values are listed in the "Polymer Handbook," the conventional values are used. For monomers not listed in the "Polymer Handbook," the catalog values of the monomer manufacturers are used. For the glass transition temperature Tg of homopolymers of monomers not listed in the "Polymer Handbook" and for which no catalog values are provided by the monomer manufacturers, the values obtained by the measurement method described in JP 2007-51271 A are used.
　アルキル（メタ）アクリレート（ａ）全量中のアルキル（メタ）アクリレート（ａ１）の含有割合は、本発明の効果をより発現させ得る点で、好ましくは５０重量％～１００重量％であり、より好ましくは７０重量％～１００重量％であり、さらに好ましくは８０重量％～１００重量％であり、特に好ましくは９０重量％～１００重量％であり、最も好ましくは９５重量％～１００重量％である。 The content of alkyl (meth)acrylate (a1) in the total amount of alkyl (meth)acrylate (a) is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, even more preferably 80% by weight to 100% by weight, particularly preferably 90% by weight to 100% by weight, and most preferably 95% by weight to 100% by weight, in order to further exert the effects of the present invention.
　その単独重合体（ホモポリマー）のガラス転移温度Ｔｇが－８０℃～－６０℃の範囲内にあるアルキル（メタ）アクリレート（ａ１）は、本発明の効果を発現させ得る側面においてアクリル系ポリマーの粘着特性等に影響を及ぼし得る。アルキル（メタ）アクリレート（ａ）が、その単独重合体（ホモポリマー）のガラス転移温度Ｔｇが－８０℃～－６０℃の範囲内にあるアルキル（メタ）アクリレート（ａ１）を、好ましくは上記の含有割合で含むことにより、本発明の効果がより発現し得る。 The alkyl (meth)acrylate (a1) whose homopolymer has a glass transition temperature Tg in the range of -80°C to -60°C can affect the adhesive properties of the acrylic polymer in terms of the aspect of manifesting the effects of the present invention. By including alkyl (meth)acrylate (a1) whose homopolymer has a glass transition temperature Tg in the range of -80°C to -60°C, preferably in the above content ratio, the effects of the present invention can be more effectively manifested.
　アルキル（メタ）アクリレート（ａ）は、アルキル（メタ）アクリレート（ａ１）以外のアルキル（メタ）アクリレートを含んでいてもよい。アルキル（メタ）アクリレート（ａ）全量中のアルキル（メタ）アクリレート（ａ１）以外のアルキル（メタ）アクリレートの含有割合は、本発明の効果をより発現させ得る点で、好ましくは０重量％～５０重量％であり、より好ましくは０重量％～３０重量％であり、さらに好ましくは０重量％～２０重量％であり、特に好ましくは０重量％～１０重量％であり、最も好ましくは０重量％～５重量％である。 The alkyl (meth)acrylate (a) may contain an alkyl (meth)acrylate other than the alkyl (meth)acrylate (a1). The content of the alkyl (meth)acrylate other than the alkyl (meth)acrylate (a1) in the total amount of the alkyl (meth)acrylate (a) is preferably 0% by weight to 50% by weight, more preferably 0% by weight to 30% by weight, even more preferably 0% by weight to 20% by weight, particularly preferably 0% by weight to 10% by weight, and most preferably 0% by weight to 5% by weight, in order to further exert the effects of the present invention.
　モノマー成分（Ｍ）中の極性基含有モノマー（ｂ）の含有割合は、本発明の効果をより発現させ得る点で、好ましくは１重量％～６０重量％であり、より好ましくは５重量％～６０重量％であり、さらに好ましくは１０重量％～６０重量％であり、特に好ましくは１５重量％～６０重量％であり、最も好ましくは２０重量％～６０重量％である。 The content of the polar group-containing monomer (b) in the monomer component (M) is preferably 1% by weight to 60% by weight, more preferably 5% by weight to 60% by weight, even more preferably 10% by weight to 60% by weight, particularly preferably 15% by weight to 60% by weight, and most preferably 20% by weight to 60% by weight, in order to further exert the effects of the present invention.
　極性基含有モノマー（ｂ）としては、極性基を有するモノマーであれば、本発明の効果を損なわない範囲で、任意の適切なモノマーを採用し得る。このような極性基含有モノマー（ｂ）としては、水酸基含有モノマー（ｂ１）を含む実施形態（Ｉ）、水酸基含有モノマー（ｂ１）を含まない実施形態（ＩＩ）が挙げられる。なお、ここにいう「水酸基」には、カルボキシル基（－ＣＯＯＨ）が有する－ＯＨ基は含まない。 Any appropriate monomer having a polar group may be used as the polar group-containing monomer (b) as long as it does not impair the effects of the present invention. Examples of such polar group-containing monomer (b) include embodiment (I) that contains hydroxyl group-containing monomer (b1) and embodiment (II) that does not contain hydroxyl group-containing monomer (b1). Note that the "hydroxyl group" referred to here does not include the -OH group possessed by a carboxyl group (-COOH).
　極性基含有モノマー（ｂ）としては、アクリル系ポリマーのガラス転移温度Ｔｇを前述した好ましい範囲に調整できる範囲で、上記の実施形態の中から適宜選択すればよい。 The polar group-containing monomer (b) may be appropriately selected from the above embodiments within the range in which the glass transition temperature Tg of the acrylic polymer can be adjusted to the above-mentioned preferred range.
　水酸基含有モノマー（ｂ１）は、１種のみであってもよいし、２種以上であってもよい。水酸基以外の極性基を有するモノマー（ｂ２）は、１種のみであってもよいし、２種以上であってもよい。 The hydroxyl group-containing monomer (b1) may be of only one type or of two or more types. The monomer (b2) having a polar group other than a hydroxyl group may be of only one type or of two or more types.
　水酸基含有モノマー（ｂ１）としては、例えば、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、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート；ポリプロピレングリコールモノ（メタ）アクリレート；Ｎ－ヒドロキシエチル（メタ）アクリルアミド；が挙げられる。 Examples of the hydroxyl group-containing monomer (b1) include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; polypropylene glycol mono(meth)acrylate; and N-hydroxyethyl (meth)acrylamide.
　本発明の効果をより発現させ得る点で、水酸基含有モノマー（ｂ１）は、その単独重合体（ホモポリマー）のガラス転移温度Ｔｇが、好ましくは－６０℃～－１０℃であり、より好ましくは－５５℃～－１０℃であり、さらに好ましくは－４５℃～－１０℃であり、特に好ましくは－３５℃～－１０℃であり、最も好ましくは－２５℃～－１０℃である。水酸基含有モノマー（ｂ１）の単独重合体（ホモポリマー）のガラス転移温度Ｔｇは、アクリル系ポリマーの粘着特性等に影響を及ぼし得る。モノマー成分（Ｍ）中に含み得る水酸基含有モノマー（ｂ１）として、その単独重合体（ホモポリマー）のガラス転移温度Ｔｇが上記範囲内にある水酸基含有モノマーを採用することにより、本発明の効果をより発現させ得る。 In terms of being able to further exert the effects of the present invention, the hydroxyl-containing monomer (b1) has a glass transition temperature Tg of its homopolymer of preferably -60°C to -10°C, more preferably -55°C to -10°C, even more preferably -45°C to -10°C, particularly preferably -35°C to -10°C, and most preferably -25°C to -10°C. The glass transition temperature Tg of the homopolymer of the hydroxyl-containing monomer (b1) can affect the adhesive properties, etc., of the acrylic polymer. By employing a hydroxyl-containing monomer whose homopolymer has a glass transition temperature Tg within the above range as the hydroxyl-containing monomer (b1) that can be contained in the monomer component (M), the effects of the present invention can be further exerted.
　水酸基含有モノマー（ｂ１）の単独重合体（ホモポリマー）のガラス転移温度Ｔｇについては、アルキル（メタ）アクリレート（ａ１）の単独重合体（ホモポリマー）のガラス転移温度Ｔｇについての説明を援用し得る。 The glass transition temperature Tg of the homopolymer of the hydroxyl group-containing monomer (b1) may be determined from the same explanation as for the glass transition temperature Tg of the homopolymer of the alkyl (meth)acrylate (a1).
　本発明の効果をより一層発現させ得る点で、水酸基含有モノマー（ｂ１）としては、好ましくは、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、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレートが挙げられ、より好ましくは、ヒドロキシアルキル基のアルキル基部分が炭素数２～４の直鎖状アルキル基であるヒドロキシアルキル（メタ）アクリレートが挙げられ、さらに好ましくは、２－ヒドロキシエチルアクリレート（ＨＥＡ）（その単独重合体（ホモポリマー）のガラス転移温度Ｔｇ＝－１５℃）、４－ヒドロキシブチルアクリレート（４ＨＢＡ）（その単独重合体（ホモポリマー）のガラス転移温度Ｔｇ＝－４０℃）が挙げられ、特に好ましくは、２－ヒドロキシエチルアクリレート（ＨＥＡ）（その単独重合体（ホモポリマー）のガラス転移温度Ｔｇ＝－１５℃）である。 In terms of being able to further exert the effects of the present invention, the hydroxyl group-containing monomer (b1) is preferably a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate, more preferably a hydroxyalkyl (meth)acrylate in which the alkyl group of the hydroxyalkyl group is a linear alkyl group having 2 to 4 carbon atoms, even more preferably 2-hydroxyethyl acrylate (HEA) (glass transition temperature of its homopolymer Tg = -15°C), 4-hydroxybutyl acrylate (4HBA) (glass transition temperature of its homopolymer Tg = -40°C), and particularly preferably 2-hydroxyethyl acrylate (HEA) (glass transition temperature of its homopolymer Tg = -15°C).
　極性基含有モノマー（ｂ）が、水酸基含有モノマー（ｂ１）を必須に含む実施形態（Ｉ）である場合、極性基含有モノマー（ｂ）中の水酸基含有モノマー（ｂ１）の含有割合は、本発明の効果をより発現させ得る点で、好ましくは１重量％～１００重量％であり、より好ましくは１０重量％～１００重量％であり、さらに好ましくは５０重量％～１００重量％であり、さらに好ましくは７０重量％～１００重量％であり、特に好ましくは９０重量％～１００重量％であり、最も好ましくは９５重量％～１００重量％である。 In the case of embodiment (I) in which the polar group-containing monomer (b) essentially contains the hydroxyl group-containing monomer (b1), the content of the hydroxyl group-containing monomer (b1) in the polar group-containing monomer (b) is preferably 1% by weight to 100% by weight, more preferably 10% by weight to 100% by weight, even more preferably 50% by weight to 100% by weight, even more preferably 70% by weight to 100% by weight, particularly preferably 90% by weight to 100% by weight, and most preferably 95% by weight to 100% by weight, in order to further exert the effects of the present invention.
　水酸基含有モノマー（ｂ１）を必須に含む実施形態（Ｉ）においては、極性基含有モノマー（ｂ）は、水酸基以外の極性基を有するモノマー（ｂ２）を含んでいてもよい。この場合、極性基含有モノマー（ｂ）中の水酸基以外の極性基を有するモノマー（ｂ２）の含有割合は、本発明の効果をより発現させ得る点で、好ましくは０重量％～９９重量％であり、より好ましくは０重量％～９０重量％であり、さらに好ましくは０重量％～５０重量％であり、さらに好ましくは０重量％～３０重量％であり、特に好ましくは０重量％～１０重量％であり、最も好ましくは０重量％～５重量％である。 In the embodiment (I) that essentially contains the hydroxyl group-containing monomer (b1), the polar group-containing monomer (b) may contain a monomer (b2) having a polar group other than a hydroxyl group. In this case, the content of the monomer (b2) having a polar group other than a hydroxyl group in the polar group-containing monomer (b) is preferably 0% to 99% by weight, more preferably 0% to 90% by weight, even more preferably 0% to 50% by weight, even more preferably 0% to 30% by weight, particularly preferably 0% to 10% by weight, and most preferably 0% to 5% by weight, in order to further exhibit the effects of the present invention.
　極性基含有モノマー（ｂ）が、水酸基含有モノマー（ｂ１）を必須に含む実施形態（Ｉ）である場合、モノマー成分（Ｍ）中の水酸基含有モノマー（ｂ１）の含有割合は、本発明の効果をより発現させ得る点で、好ましくは０．００１重量％～４０重量％であり、より好ましくは０．０１重量％～２０重量％であり、さらに好ましくは０．１重量％～１５重量％であり、特に好ましくは０．５重量％～１０重量％であり、最も好ましくは１重量％～５重量％である。 In the case of embodiment (I) in which the polar group-containing monomer (b) essentially contains the hydroxyl group-containing monomer (b1), the content of the hydroxyl group-containing monomer (b1) in the monomer component (M) is preferably 0.001% by weight to 40% by weight, more preferably 0.01% by weight to 20% by weight, even more preferably 0.1% by weight to 15% by weight, particularly preferably 0.5% by weight to 10% by weight, and most preferably 1% by weight to 5% by weight, in order to further exert the effects of the present invention.
　水酸基以外の極性基を有するモノマー（ｂ２）としては、例えば、カルボキシル基含有モノマー、スルホン酸基含有モノマー、リン酸基含有モノマー、シアノ基含有モノマー、酸無水物基含有モノマー、ビニルエステル類、複素環含有ビニル系モノマー、芳香族ビニル化合物、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、イソシアネート基含有モノマー、芳香族炭化水素基を有する（メタ）アクリル酸エステル、芳香族ビニル化合物、オレフィン類やジエン類、ビニルエーテル類、（メタ）アクリロイルモルホリン、ビニルエーテル類、ハロゲン基含有モノマーが挙げられる。 Examples of monomers (b2) having a polar group other than a hydroxyl group include carboxyl group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, cyano group-containing monomers, acid anhydride group-containing monomers, vinyl esters, heterocycle-containing vinyl monomers, aromatic vinyl compounds, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, isocyanate group-containing monomers, (meth)acrylic acid esters having aromatic hydrocarbon groups, aromatic vinyl compounds, olefins and dienes, vinyl ethers, (meth)acryloylmorpholine, vinyl ethers, and halogen group-containing monomers.
　カルボキシ基含有モノマーとしては、例えば、アクリル酸（ＡＡ）、メタクリル酸（ＭＡＡ）、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸が挙げられる。 Examples of carboxy group-containing monomers include acrylic acid (AA), methacrylic acid (MAA), carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
　スルホン酸基含有モノマーとしては、例えば、ビニルスルホン酸ナトリウムが挙げられる。 An example of a sulfonic acid group-containing monomer is sodium vinyl sulfonate.
　リン酸基含有モノマーとしては、例えば、２－ヒドロキシエチルアクリロイルフォスフェートが挙げられる。 An example of a phosphate group-containing monomer is 2-hydroxyethyl acryloyl phosphate.
　シアノ基含有モノマーとしては、例えば、アクリロニトリル、メタクリロニトリルが挙げられる。 Cyano group-containing monomers include, for example, acrylonitrile and methacrylonitrile.
　酸無水物基含有モノマーとしては、例えば、無水マレイン酸、無水イタコン酸が挙げられる。 Examples of monomers containing an acid anhydride group include maleic anhydride and itaconic anhydride.
　ビニルエステル類としては、例えば、酢酸ビニル（ＶＡｃ）、プロピオン酸ビニル、ラウリン酸ビニルが挙げられる。 Examples of vinyl esters include vinyl acetate (VAc), vinyl propionate, and vinyl laurate.
　複素環含有ビニル系モノマーとしては、例えば、Ｎ－ビニル－２－ピロリドン、（メタ）アクリロイルモルホリン、Ｎ－ビニルピペリドン、Ｎ－ビニルピペラジン、Ｎ－ビニルピロール、Ｎ－ビニルイミダゾール、ビニルピリジン、ビニルピリミジン、ビニルオキサゾールが挙げられる。 Examples of heterocycle-containing vinyl monomers include N-vinyl-2-pyrrolidone, (meth)acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, and vinyloxazole.
　芳香族ビニル化合物としては、例えば、スチレン、ビニルトルエンが挙げられる。 Examples of aromatic vinyl compounds include styrene and vinyltoluene.
　アミド基含有モノマーとしては、例えば、（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－メトキシメチル（メタ）アクリルアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド、Ｎ－ヒドロキシエチル（メタ）アクリルアミドが挙げられる。 Examples of amide group-containing monomers include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, and N-hydroxyethyl(meth)acrylamide.
　イミド基含有モノマーとしては、例えば、シクロヘキシルマレイミド、イソプロピルマレイミドが挙げられる。 Examples of imide group-containing monomers include cyclohexylmaleimide and isopropylmaleimide.
　アミノ基含有モノマーとしては、例えば、（メタ）アクリル酸アミノエチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ｔ－ブチルアミノエチルが挙げられる。 Examples of amino group-containing monomers include aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and t-butylaminoethyl (meth)acrylate.
　エポキシ基含有モノマーとしては、例えば、（メタ）アクリル酸グリシジル、（メタ）アクリル酸メチルグリシジルが挙げられる。 Examples of epoxy group-containing monomers include glycidyl (meth)acrylate and methyl glycidyl (meth)acrylate.
　イソシアネート基含有モノマーとしては、例えば、２－メタクリロイルオキシエチルイソシアネートが挙げられる。 An example of an isocyanate group-containing monomer is 2-methacryloyloxyethyl isocyanate.
　芳香族炭化水素基を有する（メタ）アクリル酸エステルとしては、例えば、フェニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレートが挙げられる。 Examples of (meth)acrylic acid esters having an aromatic hydrocarbon group include phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate.
　芳香族ビニル化合物としては、例えば、スチレン、ビニルトルエンが挙げられる。 Examples of aromatic vinyl compounds include styrene and vinyltoluene.
　オレフィン類やジエン類としては、例えば、エチレン、ブタジエン、イソプレン、イソブチレンが挙げられる。 Examples of olefins and dienes include ethylene, butadiene, isoprene, and isobutylene.
　ビニルエーテル類としては、例えば、ビニルアルキルエーテルが挙げられる。 Examples of vinyl ethers include vinyl alkyl ethers.
　ハロゲン基含有モノマーとしては、例えば、塩化ビニルが挙げられる。 An example of a halogen-containing monomer is vinyl chloride.
　本発明の効果をより発現させ得る点で、水酸基以外の極性基を有するモノマー（ｂ２）は、その単独重合体（ホモポリマー）のガラス転移温度Ｔｇが、好ましくは０℃～１３０℃であり、より好ましくは１０℃～１２０℃であり、さらに好ましくは２０℃～１１０℃である。 In order to further exert the effects of the present invention, the glass transition temperature Tg of the homopolymer of the monomer (b2) having a polar group other than a hydroxyl group is preferably 0°C to 130°C, more preferably 10°C to 120°C, and even more preferably 20°C to 110°C.
　水酸基以外の極性基を有するモノマー（ｂ２）の単独重合体（ホモポリマー）のガラス転移温度Ｔｇについては、アルキル（メタ）アクリレート（ａ１）の単独重合体（ホモポリマー）のガラス転移温度Ｔｇについての説明を援用し得る。 The glass transition temperature Tg of the homopolymer of the monomer (b2) having a polar group other than a hydroxyl group may be determined from the same explanation as for the glass transition temperature Tg of the homopolymer of the alkyl (meth)acrylate (a1).
　水酸基以外の極性基を有するモノマー（ｂ２）の一つの実施形態は、その単独重合体（ホモポリマー）のガラス転移温度Ｔｇが０℃～６０℃の水酸基以外の極性基を有するモノマー（ｂ２－１）とその単独重合体（ホモポリマー）のガラス転移温度Ｔｇが７０℃～１３０℃の水酸基以外の極性基を有するモノマー（ｂ２－２）とを含む。この実施形態においては、水酸基以外の極性基を有するモノマー（ｂ２）中の水酸基以外の極性基を有するモノマー（ｂ２－１）の含有割合は、本発明の効果をより発現させ得る点で、好ましくは５０重量％～９９重量％であり、より好ましくは７０重量％～９９重量％であり、さらに好ましくは８０重量％～９９重量％であり、特に好ましくは９０重量％～９９重量％である。この実施形態においては、水酸基以外の極性基を有するモノマー（ｂ２）中の水酸基以外の極性基を有するモノマー（ｂ２－２）の含有割合は、本発明の効果をより発現させ得る点で、好ましくは１重量％～５０重量％であり、より好ましくは１重量％～３０重量％であり、さらに好ましくは１重量％～２０重量％であり、特に好ましくは１重量％～１０重量％である。この実施形態においては、水酸基以外の極性基を有するモノマー（ｂ２）中の水酸基以外の極性基を有するモノマー（ｂ２－１）と水酸基以外の極性基を有するモノマー（ｂ２－２）との合計の含有割合は、好ましくは６０重量％～１００重量％であり、より好ましくは８０重量％～１００重量％であり、さらに好ましくは９０重量％～１００重量％であり、特に好ましくは９５重量％～１００重量％であり、最も好ましくは９８重量％～１００重量％である。 One embodiment of the monomer (b2) having a polar group other than a hydroxyl group includes a monomer (b2-1) having a polar group other than a hydroxyl group, the glass transition temperature Tg of which homopolymer is 0° C. to 60° C., and a monomer (b2-2) having a polar group other than a hydroxyl group, the glass transition temperature Tg of which homopolymer is 70° C. to 130° C. In this embodiment, the content of the monomer (b2-1) having a polar group other than a hydroxyl group in the monomer (b2) having a polar group other than a hydroxyl group is preferably 50% by weight to 99% by weight, more preferably 70% by weight to 99% by weight, even more preferably 80% by weight to 99% by weight, and particularly preferably 90% by weight to 99% by weight, in terms of being able to further exhibit the effects of the present invention. In this embodiment, the content of the monomer (b2-2) having a polar group other than a hydroxyl group in the monomer (b2) having a polar group other than a hydroxyl group is preferably 1% by weight to 50% by weight, more preferably 1% by weight to 30% by weight, even more preferably 1% by weight to 20% by weight, and particularly preferably 1% by weight to 10% by weight, in order to further exhibit the effects of the present invention. In this embodiment, the total content of the monomer (b2-1) having a polar group other than a hydroxyl group and the monomer (b2-2) having a polar group other than a hydroxyl group in the monomer (b2) having a polar group other than a hydroxyl group is preferably 60% by weight to 100% by weight, more preferably 80% by weight to 100% by weight, even more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight, and most preferably 98% by weight to 100% by weight.
　その単独重合体（ホモポリマー）のガラス転移温度Ｔｇが０℃～６０℃の水酸基以外の極性基を有するモノマー（ｂ２－１）の該ガラス転移温度Ｔｇは、好ましくは１０℃～５０℃であり、より好ましくは２０℃～４０℃である。このような水酸基以外の極性基を有するモノマー（ｂ２－１）としては、例えば、酢酸ビニル（ＶＡｃ）（その単独重合体（ホモポリマー）のガラス転移温度Ｔｇ＝３０℃）が挙げられる。 The glass transition temperature Tg of the monomer (b2-1) having a polar group other than a hydroxyl group, the glass transition temperature of which of its homopolymers is 0°C to 60°C, is preferably 10°C to 50°C, and more preferably 20°C to 40°C. An example of such a monomer (b2-1) having a polar group other than a hydroxyl group is vinyl acetate (VAc) (the glass transition temperature of its homopolymer (Tg) = 30°C).
　その単独重合体（ホモポリマー）のガラス転移温度Ｔｇが７０℃～１３０℃の水酸基以外の極性基を有するモノマー（ｂ２－２）の該ガラス転移温度Ｔｇは、好ましくは８０℃～１２０℃であり、より好ましくは９０℃～１１０℃である。このような水酸基以外の極性基を有するモノマー（ｂ２－２）としては、例えば、アクリル酸（ＡＡ）（その単独重合体（ホモポリマー）のガラス転移温度Ｔｇ＝１０６℃）が挙げられる。 The glass transition temperature Tg of the monomer (b2-2) having a polar group other than a hydroxyl group, the glass transition temperature of which of its homopolymers is 70°C to 130°C, is preferably 80°C to 120°C, and more preferably 90°C to 110°C. An example of such a monomer (b2-2) having a polar group other than a hydroxyl group is acrylic acid (AA) (the glass transition temperature of its homopolymer (Tg) = 106°C).
　極性基含有モノマー（ｂ）が、水酸基含有モノマー（ｂ１）を含まない実施形態（ＩＩ）である場合、すなわち、水酸基以外の極性基を有するモノマー（ｂ２）を必須に含む場合、モノマー成分（Ｍ）中の水酸基以外の極性基を有するモノマー（ｂ２）の含有割合は、本発明の効果をより発現させ得る点で、好ましくは１０重量％～５７重量％であり、より好ましくは２０重量％～５４重量％であり、さらに好ましくは３０重量％～５２重量％であり、特に好ましくは４０重量％～５０重量％である。 When the polar group-containing monomer (b) is embodiment (II) that does not contain a hydroxyl group-containing monomer (b1), i.e., when the monomer (b2) having a polar group other than a hydroxyl group is essentially contained, the content of the monomer (b2) having a polar group other than a hydroxyl group in the monomer component (M) is preferably 10% by weight to 57% by weight, more preferably 20% by weight to 54% by weight, even more preferably 30% by weight to 52% by weight, and particularly preferably 40% by weight to 50% by weight, in order to further exert the effects of the present invention.
　一つの実施形態としては、モノマー成分（Ｍ）は、好ましくは、アルキル（メタ）アクリレート（ａ）と極性基含有モノマー（ｂ）を含み、該モノマー成分（Ｍ）中の該アルキル（メタ）アクリレート（ａ）の含有割合が４３重量％～９０重量％であり、該アルキル（メタ）アクリレート（ａ）が、その単独重合体（ホモポリマー）のガラス転移温度Ｔｇが－８０℃～－６０℃の範囲内にあるアルキル（メタ）アクリレート（ａ１）であり、該極性基含有モノマー（ｂ）が水酸基含有モノマー（ｂ１）を含まず、水酸基以外の極性基を有するモノマー（ｂ２）を必須に含み、該水酸基含有モノマー（ｂ２）は、その単独重合体（ホモポリマー）のガラス転移温度Ｔｇが０℃～１３０℃の範囲内にあり、該モノマー成分（Ｍ）中の該極性基含有モノマー（ｂ２）の含有割合が１０重量％～５７重量％である。 In one embodiment, the monomer component (M) preferably contains an alkyl (meth)acrylate (a) and a polar group-containing monomer (b), the content of the alkyl (meth)acrylate (a) in the monomer component (M) is 43% to 90% by weight, the alkyl (meth)acrylate (a) is an alkyl (meth)acrylate (a1) whose homopolymer has a glass transition temperature Tg in the range of -80°C to -60°C, the polar group-containing monomer (b) does not contain a hydroxyl group-containing monomer (b1) but essentially contains a monomer (b2) having a polar group other than a hydroxyl group, the hydroxyl group-containing monomer (b2) has a homopolymer glass transition temperature Tg in the range of 0°C to 130°C, and the content of the polar group-containing monomer (b2) in the monomer component (M) is 10% to 57% by weight.
　本発明の効果を一層発現させ得る一つの実施形態としては、
（ｉ）モノマー成分（Ｍ）は、好ましくは、アルキル（メタ）アクリレート（ａ）と極性基含有モノマー（ｂ）を含み、
（ｉｉ）モノマー成分（Ｍ）中のアルキル（メタ）アクリレート（ａ）の含有割合が、好ましくは６０重量％～９９．９９９重量％であり、より好ましくは８０重量％～９９．９９重量％であり、さらに好ましくは８５重量％～９９．９重量％であり、特に好ましくは９０重量％～９９．５重量％であり、最も好ましくは９５重量％～９９重量％であり、
（ｉｉｉ）アルキル（メタ）アクリレート（ａ）が、好ましくは、その単独重合体（ホモポリマー）のガラス転移温度Ｔｇが－８０℃～－６０℃の範囲内にあるアルキル（メタ）アクリレート（ａ１）を必須に含み、
（ｉｖ）アルキル（メタ）アクリレート（ａ）全量中のアルキル（メタ）アクリレート（ａ１）の含有割合が、好ましくは５０重量％～１００重量％であり、より好ましくは７０重量％～１００重量％であり、さらに好ましくは８０重量％～１００重量％であり、特に好ましくは９０重量％～１００重量％であり、最も好ましくは９５重量％～１００重量％であり、
（ｖ）モノマー成分（Ｍ）中の極性基含有モノマー（ｂ）の含有割合が、好ましくは０．００１重量％～４０重量％であり、より好ましくは０．０１重量％～２０重量％であり、さらに好ましくは０．１重量％～１５重量％であり、特に好ましくは０．５重量％～１０重量％であり、最も好ましくは１重量％～５重量％であり、
（ｖｉ）極性基含有モノマー（ｂ）が、好ましくは、水酸基含有モノマー（ｂ１）を必須に含み、
（ｖｉｉ）水酸基含有モノマー（ｂ１）は、、好ましくは、その単独重合体（ホモポリマー）のガラス転移温度Ｔｇが－６０℃～－１０℃の範囲内にあり、
（ｖｉｉｉ）極性基含有モノマー（ｂ）中の水酸基含有モノマー（ｂ１）の含有割合が、好ましくは１重量％～１００重量％であり、より好ましくは１０重量％～１００重量％であり、さらに好ましくは５０重量％～１００重量％であり、さらに好ましくは７０重量％～１００重量％であり、特に好ましくは９０重量％～１００重量％であり、最も好ましくは９５重量％～１００重量％であり、
（ｉｘ）モノマー成分（Ｍ）中の極性基含有モノマー（ｂ１）の含有割合が、好ましくは０．００１重量％～４０重量％であり、より好ましくは０．０１重量％～２０重量％であり、さらに好ましくは０．１重量％～１５重量％であり、特に好ましくは０．５重量％～１０重量％であり、最も好ましくは１重量％～５重量％である。 As an embodiment that can further exhibit the effects of the present invention,
(i) The monomer component (M) preferably contains an alkyl (meth)acrylate (a) and a polar group-containing monomer (b),
(ii) the content of the alkyl (meth)acrylate (a) in the monomer component (M) is preferably 60% by weight to 99.999% by weight, more preferably 80% by weight to 99.99% by weight, even more preferably 85% by weight to 99.9% by weight, particularly preferably 90% by weight to 99.5% by weight, and most preferably 95% by weight to 99% by weight,
(iii) the alkyl(meth)acrylate (a) preferably essentially contains an alkyl(meth)acrylate (a1) having a glass transition temperature Tg of its homopolymer in the range of −80° C. to −60° C.;
(iv) the content of the alkyl (meth)acrylate (a1) in the total amount of the alkyl (meth)acrylate (a) is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, even more preferably 80% by weight to 100% by weight, particularly preferably 90% by weight to 100% by weight, and most preferably 95% by weight to 100% by weight;
(v) the content of the polar group-containing monomer (b) in the monomer component (M) is preferably 0.001% by weight to 40% by weight, more preferably 0.01% by weight to 20% by weight, even more preferably 0.1% by weight to 15% by weight, particularly preferably 0.5% by weight to 10% by weight, and most preferably 1% by weight to 5% by weight;
(vi) the polar group-containing monomer (b) preferably essentially contains a hydroxyl group-containing monomer (b1);
(vii) The hydroxyl group-containing monomer (b1) preferably has a glass transition temperature Tg of its homopolymer in the range of −60° C. to −10° C.,
(viii) the content of the hydroxyl group-containing monomer (b1) in the polar group-containing monomer (b) is preferably 1% by weight to 100% by weight, more preferably 10% by weight to 100% by weight, even more preferably 50% by weight to 100% by weight, still more preferably 70% by weight to 100% by weight, particularly preferably 90% by weight to 100% by weight, and most preferably 95% by weight to 100% by weight;
(ix) The content of the polar group-containing monomer (b1) in the monomer component (M) is preferably 0.001% by weight to 40% by weight, more preferably 0.01% by weight to 20% by weight, even more preferably 0.1% by weight to 15% by weight, particularly preferably 0.5% by weight to 10% by weight, and most preferably 1% by weight to 5% by weight.
　モノマー成分（Ｍ）は、アルキル（メタ）アクリレート（ａ）と極性基含有モノマー（ｂ）のいずれにも該当しないその他のモノマー（ｃ）を含んでいてもよい。その他のモノマー（ｃ）は、例えば、アクリル系ポリマーのガラス転移温度Ｔｇの調整、粘着性能の調整等の目的で使用することができる。その他のモノマーは、１種のみであってもよいし、２種以上であってもよい。 The monomer component (M) may contain other monomers (c) that do not fall into either the alkyl (meth)acrylate (a) or the polar group-containing monomer (b). The other monomers (c) can be used for purposes such as adjusting the glass transition temperature Tg of the acrylic polymer and adjusting the adhesive performance. The other monomers may be of only one type or of two or more types.
　モノマー成分（Ｍ）中のその他モノマー（ｃ）の含有割合は、好ましくは２０重量％以下であり、より好ましくは１０重量％以下であり、さらに好ましくは５重量％以下であり、特に好ましくは３重量％以下であり、最も好ましくは１重量％以下である。 The content of other monomers (c) in monomer component (M) is preferably 20% by weight or less, more preferably 10% by weight or less, even more preferably 5% by weight or less, particularly preferably 3% by weight or less, and most preferably 1% by weight or less.
　アクリル系ポリマーは、モノマー成分（Ｍ）を重合して得られるものである。アクリル系ポリマーの好ましい実施形態は、重合開始剤を用いた溶液重合で調製したアクリル系ポリマーである。 The acrylic polymer is obtained by polymerizing the monomer component (M). A preferred embodiment of the acrylic polymer is an acrylic polymer prepared by solution polymerization using a polymerization initiator.
　重合開始剤は、重合反応の種類に応じて、任意の適切な重合開始剤を採用し得る。重合開始剤は、１種のみであってもよいし、２種以上であってもよい。 Any appropriate polymerization initiator may be used depending on the type of polymerization reaction. The polymerization initiator may be of only one type or of two or more types.
　重合開始剤としては、代表的には、熱重合開始剤が挙げられる。 A typical example of a polymerization initiator is a thermal polymerization initiator.
　熱重合開始剤は、好ましくは、アクリル系ポリマーを溶液重合によって得る際に採用され得る。このような熱重合開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）、２，２’－アゾビス－２－メチルブチロニトリル、２，２’－アゾビス（２－メチルプロピオン酸）ジメチル、４，４’－アゾビス－４－シアノバレリアン酸、アゾビスイソバレロニトリル、２，２’－アゾビス（２－アミジノプロパン）ジヒドロクロライド、２，２’－アゾビス［２－（５－メチル－２－イミダゾリン－２－イル）プロパン］ジヒドロクロライド、２，２’－アゾビス（２－メチルプロピオンアミジン）二硫酸塩、２，２’－アゾビス（Ｎ，Ｎ’－ジメチレンイソブチルアミジン）、２，２’－アゾビス［Ｎ－（２－カルボキシエチル）－２－メチルプロピオンアミジン］ハイドレート（ＶＡ－０５７、和光純薬工業（株）製）などのアゾ系開始剤；過硫酸カリウム、過硫酸アンモニウムなどの過硫酸塩、ジ（２－エチルヘキシル）パーオキシジカーボネート、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート、ジ－ｓｅｃ－ブチルパーオキシジカーボネート、ｔ－ブチルパーオキシネオデカノエート、ｔ－ヘキシルパーオキシピバレート、ｔ－ブチルパーオキシピバレート、ジラウロイルパーオキシド、ジ－ｎ－オクタノイルパーオキシド、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート、ジ（４－メチルベンゾイル）パーオキシド、ジベンゾイルパーオキシド、ｔ－ブチルパーオキシイソブチレート、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサン、ｔ－ブチルハイドロパーオキシド、過酸化水素などの過酸化物系開始剤；過硫酸塩と亜硫酸水素ナトリウムの組み合わせ、過酸化物とアスコルビン酸ナトリウムの組み合わせなどの過酸化物と還元剤とを組み合わせたレドックス系開始剤；フェニル置換エタン等の置換エタン系開始剤；芳香族カルボニル化合物；が挙げられる。 The thermal polymerization initiator may be preferably used when obtaining an acrylic polymer by solution polymerization. Examples of such a thermal polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis(2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propionate], and 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propionate]. azo initiators such as 2,2'-azobis(2-methylpropionamidine)dihydrochloride, 2,2'-azobis(N,N'-dimethyleneisobutylamidine), and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.); persulfates such as potassium persulfate and ammonium persulfate, and di(2-ethylhexyl)peroxydicarbonate. , di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di(4-methylbenzoyl)peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di(t-hexylperoxy)cyclohexane, t-butyl hydroperoxide, peroxide-based initiators such as hydrogen peroxide; redox-based initiators combining peroxides and reducing agents, such as a combination of persulfate and sodium hydrogen sulfite, or a combination of peroxide and sodium ascorbate; substituted ethane-based initiators such as phenyl-substituted ethane; and aromatic carbonyl compounds.
　熱重合開始剤の使用量は、本発明の効果を損なわない範囲で、任意の適切な使用量に設定され得る。熱重合開始剤の使用量は、本発明の効果をより発現させ得る点で、モノマー成分（Ｍ）１００重量部に対して、好ましくは０．００１重量部～１０重量部であり、より好ましくは０．００５重量部～５重量部であり、さらに好ましくは０．００７重量部～３重量部であり、特に好ましくは０．０１重量部～１重量部である。 The amount of the thermal polymerization initiator used may be set to any appropriate amount as long as it does not impair the effects of the present invention. The amount of the thermal polymerization initiator used is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight, even more preferably 0.007 to 3 parts by weight, and particularly preferably 0.01 to 1 part by weight, relative to 100 parts by weight of the monomer component (M), in order to further exert the effects of the present invention.
　アクリル系ポリマーを溶液重合によって得る際に用いる溶剤としては、本発明の効果を損なわない範囲で、任意の適切な溶剤を採用し得る。 Any suitable solvent may be used when obtaining an acrylic polymer by solution polymerization, as long as it does not impair the effects of the present invention.
＜１－２－ｂ．架橋剤＞
　アクリル系粘着剤組成物は、架橋剤を含んでいてもよい。架橋剤を用いることにより、アクリル系粘着剤の凝集力を向上でき、本発明の効果をより発現させ得る。架橋剤は、１種のみであってもよいし、２種以上であってもよい。 <1-2-b. Crosslinking agent>
The acrylic pressure-sensitive adhesive composition may contain a crosslinking agent. By using the crosslinking agent, the cohesive strength of the acrylic pressure-sensitive adhesive can be improved, and the effects of the present invention can be more effectively exhibited. The crosslinking agent may be one type only, or two or more types.
　架橋剤としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、シリコーン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、シラン系架橋剤、アルキルエーテル化メラミン系架橋剤、金属キレート系架橋剤、過酸化物等の架橋剤が挙げられ、本発明の効果をより発現させ得る点で、好ましくは、イソシアネート系架橋剤、エポキシ系架橋剤、および、過酸化物からなる群から選ばれる少なくとも１種（ｃ成分）である。 Examples of crosslinking agents include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, silicone-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, silane-based crosslinking agents, alkyl etherified melamine-based crosslinking agents, metal chelate-based crosslinking agents, and peroxides. In terms of being able to more effectively exert the effects of the present invention, at least one type (component c) selected from the group consisting of isocyanate-based crosslinking agents, epoxy-based crosslinking agents, and peroxides is preferred.
　イソシアネート系架橋剤は、イソシアネート基（イソシアネート基をブロック剤または数量体化等により一時的に保護したイソシアネート再生型極性基を含む）を１分子中に２つ以上有する化合物を用いることができる。イソシアネート系架橋剤としては、例えば、トリレンジイソシアネート、キシレンジイソシアネート等の芳香族イソシアネート；イソホロンジイソシアネート等の脂環族イソシアネート；ヘキサメチレンジイソシアネート等の脂肪族イソシアネート；が挙げられる。 As the isocyanate-based crosslinking agent, a compound having two or more isocyanate groups (including isocyanate-regenerating polar groups in which the isocyanate group is temporarily protected by a blocking agent or oligomerization) in one molecule can be used. Examples of isocyanate-based crosslinking agents include aromatic isocyanates such as tolylene diisocyanate and xylylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and aliphatic isocyanates such as hexamethylene diisocyanate.
　イソシアネート系架橋剤としては、例えば、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等の低級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等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、ポリメチレンポリフェニルイソシアネート等の芳香族ジイソシアネート類；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（例えば、東ソー社製、商品名コロネートＬ）、トリメチロールプロパン／ヘキサメチレンジイソシアネート３量体付加物（例えば、東ソー社製、商品名：コロネートＨＬ）、ヘキサメチレンジイソシアネートのイソシアヌレート体（例えば、東ソー社製、商品名：コロネートＨＸ）等のイソシアネート付加物；キシリレンジイソシアネートのトリメチロールプロパン付加物（例えば、三井化学社製、商品名：タケネートＤ１１０Ｎ）、キシリレンジイソシアネートのトリメチロールプロパン付加物（例えば、三井化学社製、商品名：タケネートＤ１２０Ｎ）、イソホロンジイソシアネートのトリメチロールプロパン付加物（例えば、三井化学社製、商品名：タケネートＤ１４０Ｎ）、ヘキサメチレンジイソシアネートのトリメチロールプロパン付加物（例えば、三井化学社製、商品名：タケネートＤ１６０Ｎ）；ポリエーテルポリイソシアネート、ポリエステルポリイソシアネート、ならびにこれらと各種のポリオールとの付加物；イソシアヌレート結合、ビューレット結合、アロファネート結合等で多官能化したポリイソシアネート；が挙げられる。これらの中でも、変形性と凝集力とをバランスよく両立し得る点で、好ましくは、芳香族イソシアネート、脂環式イソシアネートである。 Examples of isocyanate-based crosslinking agents include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate; aromatic diisocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and polymethylene polyphenyl isocyanate; trimethylolpropane/tolylene diisocyanate trimer adduct (e.g., manufactured by Tosoh Corporation, product name: Coronate L), trimethylolpropane/hexamethylene diisocyanate trimer adduct (e.g., manufactured by Tosoh Corporation, product name: Coronate HL), and isocyanurate of hexamethylene diisocyanate (e.g., manufactured by Tosoh Corporation, product name: Coronate HL). , trade name: Coronate HX); trimethylolpropane adduct of xylylene diisocyanate (e.g., Mitsui Chemicals, Inc., trade name: Takenate D110N), trimethylolpropane adduct of xylylene diisocyanate (e.g., Mitsui Chemicals, Inc., trade name: Takenate D120N), trimethylolpropane adduct of isophorone diisocyanate (e.g., Mitsui Chemicals, Inc., trade name: Takenate D140N), trimethylolpropane adduct of hexamethylene diisocyanate (e.g., Mitsui Chemicals, Inc., trade name: Takenate D160N); polyether polyisocyanate, polyester polyisocyanate, and adducts of these with various polyols; and polyisocyanates multifunctionalized with isocyanurate bonds, biuret bonds, allophanate bonds, etc. Among these, aromatic isocyanates and alicyclic isocyanates are preferred because they provide a good balance between deformability and cohesive strength.
　エポキシ系架橋剤としては、エポキシ基を１分子中に２つ以上有する多官能エポキシ化合物を用いることができる。エポキシ系架橋剤としては、例えば、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン、ジグリシジルアニリン、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、１，６－ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビタンポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、アジピン酸ジグリシジルエステル、ｏ－フタル酸ジグリシジルエステル、トリグリシジル－トリス（２－ヒドロキシエチル）イソシアヌレート、レゾルシンジグリシジルエーテル、ビスフェノール－Ｓ－ジグリシジルエーテル、分子内にエポキシ基を２つ以上有するエポキシ系樹脂が挙げられる。エポキシ系架橋剤の市販品としては、例えば、三菱ガス化学社製の商品名「テトラッドＣ」、「テトラッドＸ」が挙げられる。 As an epoxy-based crosslinking agent, a multifunctional epoxy compound having two or more epoxy groups in one molecule can be used. Examples of epoxy crosslinking agents include N,N,N',N'-tetraglycidyl-m-xylylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris(2-hydroxyethyl)isocyanurate, resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy resins having two or more epoxy groups in the molecule. Commercially available epoxy crosslinking agents include, for example, "Tetrad C" and "Tetrad X" manufactured by Mitsubishi Gas Chemical Company, Inc.
　過酸化物としては、例えば、ジベンゾイルパーオキシド、ジクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド、ジ－ｔ－ブチルパーオキシ－３，３，５－トリメチルシクロヘキサン、ｔ－ブチルヒドロパーオキサイド、ｔ－ブチルクミルパーオキサイド、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシン）ヘキシン－３、２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン、２，５－ジメチル－２，５－モノ（ｔ－ブチルパーオキシ）－ヘキサン、α，α'－ビス（ｔ－ブチルパーオキシ－ｍ－イソプロピル）ベンゼン、ジ（２－エチルヘキシル）パーオキシジカーボネート、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート、ジ－ｓｅｃ－ブチルパーオキシジカーボネート、ｔ－ブチルパーオキシネオデカノエート、ｔ－ヘキシルパーオキシピバレート、ｔ－ブチルパーオキシピバレート、ジラウロイルパーオキシド、ジ－ｎ－オクタノイルパーオキシド、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート、ジ（４－メチルベンゾイル）パーオキシド、ｔ－ブチルパーオキシイソブチレート、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサン、１，１－ジ（ｔ－ブチルパーオキシ）シクロヘキサン、ｔ－ブチルパーオキシ－２－エチルへキシルカーボネート、ｔ－アミルパーオキシイソプロピルカーボネート、３，５，５－トリメチルヘキサノイルパーオキサイド、ｔ－ブチルパーオキシ－２－ヘキサノエートレート、ｔ－ブチルパーオキシピバレート、ｔ－へキシルパーオキシピバレートが挙げられる。過酸化物の市販品としては、例えば、日本油脂株式会社製の商品名「ナイパーＢＭＴ」シリーズ、「ナイパーＢＷ」シリーズが挙げられる。 Examples of peroxides include dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl hydroperoxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxine)hexyne-3, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-mono(t-butylperoxy)-hexane, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxy Examples of peroxides include cineodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, di(4-methylbenzoyl)peroxide, t-butylperoxyisobutyrate, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, t-butylperoxy-2-ethylhexyl carbonate, t-amylperoxyisopropyl carbonate, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-hexanoate, t-butylperoxypivalate, and t-hexylperoxypivalate. Commercially available peroxides include, for example, the "Niper BMT" series and "Niper BW" series manufactured by Nippon Oil & Fats Co., Ltd.
　アクリル系粘着剤組成物中の架橋剤の含有量は、本発明の効果を損なわない範囲で、任意の適切な含有量を採用し得る。このような含有量としては、例えば、本発明の効果をより発現させ得る点で、アクリル系ポリマーの固形分（１００重量部）に対して、好ましくは０．０５重量部～２０重量部であり、より好ましくは０．１重量部～１８重量部であり、さらに好ましくは０．５重量部～１５重量部であり、特に好ましくは０．５重量部～１０重量部である。 The content of the crosslinking agent in the acrylic adhesive composition may be any appropriate content within the range that does not impair the effects of the present invention. For example, such a content is preferably 0.05 parts by weight to 20 parts by weight, more preferably 0.1 parts by weight to 18 parts by weight, even more preferably 0.5 parts by weight to 15 parts by weight, and particularly preferably 0.5 parts by weight to 10 parts by weight, relative to the solid content (100 parts by weight) of the acrylic polymer, in order to further exert the effects of the present invention.
＜１－２－ｃ．多官能アルコール＞
　アクリル系粘着剤組成物は、多官能アルコールを含んでいてもよい。多官能アルコールを用いることにより、アクリル系粘着剤に適度なやわらかさを付与し得る。多官能アルコールは、１種のみであってもよいし、２種以上であってもよい。 <1-2-c. Polyfunctional alcohol>
The acrylic pressure-sensitive adhesive composition may contain a polyfunctional alcohol. By using the polyfunctional alcohol, it is possible to impart appropriate softness to the acrylic pressure-sensitive adhesive. The polyfunctional alcohol may be one type only, or two or more types.
　多官能アルコールの官能基数としては、本発明の効果がより発現し得る点で、好ましくは２以上であり、より好ましくは３～６であり、さらに好ましくは３～５であり、特に好ましくは３～４であり、最も好ましくは３である。 The number of functional groups of the polyfunctional alcohol is preferably 2 or more, more preferably 3 to 6, even more preferably 3 to 5, particularly preferably 3 to 4, and most preferably 3, in order to better demonstrate the effects of the present invention.
　多官能アルコールとしては、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などが挙げられる。 Examples of polyfunctional alcohols include polyether polyols and polyester polyols.
　ポリエーテルポリオールとしては、例えば、ポリプロピレングリコール（２官能）、ビスフェノールＡにプロピレンオキシドを付加させたジオール（２官能）、グリセリンにプロピレンオキシドを付加させたトリオール（３官能）、トリメチロールプロパンにプロピレンオキシドを付加させたトリオール（３官能）、エチレンジアミンの活性水素にプロピレンオキシドを付加させたテトラオール（４官能）、ソルビトールまたはシュークローズにプロピレンオキシドを付加させたポリオール（多官能）、グリセリンにプロピレンオキシドとエチレンオキシドを付加させたトリオールであってエチレンオキシドで末端がブロックされているトリオール（３官能）、エチレンジアミンの活性水素にプロピレンオキシドとエチレンオキシドを付加させたテトラオールであってエチレンオキシドで末端がブロックされているテトラオール（４官能）、ポリプロピレンポリエチレングリコールであってエチレンオキシドで末端がブロックされているポリプロピレンポリエチレングリコール（２官能）、ビスフェノールＡにプロピレンオキシドとエチレンオキシドを付加させたジオールであってエチレンオキシドで末端がブロックされているジオール（２官能）、トリメチロールプロパンにエチレンオキシドを付加させたトリオール（３官能）、ポリプロピレンポリエチレングリコールであってエチレンオキシドとプロピレンオキシドがランダムに付加したポリプロピレンポリエチレングリコール（２官能）、グリセリンにプロピレンオキシドとエチレンオキシドを付加させたトリオールであってエチレンオキシドとプロピレンオキシドがランダムに付加したトリオール（３官能）、難燃ポリオール（２官能）などが挙げられる。 Examples of polyether polyols include polypropylene glycol (bifunctional), diol (bifunctional) with propylene oxide added to bisphenol A, triol (trifunctional) with propylene oxide added to glycerin, triol (trifunctional) with propylene oxide added to trimethylolpropane, tetraol (tetrafunctional) with propylene oxide added to the active hydrogen of ethylenediamine, polyol (multifunctional) with propylene oxide added to sorbitol or sucrose, triol (trifunctional) with propylene oxide and ethylene oxide added to glycerin, the ends of which are blocked with ethylene oxide, and tetraol (trifunctional) with propylene oxide and ethylene oxide added to the active hydrogen of ethylenediamine, the ends of which are blocked with ethylene oxide. Examples of such polyols include tetraols (4 functional), polypropylene polyethylene glycols (2 functional) in which the terminals are blocked with ethylene oxide, diols (2 functional) in which propylene oxide and ethylene oxide are added to bisphenol A and the terminals are blocked with ethylene oxide, triols (3 functional) in which ethylene oxide is added to trimethylolpropane, polypropylene polyethylene glycols (2 functional) in which ethylene oxide and propylene oxide are randomly added, triols (3 functional) in which propylene oxide and ethylene oxide are added to glycerin and the terminals are blocked with ethylene oxide and propylene oxide, and flame retardant polyols (2 functional).
　ポリエーテルポリオールの市販品としては、例えば、株式会社ＡＤＥＫＡのアデカポリオール（例えば、Ｐシリーズ、ＢＰＸシリーズ、Ｇシリーズ、Ｔシリーズ、ＥＤＰシリーズ、ＳＰシリーズ、ＳＣシリーズ、Ｒシリーズ、ＲＤシリーズ、ＡＭシリーズ、ＢＭシリーズ、ＣＭシリーズ、ＥＭシリーズ、ＧＭシリーズ、ＰＲシリーズ、ＧＲシリーズ、難燃ポリオールなど）、三洋化成工業株式会社のポリオール（例えば、サンニックスＧＰシリーズ、サンニックスＰＰシリーズ、サンニックスＴＰ－４００シリーズ、サンニックスＳＰ－７５０シリーズ、サンニックスＰＬ－２１００・ＰＰシリーズ、サンエスターシリーズ、プライムポールシリーズ、ニューポールシリーズ、メルポールシリーズ、ＰＥＧシリーズ、マクロゴールシリーズなど）などが挙げられる。 Commercially available polyether polyols include, for example, ADEKA Polyols from ADEKA Corporation (e.g., P series, BPX series, G series, T series, EDP series, SP series, SC series, R series, RD series, AM series, BM series, CM series, EM series, GM series, PR series, GR series, flame-retardant polyols, etc.), and polyols from Sanyo Chemical Industries, Ltd. (e.g., Sannix GP series, Sannix PP series, Sannix TP-400 series, Sannix SP-750 series, Sannix PL-2100/PP series, SunEstar series, Primepol series, Newpol series, Melpol series, PEG series, Macrogol series, etc.).
　ポリエーテルポリオールとしては、本発明の効果がより発現し得る点で、好ましくは、グリセリンにプロピレンオキシドを付加させたトリオール（３官能）、トリメチロールプロパンにプロピレンオキシドを付加させたトリオール（３官能）、グリセリンにプロピレンオキシドとエチレンオキシドを付加させたトリオールであってエチレンオキシドで末端がブロックされているトリオール（３官能）、トリメチロールプロパンにエチレンオキシドを付加させたトリオール（３官能）、グリセリンにプロピレンオキシドとエチレンオキシドを付加させたトリオールであってエチレンオキシドとプロピレンオキシドがランダムに付加したトリオール（３官能）であり、より好ましくは、グリセリンにプロピレンオキシドを付加させたトリオール（３官能）、グリセリンにプロピレンオキシドとエチレンオキシドを付加させたトリオールであってエチレンオキシドで末端がブロックされているトリオール（３官能）、グリセリンにプロピレンオキシドとエチレンオキシドを付加させたトリオールであってエチレンオキシドとプロピレンオキシドがランダムに付加したトリオール（３官能）であり、さらに好ましくは、グリセリンにプロピレンオキシドを付加させたトリオール（３官能）である。 As the polyether polyol, in terms of the effect of the present invention being more effectively exhibited, triol (trifunctional) obtained by adding propylene oxide to glycerin, triol (trifunctional) obtained by adding propylene oxide to trimethylolpropane, triol (trifunctional) obtained by adding propylene oxide and ethylene oxide to glycerin, the ends of which are blocked with ethylene oxide, triol (trifunctional) obtained by adding ethylene oxide to trimethylolpropane, triol (trifunctional) obtained by adding propylene oxide and ethylene oxide to glycerin, the ends of which are blocked with ethylene oxide, A triol (trifunctional) in which propylene oxide is added randomly to glycerin, more preferably a triol (trifunctional) in which propylene oxide is added to glycerin, a triol (trifunctional) in which propylene oxide and ethylene oxide are added to glycerin and the ends are blocked with ethylene oxide, a triol (trifunctional) in which propylene oxide and ethylene oxide are added to glycerin and the ethylene oxide and propylene oxide are added randomly, and even more preferably a triol (trifunctional) in which propylene oxide is added to glycerin.
　ポリエステルポリオールとしては、例えば、酸成分とグリコール成分とを反応させて得られるポリエステルポリオールが挙げられる。酸成分としては、例えば、テレフタル酸、アジピン酸、アゼライン酸、セバチン酸、無水フタル酸、イソフタル酸、トリメリット酸などが挙げられる。グリコール成分としては、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、ブチレングリコール、１，６－ヘキサングリコール、３－メチル－１，５－ペンタンジオール、３，３’－ジメチロールヘプタン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、１，４－ブタンジオール、ネオペンチルグリコール、ブチルエチルペンタンジオール、ポリオール成分としてグリセリン、トリメチロールプロパン、ペンタエリスリトールなどが挙げられる。ポリエステルポリオール（ａ１）としては、その他に、ポリカプロラクトン、ポリ（β－メチル－γ－バレロラクトン）、ポリバレロラクトン等のラクトン類を開環重合して得られるポリエステルポリオールなども挙げられる。 The polyester polyol may be, for example, a polyester polyol obtained by reacting an acid component with a glycol component. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid. Examples of the glycol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, and butylethylpentanediol. Examples of the polyol component include glycerin, trimethylolpropane, and pentaerythritol. Other examples of the polyester polyol (a1) include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone), and polyvalerolactone.
　ポリエステルポリオールの市販品としては、例えば、株式会社ＡＤＥＫＡのアデカニューエース（例えば、Ｆ１８－６２、Ｆ７－６７、Ｙ９－１０、Ｙ４－５、Ｙ５２－１３、Ｙ５２－２１、Ｖ１４－９０、ＹＧ－１０８、Ｆ１２１２－２９、＃５０、Ｙ６５－５５、ＹＴ－１０１、ＹＴ－６５１、ＮＳ－２４００など）などが挙げられる。 Commercially available polyester polyols include, for example, ADEKA New Ace from ADEKA Corporation (e.g., F18-62, F7-67, Y9-10, Y4-5, Y52-13, Y52-21, V14-90, YG-108, F1212-29, #50, Y65-55, YT-101, YT-651, NS-2400, etc.).
　多官能アルコールの数平均分子量は、本発明の効果がより発現し得る点で、好ましくは５０～１００００であり、より好ましくは６０～５０００である。 The number average molecular weight of the polyfunctional alcohol is preferably 50 to 10,000, more preferably 60 to 5,000, in order to better demonstrate the effects of the present invention.
　アクリル系粘着剤組成物中の多官能アルコールの含有量は、本発明の効果を損なわない範囲で、任意の適切な含有量を採用し得る。このような含有量としては、例えば、本発明の効果をより発現させ得る点で、アクリル系ポリマーの固形分（１００重量部）に対して、好ましくは０．０００１重量部～２０重量部であり、より好ましくは０．００１重量部～１５重量部であり、さらに好ましくは０．０１重量部～１０重量部であり、特に好ましくは０．１重量部～５重量部である。 The content of the polyfunctional alcohol in the acrylic adhesive composition may be any appropriate content within the range that does not impair the effects of the present invention. For example, such a content is preferably 0.0001 parts by weight to 20 parts by weight, more preferably 0.001 parts by weight to 15 parts by weight, even more preferably 0.01 parts by weight to 10 parts by weight, and particularly preferably 0.1 parts by weight to 5 parts by weight, relative to the solid content (100 parts by weight) of the acrylic polymer, in order to further exert the effects of the present invention.
＜１－２－ｄ．他の成分＞
　アクリル系粘着剤組成物は、本発明の効果を損なわない範囲で、任意の適切な他の成分を含有し得る。このような他の成分としては、例えば、アクリル系ポリマー以外のポリマー成分、架橋促進剤、架橋触媒、シランカップリング剤、粘着付与樹脂（ロジン誘導体、ポリテルペン樹脂、石油樹脂、油溶性フェノールなど）、老化防止剤、無機充填剤、有機充填剤、金属粉、着色剤（顔料や染料など）、箔状物、紫外線吸収剤、酸化防止剤、光安定剤、造核剤、連鎖移動剤、可塑剤、軟化剤、界面活性剤、帯電防止剤、導電剤、安定剤、表面潤滑剤、レベリング剤、腐食防止剤、耐熱安定剤、重合禁止剤、滑剤、溶剤、触媒などが挙げられる。 <1-2-d. Other ingredients>
The acrylic adhesive composition may contain any other suitable components within the scope that does not impair the effect of the present invention.Such other components include, for example, polymer components other than acrylic polymers, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifier resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), antiaging agents, inorganic fillers, organic fillers, metal powders, colorants (pigments, dyes, etc.), foil-like materials, ultraviolet absorbers, antioxidants, light stabilizers, nucleating agents, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, etc.
≪≪２．被着体≫≫
　被着体は、表面保護フィルムが積層される側の表面の水接触角および算術平均表面粗さＲａが前述の好ましい範囲にある被着体であれば、本発明の効果を損なわない範囲で、任意の適切な被着体を採用し得る。 <<2. Substrate≫≫
As long as the adherend has a water contact angle and an arithmetic mean surface roughness Ra of the surface on which the surface protective film is laminated within the above-mentioned preferred ranges, the effect of the present invention is not impaired. Any suitable adherend may be employed.
　被着体の表面保護フィルム側（表面保護フィルムが積層されている側）の表面の水接触角は、前述したように、好ましくは８５°以上であり、より好ましくは８５°～１１０°であり、さらに好ましくは８５°～１０５°であり、特に好ましくは９０°～１００°であり、最も好ましくは９１°～１００°である。上記水接触角が上記範囲内にあれば、本発明の効果がより発現し得る。上記水接触角が上記範囲を外れて小さすぎると、表面保護フィルムが被着体に過度に密着しやすくなり、例えば、被着体からの表面保護フィルムの初期剥離力が高くなって、被着体から表面保護フィルムを剥離できなくなるおそれがあり、被着体からの表面保護フィルムの剥離力が経時で大きく上昇しすぎて、被着体から表面保護フィルムを剥離できなくなるおそれがある。上記水接触角が上記範囲を外れて大きすぎると、表面保護フィルムが被着体に過度に密着しにくくなり、例えば、被着体からの表面保護フィルムの初期剥離力が低すぎることとなり、被着体からの表面保護フィルムの浮きが生じるおそれや、表面保護フィルムに最表面に設けられ得るはく離ライナーをはく離する際のはく離不良が生じるおそれがある。 As described above, the water contact angle of the surface of the adherend on the surface protection film side (the side on which the surface protection film is laminated) is preferably 85° or more, more preferably 85° to 110°, even more preferably 85° to 105°, particularly preferably 90° to 100°, and most preferably 91° to 100°. If the water contact angle is within the above range, the effects of the present invention can be more effectively achieved. If the water contact angle is outside the above range and is too small, the surface protection film is likely to adhere excessively to the adherend, and, for example, the initial peeling force of the surface protection film from the adherend may become too high, making it impossible to peel the surface protection film from the adherend, or the peeling force of the surface protection film from the adherend may increase too much over time, making it impossible to peel the surface protection film from the adherend. If the water contact angle is too large outside the above range, the surface protection film will not adhere too closely to the adherend, and for example, the initial peel strength of the surface protection film from the adherend will be too low, which may cause the surface protection film to lift off the adherend or cause poor peeling when peeling off a release liner that may be provided on the outermost surface of the surface protection film.
　被着体の表面保護フィルム側（表面保護フィルムが積層されている側）の表面の算術平均表面粗さＲａは、前述したように、好ましくは０．６μｍ以下であり、より好ましくは０．３５μｍ以下であり、さらに好ましくは０．２μ以下であり、特に好ましくは０．１μｍ以下であり、最も好ましくは０．０８μｍ以下である。上記算術平均表面粗さＲａの下限値は小さければ小さいほどよく、好ましくは０μｍ以上である。上記算術平均表面粗さＲａが上記範囲内にあれば、本発明の効果がより発現し得る。上記算術平均表面粗さＲａが上記範囲を外れて大きすぎると、例えば、表面保護フィルムが有する粘着剤層の厚みが大きい場合、被着体からの表面保護フィルムの剥離力が経時で大きく上昇しすぎて、被着体から表面保護フィルムを剥離できなくなるおそれがある。 As described above, the arithmetic mean surface roughness Ra of the surface of the adherend on the surface protection film side (the side on which the surface protection film is laminated) is preferably 0.6 μm or less, more preferably 0.35 μm or less, even more preferably 0.2 μm or less, particularly preferably 0.1 μm or less, and most preferably 0.08 μm or less. The lower limit of the arithmetic mean surface roughness Ra is preferably as small as possible, and is preferably 0 μm or more. If the arithmetic mean surface roughness Ra is within the above range, the effect of the present invention can be more effectively achieved. If the arithmetic mean surface roughness Ra is too large outside the above range, for example, when the thickness of the adhesive layer of the surface protection film is large, the peeling force of the surface protection film from the adherend increases too much over time, and it may become impossible to peel the surface protection film from the adherend.
　被着体は、代表的には、光学部材である。光学部材としては、本発明の効果を損なわない範囲で、任意の適切な光学部材を採用し得る。このような光学部材としては、例えば、任意の適切な基材上に任意の適切な層を有する部材が挙げられる。具体的な光学部材としては、例えば、偏光板、位相差板、ディスプレイ、撮像装置、レンズ、（ハーフ）ミラーなどが挙げられる。 The adherend is typically an optical member. Any suitable optical member may be used as the optical member as long as it does not impair the effects of the present invention. Examples of such optical members include members having any suitable layer on any suitable substrate. Specific examples of optical members include polarizing plates, retardation plates, displays, imaging devices, lenses, and (half) mirrors.
　なお、被着体としては、表面保護フィルムを積層する側の表面の水接触角と表面保護フィルムを積層する側の表面の算術平均表面粗さＲａが前述した好ましい範囲に入るような被着体を選択すればよく、その表面の材料については任意の適切な材料を採用し得る。しかしながら、本発明の効果をより発現させ得る点で、このような材料としては、代表的には、樹脂が挙げられ、被着体としては、好ましくは、任意の適切な樹脂層を有する部材が挙げられる。 The adherend may be selected so that the water contact angle and the arithmetic mean surface roughness Ra of the surface on which the surface protective film is laminated are within the above-mentioned preferred ranges, and any appropriate material may be used for the surface. However, in terms of being able to more effectively exert the effects of the present invention, a representative example of such a material is a resin, and the adherend is preferably a member having any appropriate resin layer.
　被着体の厚みは、その種類によって、任意の適切な厚みを採用し得る。代表的には、被着体の厚みは、好ましくは５μｍ～９５０μｍであり、より好ましくは２０μｍ～７５０μｍであり、さらに好ましくは３０μｍ～５５０μｍであり、特に好ましくは４０μｍ～４５０μｍである。 The thickness of the adherend may be any appropriate thickness depending on the type of adherend. Typically, the thickness of the adherend is preferably 5 μm to 950 μm, more preferably 20 μm to 750 μm, even more preferably 30 μm to 550 μm, and particularly preferably 40 μm to 450 μm.
　以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例になんら限定されるものではない。なお、実施例等における、試験および評価方法は以下のとおりである。なお、「部」と記載されている場合は、特記事項がない限り「重量部」を意味し、「％」と記載されている場合は、特記事項がない限り「重量％」を意味する。 The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples. The test and evaluation methods used in the examples are as follows. Note that "parts" means "parts by weight" unless otherwise specified, and "%" means "% by weight" unless otherwise specified.
＜水接触角の測定＞
　被着体の表面保護フィルム側（表面保護フィルムが積層されている側）の表面に水２μLを滴下し、滴下０．５秒後の水接触角［°］を求めた。水接触角の測定は、市販の接触角測定装置を用いて、ＪＩＳ　Ｒ　３２５７：１９９９に準拠して測定した（液滴法）。具体的には、下記の条件で測定した。測定は５回行い、その平均値を採用した（ｎ＝５）。
［水接触角測定条件］
測定装置：接触角測定器　ＤｒｏｐＭａｓｔｅｒ　ＤＭ７００（協和界面科学社製）
測定雰囲気：２３℃、５０％ＲＨ
測定液体：蒸留水
測定時間：着滴５００ｍｓ後 <Measurement of Water Contact Angle>
2 μL of water was dropped onto the surface of the adherend on the surface protection film side (the side on which the surface protection film was laminated), and the water contact angle [°] was measured 0.5 seconds after the drop. The water contact angle was measured using a commercially available contact angle measuring device in accordance with JIS R 3257:1999 (sessile drop method). Specifically, the measurement was performed under the following conditions. The measurement was performed five times, and the average value was used (n=5).
[Water contact angle measurement conditions]
Measurement device: Contact angle measuring device DropMaster DM700 (manufactured by Kyowa Interface Science Co., Ltd.)
Measurement atmosphere: 23°C, 50% RH
Measurement liquid: distilled water Measurement time: 500 ms after droplets
＜算術平均表面粗さＲａの測定＞
　被着体の表面保護フィルム側（表面保護フィルムが積層されている側）の表面の、算術平均表面粗さＲａを測定した。具体的には、下記の条件で測定した。
［算術平均表面粗さＲａの測定条件］
測定装置：高精度微細形状測定機　ＳＵＲＦＣＯＲＤＥＲ　ＥＴ４０００Ａ（小坂研究所社製）
検出部の触針：先端曲率半径０．５μｍ、頂角６０度、材質ダイヤモンド
基準長さ（粗さ曲線のカットオフ値λｃ）：０．８ｍｍ
評価長さ（基準長さ）：１２ｍｍ
触針の送り速さ：１ｍｍ／ｓ
縦倍率：２００００倍
横倍率：１０倍 <Measurement of arithmetic mean surface roughness Ra>
The arithmetic mean surface roughness Ra of the surface of the adherend on the surface protective film side (the side on which the surface protective film was laminated) was measured. Specifically, the measurement was performed under the following conditions.
[Measurement conditions for arithmetic mean surface roughness Ra]
Measuring device: High-precision micro-shape measuring device SURFCORDER ET4000A (manufactured by Kosaka Laboratory)
Stylus of detection part: Tip curvature radius 0.5 μm, apex angle 60 degrees, material diamond Reference length (cutoff value λc of roughness curve): 0.8 mm
Evaluation length (reference length): 12 mm
Stylus feed speed: 1 mm/s
Vertical magnification: 20,000 times Horizontal magnification: 10 times
＜変形の評価＞
　図２に示すように、上面に、縦２５ｍｍ、横２５ｍｍ、深さ１ｍｍのサイズの凹部が形成された試験板２０００の上面に、実施例、比較例で得られた積層体（表面保護フィルム付被着体）を縦６０ｍｍ、横６０ｍｍに切り取った試験片）１０００を載置した。この状態で、半径Ｒ＝８ｍｍの棒３０００を、積層体１０００の上面（表面保護フィルム側）から試験板２０００の凹部中央部の底面に向かって１ｍｍ押し込み、この状態を１．０秒間保持してから棒を積層体１０００から離したとき、積層体１０００に押し跡が残るか否かを確認した。
（評価）
なし（〇）：押し跡が残らない。
あり（×）：押し跡が残る。 <Deformation evaluation>
As shown in Fig. 2, a test piece 1000 was placed on the upper surface of a test plate 2000 having a recess of 25 mm length, 25 mm width and 1 mm depth formed on the upper surface. The laminate (adherend with surface protective film) obtained in the Examples and Comparative Examples was cut to a length of 60 mm and a width of 60 mm. In this state, a rod 3000 with a radius R = 8 mm was pressed 1 mm from the upper surface (surface protective film side) of the laminate 1000 toward the bottom surface of the center of the recess of the test plate 2000. This state was maintained for 1.0 second, and then the rod was removed from the laminate 1000. When this state was maintained, it was confirmed whether or not a pressing mark remained on the laminate 1000.
(evaluation)
None (〇): No indentation remains.
Yes (×): Indentations remain.
＜初期剥離力（Ａ）＞
　実施例、比較例で得られた積層体（表面保護フィルム付被着体）について、製造後、温度２３℃、相対湿度５０％の環境に３０分間静置した後、同環境下で、剥離角度１８０°、引張速度３００ｍｍ／分でピール試験を行って１８０°剥離力を測定し、これを初期剥離力とした。
　なお、本発明の実施形態の積層体においては、本発明の効果をより発現し得る点で、この初期剥離力（Ａ）は、好ましくは０．０２５Ｎ／２５ｍｍ以上０．１００Ｎ／２５ｍｍ未満であり、より好ましくは０．０３０Ｎ／２５ｍｍ以上０．０９０Ｎ／２５ｍｍ未満であり、さらに好ましくは０．０３５Ｎ／２５ｍｍ以上０．０８５Ｎ／２５ｍｍ未満であり、さらに好ましくは０．０４０Ｎ／２５ｍｍ以上０．０８５Ｎ／２５ｍｍ未満であり、さらに好ましくは０．０４０Ｎ／２５ｍｍ以上０．０８０Ｎ／２５ｍｍ未満であり、特に好ましくは０．０４０Ｎ／２５ｍｍ以上０．０７５Ｎ／２５ｍｍ未満であり、最も好ましくは０．０４０Ｎ／２５ｍｍ以上０．０７０Ｎ／２５ｍｍ未満である。
　評価基準は下記の通りとした。
（評価基準）
◎：０．０４０Ｎ／２５ｍｍ以上０．０８５Ｎ／２５ｍｍ未満
〇：０．０３０Ｎ／２５ｍｍ以上０．０４０Ｎ／２５ｍｍ未満または０．０８５Ｎ／２５ｍｍ以上０．０９０Ｎ／２５ｍｍ未満
△：０．０２５Ｎ／２５ｍｍ以上０．０３０Ｎ／２５ｍｍ未満または０．０９０Ｎ／２５ｍｍ以上０．１００Ｎ／２５ｍｍ未満
×：０．０２５Ｎ／２５ｍｍ未満または０．１００Ｎ／２５ｍｍ以上 <Initial peel strength (A)>
After production, the laminates (adherends with surface protective films) obtained in the examples and comparative examples were allowed to stand for 30 minutes in an environment at a temperature of 23°C and a relative humidity of 50%, and then a peel test was carried out in the same environment at a peel angle of 180° and a tensile speed of 300 mm/min to measure the 180° peel strength, which was recorded as the initial peel strength.
In the laminate according to the embodiment of the present invention, in order to more effectively exhibit the effects of the present invention, the initial peel force (A) is preferably 0.025 N/25 mm or more and less than 0.100 N/25 mm, more preferably 0.030 N/25 mm or more and less than 0.090 N/25 mm, even more preferably 0.035 N/25 mm or more and less than 0.085 N/25 mm, even more preferably 0.040 N/25 mm or more and less than 0.085 N/25 mm, even more preferably 0.040 N/25 mm or more and less than 0.080 N/25 mm, particularly preferably 0.040 N/25 mm or more and less than 0.075 N/25 mm, and most preferably 0.040 N/25 mm or more and less than 0.070 N/25 mm.
The evaluation criteria were as follows.
(Evaluation criteria)
◎: 0.040N/25mm or more and less than 0.085N/25mm 〇: 0.030N/25mm or more and less than 0.040N/25mm or 0.085N/25mm or more and less than 0.090N/25mm △: 0.025N/25mm or more and less than 0.030N/25mm or 0.090N/25mm or more and less than 0.100N/25mm ×: Less than 0.025N/25mm or 0.100N/25mm or more
＜６０℃×７２時間保管後の剥離力（Ｂ）＞
　実施例、比較例で得られた積層体（表面保護フィルム付被着体）について、製造後、温度６０℃の環境に７２時間保管し、その後、温度２３℃、相対湿度５０％の環境に３０分間静置した後、同環境下で、剥離角度１８０°、引張速度３００ｍｍ／分でピール試験を行って１８０°剥離力を測定し、これを６０℃×７２時間保管後の剥離力とした。
　なお、本発明の実施形態の積層体においては、本発明の効果をより発現し得る点で、この６０℃×７２時間保管後の剥離力（Ｂ）は、好ましくは０．０３０Ｎ／２５ｍｍ以上０．１１５Ｎ／２５ｍｍ未満であり、より好ましくは０．０４０Ｎ／２５ｍｍ以上０．１０５Ｎ／２５ｍｍ未満であり、さらに好ましくは０．０４０Ｎ／２５ｍｍ以上０．１００Ｎ／２５ｍｍ未満であり、さらに好ましくは０．０４５Ｎ／２５ｍｍ以上０．０９５Ｎ／２５ｍｍ未満であり、さらに好ましくは０．０５０Ｎ／２５ｍｍ以上０．０９５Ｎ／２５ｍｍ未満であり、特に好ましくは０．０５５Ｎ／２５ｍｍ以上０．０９５Ｎ／２５ｍｍ未満であり、最も好ましくは０．０５５Ｎ／２５ｍｍ以上０．０９２Ｎ／２５ｍｍ未満である。
　評価基準は下記の通りとした。
（評価基準）
◎：０．０５５Ｎ／２５ｍｍ以上０．０９５Ｎ／２５ｍｍ未満
〇：０．０４０Ｎ／２５ｍｍ以上０．０５５Ｎ／２５ｍｍ未満または０．０９５Ｎ／２５ｍｍ以上０．１００Ｎ／２５ｍｍ未満
△：０．０３０Ｎ／２５ｍｍ以上０．０４０Ｎ／２５ｍｍ未満または０．１００Ｎ／２５ｍｍ以上０．１１５Ｎ／２５ｍｍ未満
×：０．０３０Ｎ／２５ｍｍ未満または０．１１５Ｎ／２５ｍｍ以上 <Peeling force after storage at 60° C. for 72 hours (B)>
After production, the laminates (adherends with surface protective films) obtained in the examples and comparative examples were stored in an environment at a temperature of 60°C for 72 hours, and then allowed to stand for 30 minutes in an environment at a temperature of 23°C and a relative humidity of 50%, and then a peel test was carried out in the same environment at a peel angle of 180° and a tensile speed of 300 mm/min to measure the 180° peel strength, which was recorded as the peel strength after storage at 60°C for 72 hours.
In the laminate of the embodiment of the present invention, in order to more effectively exhibit the effects of the present invention, the peel force (B) after storage at 60°C for 72 hours is preferably 0.030 N/25 mm or more and less than 0.115 N/25 mm, more preferably 0.040 N/25 mm or more and less than 0.105 N/25 mm, even more preferably 0.040 N/25 mm or more and less than 0.100 N/25 mm, still more preferably 0.045 N/25 mm or more and less than 0.095 N/25 mm, still more preferably 0.050 N/25 mm or more and less than 0.095 N/25 mm, particularly preferably 0.055 N/25 mm or more and less than 0.095 N/25 mm, and most preferably 0.055 N/25 mm or more and less than 0.092 N/25 mm.
The evaluation criteria were as follows.
(Evaluation criteria)
◎: 0.055N/25mm or more and less than 0.095N/25mm 〇: 0.040N/25mm or more and less than 0.055N/25mm or 0.095N/25mm or more and less than 0.100N/25mm △: 0.030N/25mm or more and less than 0.040N/25mm or 0.100N/25mm or more and less than 0.115N/25mm ×: Less than 0.030N/25mm or 0.115N/25mm or more
＜剥離力変化（Ｂ）－（Ａ）＞
　本発明の実施形態の積層体においては、本発明の効果をより発現し得る点で、この剥離力変化（Ｂ）－（Ａ）は、小さければ小さいほど好ましく、好ましくは０．０４５Ｎ／２５ｍｍ未満であり、より好ましくは０．０４２Ｎ／２５ｍｍ未満であり、さらに好ましくは０．０４０Ｎ／２５ｍｍ未満であり、さらに好ましくは０．０３７Ｎ／２５ｍｍ未満であり、さらに好ましくは０．０３５Ｎ／２５ｍｍ未満であり、特に好ましくは０．０３２Ｎ／２５ｍｍ未満であり、最も好ましくは０．０３０Ｎ／２５ｍｍ未満である。
　評価基準は下記の通りとした。
（評価基準）
◎：０．０３５Ｎ／２５ｍｍ未満
〇：０．０３５Ｎ／２５ｍｍ以上０．０４２Ｎ／２５ｍｍ未満
△：０．０４２Ｎ／２５ｍｍ以上０．０４５Ｎ／２５ｍｍ未満
×：０．０４５Ｎ／２５ｍｍ以上 <Change in peel force (B) - (A)>
In the laminate of the embodiment of the present invention, in order to more effectively exhibit the effects of the present invention, the smaller this peel force change (B) - (A) is, the more preferable, and is preferably less than 0.045 N/25 mm, more preferably less than 0.042 N/25 mm, even more preferably less than 0.040 N/25 mm, even more preferably less than 0.037 N/25 mm, even more preferably less than 0.035 N/25 mm, particularly preferably less than 0.032 N/25 mm, and most preferably less than 0.030 N/25 mm.
The evaluation criteria were as follows.
(Evaluation criteria)
◎: Less than 0.035N/25mm ◯: 0.035N/25mm or more and less than 0.042N/25mm △: 0.042N/25mm or more and less than 0.045N/25mm ×: 0.045N/25mm or more
＜粘着剤層のクリープリカバリー値＞
　積層体から粘着剤層のみを取り出し、積層して約１ｍｍの厚みとし、これをφ８ｍｍに打ち抜き、円柱状のペレットを作製して測定用サンプルとした。
　動的粘弾性測定装置（ＴＡ　Ｉｎｓｔｒｕｍｅｎｔｓ社製、ＤＨＲ２）を用い、得られた測定サンプルをφ８ｍｍパラレルプレートの治具に固定した。２５℃において、５ＫＰａの変形応力を加えて３００秒間保持した後の変形歪み（％）をＡ値、さらに変形応力を０にして３００秒間保持した後の変形歪み（％）をＢ値とし、［｛（Ａ値－Ｂ値）／Ａ値｝×１００］で算出される値をクリープリカバリー値とした。 <Creep recovery value of adhesive layer>
Only the pressure-sensitive adhesive layer was taken out from the laminate, laminated to a thickness of about 1 mm, and punched out to a diameter of 8 mm to prepare a cylindrical pellet, which was used as a measurement sample.
Using a dynamic viscoelasticity measuring device (TA Instruments, DHR2), the obtained measurement sample was fixed to a jig with a φ8 mm parallel plate. At 25°C, the deformation strain (%) after applying a deformation stress of 5 KPa and holding for 300 seconds was defined as A value, and the deformation strain (%) after further reducing the deformation stress to 0 and holding for 300 seconds was defined as B value. The value calculated by [{(A value-B value)/A value}×100] was defined as the creep recovery value.
＜せん断弾性係数＞
　実施例、比較例で得られた積層体に用いられている表面保護フィルムを５ｍｍ（ＴＤ）×５０ｍｍ（ＭＤ）に切り出し、アクリル板（三菱ケミカル製、商品名「アクリライトＬ」）を被着体として、該表面保護フィルムの粘着剤層を接地面積５ｍｍ×１０ｍｍとなるようにして貼り合わせた。その後、温度２３℃、相対湿度５０％の環境に３０分間静置した後、同環境下で、精密万能試験機（島津製作所社製、ＡＵＴＯＧＲＡＰＨ　ＡＧ－Ｘ　ｐｌｕｓ）を用いて、せん断方向に、引張速度０．０６ｍｍ／ｍｉｎでせん断応力を測定し、せん断ひずみ（横軸）－せん断応力（縦軸）曲線を得た。
　せん断弾性係数Ｇは、せん断ひずみ０．０５ｍｍから０．２ｍｍまでの傾きとして、下記式より算出した。
　Ｇ＝τ／γ＝（τ0.2－τ0.05）／（０．２－０．０５）
τ：せん断応力［Ｎ／５０ｍｍ2］
γ：せん断ひずみ［ｍｍ］
τ0.2：せん断ひずみ０．２ｍｍにおけるせん断応力［Ｎ／５０ｍｍ2］
τ0.05：せん断ひずみ０．０５ｍｍにおけるせん断応力［Ｎ／５０ｍｍ2］ <Shear modulus>
The surface protection film used in the laminate obtained in the examples and comparative examples was cut to 5 mm (TD) x 50 mm (MD), and the adhesive layer of the surface protection film was attached to an acrylic plate (manufactured by Mitsubishi Chemical, product name "Acrylite L") as an adherend so that the contact area was 5 mm x 10 mm. After that, it was left to stand for 30 minutes in an environment of 23 ° C. and 50% relative humidity, and then, in the same environment, a precision universal testing machine (manufactured by Shimadzu Corporation, AUTOGRAPH AG-X plus) was used to measure the shear stress in the shear direction at a tensile speed of 0.06 mm / min, and a shear strain (horizontal axis) - shear stress (vertical axis) curve was obtained.
The shear modulus G was calculated from the following formula as the slope from a shear strain of 0.05 mm to 0.2 mm.
G = τ/γ = (τ 0.2 - τ 0.05 )/(0.2 - 0.05)
τ: shear stress [N/50 mm 2 ]
γ: Shear strain [mm]
τ 0.2 : Shear stress at shear strain of 0.2 mm [N/50 mm 2 ]
τ 0.05 : Shear stress at shear strain of 0.05 mm [N/50 mm 2 ]
［製造例１］：アクリル系ポリマー（１）の製造
　温度計、攪拌機、冷却器および窒素ガス導入管を備える反応容器内に、モノマー成分として、２－エチルヘキシルアクリレート（２ＥＨＡ）：９６．２重量部、２－ヒドロキシエチルアクリレート（ＨＥＡ）：３．８重量部、ならびに、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重量部を、酢酸エチル：１５０重量部とともに仕込み、２３℃で緩やかに攪拌しながら窒素ガスを導入して窒素置換を行った。その後、液温を６５℃付近に保って６時間重合反応を行い、アクリル系ポリマー（１）の溶液（濃度４０重量％）を製造した。アクリル系ポリマー（１）の重量平均分子量は５４万であった。
　また、アクリル系ポリマー（１）のＴｇは、ＦＯＸの式により算出すると、（－７０℃×０．９６２）＋（－１５℃×０．０３８）＝（－６７．３４℃）＋（－０．５７℃）＝－６７．９１℃であった。 [Production Example 1]: Production of Acrylic Polymer (1) In a reaction vessel equipped with a thermometer, a stirrer, a cooler and a nitrogen gas inlet tube, 96.2 parts by weight of 2-ethylhexyl acrylate (2EHA), 3.8 parts by weight of 2-hydroxyethyl acrylate (HEA), and 0.2 parts by weight of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator were charged together with 150 parts by weight of ethyl acetate, and nitrogen gas was introduced while gently stirring at 23°C to perform nitrogen substitution. Thereafter, the liquid temperature was kept at around 65°C and a polymerization reaction was carried out for 6 hours to produce a solution of acrylic polymer (1) (concentration 40% by weight). The weight average molecular weight of the acrylic polymer (1) was 540,000.
The Tg of the acrylic polymer (1) was calculated according to the FOX formula as follows: (-70°C x 0.962) + (-15°C x 0.038) = (-67.34°C) + (-0.57°C) = -67.91°C.
［製造例２］：アクリル系ポリマー（２）の製造
　温度計、攪拌機、冷却器および窒素ガス導入管を備える反応容器内に、モノマー成分として、２－エチルヘキシルアクリレート（２ＥＨＡ）：１００．０重量部、酢酸ビニル（ＶＡｃ）：８０重量部、アクリル酸（ＡＡ）：５．０重量部、ならびに、重合開始剤としてベンゾイルパーオキサイド（ＢＰＯ、日油（株）製「ナイパー（登録商標）ＢＷ」）：０．３重量部を、トルエン：２６３重量部とともに仕込み、２３℃で緩やかに攪拌しながら窒素ガスを導入して窒素置換を行った。その後、液温を６３℃付近に保って６時間重合反応を行った。その後、容器内容物の温度を８０℃に昇温して３．５時間熟成し、アクリル系ポリマー（２）の溶液（濃度４０重量％）を製造した。アクリル系ポリマー（２）の重量平均分子量は６５万であった。
　また、アクリル系ポリマー（２）のＴｇは、ＦＯＸの式により算出すると、（－７０℃×０．５４１）＋（３０℃×０．４３２）＋（１０６℃×０．０２７）＝（－３７．８７℃）＋（１２．９６℃）＋（２．８６℃）＝－２２．０５℃であった。 [Production Example 2]: Production of Acrylic Polymer (2) In a reaction vessel equipped with a thermometer, a stirrer, a cooler and a nitrogen gas inlet tube, 100.0 parts by weight of 2-ethylhexyl acrylate (2EHA), 80 parts by weight of vinyl acetate (VAc), 5.0 parts by weight of acrylic acid (AA), and 0.3 parts by weight of benzoyl peroxide (BPO, NOF Corp.'s "Niper (registered trademark) BW") as a polymerization initiator were charged together with 263 parts by weight of toluene, and nitrogen gas was introduced while gently stirring at 23°C to perform nitrogen substitution. Thereafter, the liquid temperature was kept at around 63°C and a polymerization reaction was carried out for 6 hours. Thereafter, the temperature of the contents of the vessel was raised to 80°C and aged for 3.5 hours to produce a solution of acrylic polymer (2) (concentration 40% by weight). The weight average molecular weight of the acrylic polymer (2) was 650,000.
The Tg of the acrylic polymer (2) was calculated according to the FOX formula as follows: (-70°C x 0.541) + (30°C x 0.432) + (106°C x 0.027) = (-37.87°C) + (12.96°C) + (2.86°C) = -22.05°C.
［製造例３］：アクリル系ポリマー（３）の製造
　６時間重合反応を行った後、熟成を行わなかった以外は、製造例２と同様に行い、アクリル系ポリマー（３）の溶液（濃度４０重量％）を製造した。アクリル系ポリマー（３）の重量平均分子量は８１万であった。 [Production Example 3]: Production of acrylic polymer (3) A solution of acrylic polymer (3) (concentration: 40% by weight) was produced in the same manner as in Production Example 2, except that the polymerization reaction was carried out for 6 hours and then aging was not carried out. The weight average molecular weight of the acrylic polymer (3) was 810,000.
［製造例４］：アクリル系ポリマー（４）の製造
　熟成時間を３．５時間から２時間に変更した以外は、製造例２と同様に行い、アクリル系ポリマー（４）の溶液（濃度４０重量％）を製造した。アクリル系ポリマー（４）の重量平均分子量は７１万であった。 [Production Example 4]: Production of acrylic polymer (4) A solution of acrylic polymer (4) (concentration 40% by weight) was produced in the same manner as in Production Example 2, except that the maturation time was changed from 3.5 hours to 2 hours. The weight average molecular weight of the acrylic polymer (4) was 710,000.
［製造例５］：アクリル系ポリマー（５）の製造
　熟成時間を３．５時間から７時間に変更した以外は、製造例２と同様に行い、アクリル系ポリマー（５）の溶液（濃度４０重量％）を製造した。アクリル系ポリマー（５）の重量平均分子量は４６万であった。 [Production Example 5]: Production of acrylic polymer (5) A solution of acrylic polymer (5) (concentration: 40% by weight) was produced in the same manner as in Production Example 2, except that the maturation time was changed from 3.5 hours to 7 hours. The weight average molecular weight of the acrylic polymer (5) was 460,000.
［製造例６］：アクリル系粘着剤組成物（１）の製造
　製造例１で得られたアクリル系ポリマー（１）の溶液の固形分１００重量部に対して、添加剤としてサンニックスＰＰ－３０００（三洋化成工業社製）を固形分換算で０．５重量部加え、架橋剤としてタケネートＤ－１０１Ｅ（三井化学社製）を固形分換算で３．０重量部を加えて、全体の固形分が２９重量％となるようにトルエンで希釈し、ディスパーで攪拌し、アクリル系粘着剤組成物（１）を製造した。 [Production Example 6]: Production of acrylic pressure-sensitive adhesive composition (1) To 100 parts by weight of the solid content of the solution of the acrylic polymer (1) obtained in Production Example 1, 0.5 parts by weight, calculated as solid content, of Sannix PP-3000 (manufactured by Sanyo Chemical Industries, Ltd.) was added as an additive, and 3.0 parts by weight, calculated as solid content, of Takenate D-101E (manufactured by Mitsui Chemicals, Inc.) was added as a crosslinking agent, and the mixture was diluted with toluene to a total solid content of 29% by weight, and stirred with a disper to produce an acrylic pressure-sensitive adhesive composition (1).
［製造例７］：アクリル系粘着剤組成物（２）の製造
　製造例２で得られたアクリル系ポリマー（２）の溶液の固形分１００重量部に対して、架橋剤としてＴＥＴＲＡＤ－Ｃ（三菱瓦斯化学社製）を固形分換算で４．０重量部を加えて、全体の固形分が２２重量％となるようにメチルエチルケトンで希釈し、ディスパーで攪拌し、アクリル系粘着剤組成物（２）を製造した。 [Production Example 7]: Production of acrylic pressure-sensitive adhesive composition (2) To 100 parts by weight of the solid content of the solution of the acrylic polymer (2) obtained in Production Example 2, 4.0 parts by weight, calculated as solid content, of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent was added, and the mixture was diluted with methyl ethyl ketone so that the total solid content became 22% by weight, and stirred with a disper to produce an acrylic pressure-sensitive adhesive composition (2).
［製造例８］：アクリル系粘着剤組成物（３）の製造
　製造例３で得られたアクリル系ポリマー（３）の溶液の固形分１００重量部に対して、架橋剤としてＴＥＴＲＡＤ－Ｃ（三菱瓦斯化学社製）を固形分換算で４．０重量部を加えて、全体の固形分が２２重量％となるようにメチルエチルケトンで希釈し、ディスパーで攪拌し、アクリル系粘着剤組成物（３）を製造した。 [Production Example 8]: Production of acrylic pressure-sensitive adhesive composition (3) To 100 parts by weight of the solid content of the solution of the acrylic polymer (3) obtained in Production Example 3, 4.0 parts by weight, calculated as solid content, of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent was added, and the mixture was diluted with methyl ethyl ketone so that the total solid content became 22% by weight, and stirred with a disper to produce an acrylic pressure-sensitive adhesive composition (3).
［製造例９］：アクリル系粘着剤組成物（４）の製造
　製造例４で得られたアクリル系ポリマー（４）の溶液の固形分１００重量部に対して、架橋剤としてＴＥＴＲＡＤ－Ｃ（三菱瓦斯化学社製）を固形分換算で４．０重量部を加えて、全体の固形分が２２重量％となるようにメチルエチルケトンで希釈し、ディスパーで攪拌し、アクリル系粘着剤組成物（４）を製造した。 [Production Example 9]: Production of acrylic pressure-sensitive adhesive composition (4) To 100 parts by weight of the solid content of the solution of the acrylic polymer (4) obtained in Production Example 4, 4.0 parts by weight, calculated as solid content, of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent was added, and the mixture was diluted with methyl ethyl ketone so that the total solid content became 22% by weight, and stirred with a disper to produce an acrylic pressure-sensitive adhesive composition (4).
［製造例１０］：アクリル系粘着剤組成物（５）の製造
　製造例５で得られたアクリル系ポリマー（５）の溶液の固形分１００重量部に対して、架橋剤としてＴＥＴＲＡＤ－Ｃ（三菱瓦斯化学社製）を固形分換算で４．０重量部を加えて、全体の固形分が２２重量％となるようにメチルエチルケトンで希釈し、ディスパーで攪拌し、アクリル系粘着剤組成物（５）を製造した。 [Production Example 10]: Production of acrylic pressure-sensitive adhesive composition (5) To 100 parts by weight of the solid content of the solution of the acrylic polymer (5) obtained in Production Example 5, 4.0 parts by weight, calculated as solid content, of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent was added, and the mixture was diluted with methyl ethyl ketone so that the total solid content became 22% by weight, and stirred with a disper to produce an acrylic pressure-sensitive adhesive composition (5).
［製造例１１］：表面保護フィルム（１）の製造
　二軸延伸ポリエステルフィルム（三菱ケミカル製「Ｔ１００Ｃ３８」、厚み３８μｍ）のコロナ面に、製造例６で得られたアクリル系粘着剤組成物（１）を塗布し、１３０℃で２分間加熱して、厚み２１μｍの粘着剤層を形成した。粘着剤層の表面に、はく離ライナー（片面がシリコーン離型処理された厚み２５μｍのポリエステルフィルム）の離型処理面を貼り合わせ、はく離ライナー付きの表面保護フィルム（１）を製造した。 [Production Example 11]: Production of Surface Protective Film (1) The acrylic pressure-sensitive adhesive composition (1) obtained in Production Example 6 was applied to the corona surface of a biaxially stretched polyester film ("T100C38" manufactured by Mitsubishi Chemical, thickness 38 μm) and heated at 130° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 21 μm. The release-treated surface of a release liner (a polyester film having a thickness of 25 μm and one side of which was treated with silicone release) was bonded to the surface of the pressure-sensitive adhesive layer to produce a surface protective film (1) with a release liner.
［製造例１２］：表面保護フィルム（２）の製造
　二軸延伸ポリエステルフィルム（三菱ケミカル製「Ｔ１００Ｃ３８」、厚み３８μｍ）のコロナ面に、製造例７で得られたアクリル系粘着剤組成物（２）を塗布し、１３０℃で２分間加熱して、厚み２１μｍの粘着剤層を形成した。粘着剤層の表面に、はく離ライナー（片面がシリコーン離型処理された厚み２５μｍのポリエステルフィルム）の離型処理面を貼り合わせ、はく離ライナー付きの表面保護フィルム（２）を製造した。 [Production Example 12]: Production of Surface Protective Film (2) The acrylic pressure-sensitive adhesive composition (2) obtained in Production Example 7 was applied to the corona surface of a biaxially stretched polyester film ("T100C38" manufactured by Mitsubishi Chemical, thickness 38 μm) and heated at 130° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 21 μm. The release-treated surface of a release liner (a polyester film having a thickness of 25 μm and one side of which was treated with silicone release) was bonded to the surface of the pressure-sensitive adhesive layer to produce a surface protective film (2) with a release liner.
［製造例１３］：表面保護フィルム（３）の製造
　二軸延伸ポリエステルフィルム（三菱ケミカル製「Ｔ１００Ｃ３８」、厚み３８μｍ）のコロナ面に、製造例８で得られたアクリル系粘着剤組成物（３）を塗布し、１３０℃で２分間加熱して、厚み１０μｍの粘着剤層を形成した。粘着剤層の表面に、はく離ライナー（片面がシリコーン離型処理された厚み２５μｍのポリエステルフィルム）の離型処理面を貼り合わせ、はく離ライナー付きの表面保護フィルム（３）を製造した。 [Production Example 13]: Production of Surface Protective Film (3) The acrylic pressure-sensitive adhesive composition (3) obtained in Production Example 8 was applied to the corona surface of a biaxially stretched polyester film ("T100C38" manufactured by Mitsubishi Chemical, thickness 38 μm) and heated at 130° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 10 μm. The release-treated surface of a release liner (a polyester film having a thickness of 25 μm and one side of which was treated with silicone release) was bonded to the surface of the pressure-sensitive adhesive layer to produce a surface protective film (3) with a release liner.
［製造例１４］：表面保護フィルム（４）の製造
　二軸延伸ポリエステルフィルム（三菱ケミカル製「Ｔ１００Ｃ３８」、厚み３８μｍ）のコロナ面に、製造例９で得られたアクリル系粘着剤組成物（４）を塗布し、１３０℃で２分間加熱して、厚み１０μｍの粘着剤層を形成した。粘着剤層の表面に、はく離ライナー（片面がシリコーン離型処理された厚み２５μｍのポリエステルフィルム）の離型処理面を貼り合わせ、はく離ライナー付きの表面保護フィルム（４）を製造した。 [Production Example 14]: Production of Surface Protective Film (4) The acrylic pressure-sensitive adhesive composition (4) obtained in Production Example 9 was applied to the corona surface of a biaxially stretched polyester film ("T100C38" manufactured by Mitsubishi Chemical, thickness 38 μm) and heated at 130° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 10 μm. The release-treated surface of a release liner (a polyester film having a thickness of 25 μm and one side of which was treated with silicone release) was bonded to the surface of the pressure-sensitive adhesive layer to produce a surface protective film (4) with a release liner.
［製造例１５］：表面保護フィルム（５）の製造
　二軸延伸ポリエステルフィルム（三菱ケミカル製「Ｔ１００Ｃ３８」、厚み３８μｍ）のコロナ面に、製造例１０で得られたアクリル系粘着剤組成物（５）を塗布し、１３０℃で２分間加熱して、厚み１０μｍの粘着剤層を形成した。粘着剤層の表面に、はく離ライナー（片面がシリコーン離型処理された厚み２５μｍのポリエステルフィルム）の離型処理面を貼り合わせ、はく離ライナー付きの表面保護フィルム（５）を製造した。 [Production Example 15]: Production of Surface Protective Film (5) The acrylic pressure-sensitive adhesive composition (5) obtained in Production Example 10 was applied to the corona surface of a biaxially stretched polyester film ("T100C38" manufactured by Mitsubishi Chemical, thickness 38 μm) and heated at 130° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 10 μm. The release-treated surface of a release liner (a polyester film having a thickness of 25 μm and one side of which was treated with silicone release) was bonded to the surface of the pressure-sensitive adhesive layer to produce a surface protective film (5) with a release liner.
［製造例１６］：塗工液（１）の製造
　紫外線硬化型ウレタンアクリレート樹脂（新中村化学社製、商品名「ＵＡ５３Ｈ－８０ＭＢ」、固形分８０％）：５０重量部、および、ペンタエリスリトールトリアクリレートを主成分とする多官能アクリレート（大阪有機化学工業社製、商品名「ビスコート＃３００」、固形分１００％）：５０重量部を準備した。これらの樹脂と、これらの樹脂の合計の樹脂固形分１００重量部あたり、粒子としてアクリルとスチレンの共重合粒子（積水化成品工業社製、商品名「テクポリマーＳＳＸ１０５５ＱＸＥ」）を０．５重量部、増粘剤として有機粘土である合成スメクタイト（クニミネ工業社製、商品名「スメクトンＳＡＮ」）を１．５重量部、光重合開始剤（ＢＡＳＦ社製、商品名「ＯＭＮＩＲＡＤ９０７」）を５重量部、レベリング剤（ＤＩＣ社製、商品名「ＧＲＡＮＤＩＣ　ＰＣ４１００」、固形分１０％）を０．１重量部混合した。この混合物を固形分濃度が４０％となるように、トルエン／シクロペンタノン混合溶媒（７０／３０）で希釈して、塗工液（１）を製造した。 [Production Example 16]: Production of Coating Liquid (1) 50 parts by weight of an ultraviolet-curable urethane acrylate resin (manufactured by Shin-Nakamura Chemical Co., Ltd., product name "UA53H-80MB", solid content 80%) and 50 parts by weight of a polyfunctional acrylate containing pentaerythritol triacrylate as a main component (manufactured by Osaka Organic Chemical Industry Ltd., product name "Viscoat #300", solid content 100%) were prepared. These resins and the total resin solid content of these resins per 100 parts by weight were mixed with 0.5 parts by weight of copolymer particles of acrylic and styrene (manufactured by Sekisui Chemical Co., Ltd., trade name "Techpolymer SSX1055QXE") as particles, 1.5 parts by weight of synthetic smectite (manufactured by Kunimine Kogyo Co., Ltd., trade name "Sumecton SAN") which is an organic clay as a thickener, 5 parts by weight of a photopolymerization initiator (manufactured by BASF, trade name "OMNIRAD907"), and 0.1 parts by weight of a leveling agent (manufactured by DIC, trade name "GRANDIC PC4100", solid content 10%). This mixture was diluted with a toluene/cyclopentanone mixed solvent (70/30) so that the solid content concentration was 40%, to produce a coating liquid (1).
［製造例１７］：塗工液（２）の製造
　製造例１６において、レベリング剤（ＤＩＣ社製、商品名「ＧＲＡＮＤＩＣ　ＰＣ４１００」、固形分１０％）を信越化学工業社製の商品名「ＫＹ－１２０３」（固形分２０％）に変更した以外は、製造例１６と同様に行い、塗工液（２）を製造した。 [Production Example 17]: Production of Coating Liquid (2) [0213] The same procedure as in Production Example 16 was carried out, except that the leveling agent (manufactured by DIC Corporation, product name "GRANDIC PC4100", solid content 10%) was changed to a product name "KY-1203" (solid content 20%) manufactured by Shin-Etsu Chemical Co., Ltd., to produce a coating liquid (2).
［製造例１８］：塗工液（３）の製造
　製造例１６において、アクリルとスチレンの共重合粒子（積水化成品工業社製、商品名「テクポリマーＳＳＸ１０５５ＱＸＥ」）の使用量を０．５重量部から３．０重量部に変更した以外は、製造例１６と同様に行い、塗工液（３）を製造した。 [Production Example 18]: Production of Coating Solution (3) [0213] The same procedure as in Production Example 16 was repeated, except that the amount of acrylic and styrene copolymer particles (manufactured by Sekisui Chemical Co., Ltd., product name "Techpolymer SSX1055QXE") used was changed from 0.5 parts by weight to 3.0 parts by weight, to produce a coating solution (3).
［製造例１９］：塗工液（４）の製造
　製造例１６において、レベリング剤（ＤＩＣ社製、商品名「ＧＲＡＮＤＩＣ　ＰＣ４１００」、固形分１０％）の使用量を０．１重量部から０．０１重量部に変更した以外は、製造例１６と同様に行い、塗工液（４）を製造した。 [Production Example 19]: Production of Coating Solution (4) [0223] The same procedure as in Production Example 16 was repeated, except that the amount of a leveling agent (manufactured by DIC Corporation, product name "GRANDIC PC4100", solid content 10%) used was changed from 0.1 part by weight to 0.01 part by weight, to produce a coating solution (4).
［製造例２０］：塗工液（５）の製造
　製造例１６において、レベリング剤（ＤＩＣ社製、商品名「ＧＲＡＮＤＩＣ　ＰＣ４１００」、固形分１０％）の使用量を０．１重量部から０．０５重量部に変更した以外は、製造例１６と同様に行い、塗工液（５）を製造した。 [Production Example 20]: Production of Coating Solution (5) [0213] The same procedure as in Production Example 16 was repeated, except that the amount of a leveling agent (manufactured by DIC Corporation, product name "GRANDIC PC4100", solid content 10%) used was changed from 0.1 part by weight to 0.05 part by weight, to produce a coating solution (5).
［製造例２１］：塗工液（６）の製造
　製造例１６において、レベリング剤（ＤＩＣ社製、商品名「ＧＲＡＮＤＩＣ　ＰＣ４１００」、固形分１０％）の使用量を０．１重量部から０．１５重量部に変更した以外は、製造例１６と同様に行い、塗工液（６）を製造した。 [Production Example 21]: Production of Coating Solution (6) [0213] The same procedure as in Production Example 16 was carried out, except that the amount of a leveling agent (manufactured by DIC Corporation, product name "GRANDIC PC4100", solid content 10%) used was changed from 0.1 part by weight to 0.15 part by weight, to produce a coating solution (6).
［製造例２２］：被着体（１）の製造
　基材として、二軸延伸ポリエステルフィルム（三菱ケミカル社製、商品名「Ｔ１００Ｃ＃３８」）を準備した。
　基材のコロナ面に、製造例１６で製造した塗工液（１）を、ワイヤーバーを用いて塗工し、未乾燥の塗膜を形成した。そして、この未乾燥の塗膜が形成された基材を、１００℃で１分間加熱することにより、未乾燥の塗膜を乾燥させた。その後、高圧水銀ランプにて積算光量３００ｍＪ／ｃｍ2の紫外線を照射し、塗膜を硬化処理して、塗膜厚み５μｍの被着体（１）を製造した。 [Production Example 22]: Production of Adherend (1) As a substrate, a biaxially stretched polyester film (manufactured by Mitsubishi Chemical Corporation, product name "T100C#38") was prepared.
The coating liquid (1) produced in Production Example 16 was applied to the corona surface of the substrate using a wire bar to form a wet coating film. The substrate on which the wet coating film was formed was then heated at 100° C. for 1 minute to dry the wet coating film. Thereafter, the coating film was cured by irradiating it with ultraviolet light from a high-pressure mercury lamp at an integrated light quantity of 300 mJ/cm 2 to produce an adherend (1) with a coating film thickness of 5 μm.
［製造例２３］：被着体（２）の製造
　基材として、二軸延伸ポリエステルフィルム（三菱ケミカル社製、商品名「Ｔ１００Ｃ＃３８」）を準備した。
　基材のコロナ面に、製造例１７で製造した塗工液（２）を、ワイヤーバーを用いて塗工し、未乾燥の塗膜を形成した。そして、この未乾燥の塗膜が形成された基材を、１００℃で１分間加熱することにより、未乾燥の塗膜を乾燥させた。その後、高圧水銀ランプにて積算光量３００ｍＪ／ｃｍ2の紫外線を照射し、塗膜を硬化処理して、塗膜厚み５μｍの被着体（２）を製造した。 [Production Example 23]: Production of Adherend (2) As a substrate, a biaxially stretched polyester film (manufactured by Mitsubishi Chemical Corporation, product name "T100C#38") was prepared.
The coating liquid (2) produced in Production Example 17 was applied to the corona surface of the substrate using a wire bar to form a wet coating film. The substrate on which the wet coating film was formed was then heated at 100°C for 1 minute to dry the wet coating film. Thereafter, the coating film was cured by irradiating it with ultraviolet light from a high-pressure mercury lamp at an integrated light quantity of 300 mJ/ cm2 to produce an adherend (2) with a coating film thickness of 5 μm.
［製造例２４］：被着体（３）の製造
　基材として、二軸延伸ポリエステルフィルム（三菱ケミカル社製、商品名「Ｔ１００Ｃ＃３８」）を準備した。
　基材のコロナ面に、製造例１６で製造した塗工液（１）を、ワイヤーバーを用いて塗工し、未乾燥の塗膜を形成した。そして、この未乾燥の塗膜が形成された基材を、１００℃で１分間加熱することにより、未乾燥の塗膜を乾燥させた。その後、高圧水銀ランプにて積算光量３００ｍＪ／ｃｍ2の紫外線を照射し、塗膜を硬化処理して、塗膜厚み３μｍの被着体（３）を製造した。 [Production Example 24]: Production of Adherend (3) As a substrate, a biaxially stretched polyester film (manufactured by Mitsubishi Chemical Corporation, product name "T100C#38") was prepared.
The coating liquid (1) produced in Production Example 16 was applied to the corona surface of the substrate using a wire bar to form a wet coating film. The substrate on which the wet coating film was formed was then heated at 100°C for 1 minute to dry the wet coating film. Thereafter, the coating film was cured by irradiating it with ultraviolet light from a high-pressure mercury lamp at an integrated light quantity of 300 mJ/ cm2 to produce an adherend (3) with a coating film thickness of 3 μm.
［製造例２５］：被着体（４）の製造
　基材として、二軸延伸ポリエステルフィルム（三菱ケミカル社製、商品名「Ｔ１００Ｃ＃３８」）を準備した。
　基材のコロナ面に、製造例１８で製造した塗工液（３）を、ワイヤーバーを用いて塗工し、未乾燥の塗膜を形成した。そして、この未乾燥の塗膜が形成された基材を、１００℃で１分間加熱することにより、未乾燥の塗膜を乾燥させた。その後、高圧水銀ランプにて積算光量３００ｍＪ／ｃｍ2の紫外線を照射し、塗膜を硬化処理して、塗膜層厚み３μｍの被着体（４）を製造した。 [Production Example 25]: Production of Adherend (4) As a substrate, a biaxially stretched polyester film (manufactured by Mitsubishi Chemical Corporation, product name "T100C#38") was prepared.
The coating liquid (3) produced in Production Example 18 was applied to the corona surface of the substrate using a wire bar to form a wet coating film. The substrate on which the wet coating film was formed was then heated at 100° C. for 1 minute to dry the wet coating film. The coating film was then cured by irradiating it with ultraviolet light from a high-pressure mercury lamp at an integrated light quantity of 300 mJ/cm 2 to produce an adherend (4) with a coating film layer thickness of 3 μm.
［製造例２６］：被着体（５）の製造
　基材として、二軸延伸ポリエステルフィルム（三菱ケミカル社製、商品名「Ｔ１００Ｃ＃３８」）を準備した。
　基材のコロナ面に、製造例１９で製造した塗工液（４）を、ワイヤーバーを用いて塗工し、未乾燥の塗膜を形成した。そして、この未乾燥の塗膜が形成された基材を、１００℃で１分間加熱することにより、未乾燥の塗膜を乾燥させた。その後、高圧水銀ランプにて積算光量３００ｍＪ／ｃｍ2の紫外線を照射し、塗膜を硬化処理して、塗膜層厚み５μｍの被着体（５）を製造した。 [Production Example 26]: Production of Adherend (5) As a substrate, a biaxially stretched polyester film (manufactured by Mitsubishi Chemical Corporation, product name "T100C#38") was prepared.
The coating liquid (4) produced in Production Example 19 was applied to the corona surface of the substrate using a wire bar to form a wet coating film. The substrate on which the wet coating film was formed was then heated at 100° C. for 1 minute to dry the wet coating film. Thereafter, the coating film was cured by irradiating it with ultraviolet light from a high-pressure mercury lamp at an integrated light quantity of 300 mJ/cm 2 to produce an adherend (5) with a coating film layer thickness of 5 μm.
［製造例２７］：被着体（６）の製造
　基材として、二軸延伸ポリエステルフィルム（三菱ケミカル社製、商品名「Ｔ１００Ｃ＃３８」）を準備した。
　基材のコロナ面に、製造例２０で製造した塗工液（５）を、ワイヤーバーを用いて塗工し、未乾燥の塗膜を形成した。そして、この未乾燥の塗膜が形成された基材を、１００℃で１分間加熱することにより、未乾燥の塗膜を乾燥させた。その後、高圧水銀ランプにて積算光量３００ｍＪ／ｃｍ2の紫外線を照射し、塗膜を硬化処理して、塗膜層厚み５μｍの被着体（６）を得た。 [Production Example 27]: Production of Adherend (6) As a substrate, a biaxially stretched polyester film (manufactured by Mitsubishi Chemical Corporation, product name "T100C#38") was prepared.
The coating liquid (5) produced in Production Example 20 was applied to the corona surface of the substrate using a wire bar to form a wet coating film. The substrate on which the wet coating film was formed was then heated at 100° C. for 1 minute to dry the wet coating film. The coating film was then cured by irradiating it with ultraviolet light from a high-pressure mercury lamp at an integrated light quantity of 300 mJ/cm 2 to obtain an adherend (6) with a coating film layer thickness of 5 μm.
［製造例２８］：被着体（７）の製造
　基材として、二軸延伸ポリエステルフィルム（三菱ケミカル社製、商品名「Ｔ１００Ｃ＃３８」）を準備した。
　基材のコロナ面に、製造例２１で製造した塗工液（６）を、ワイヤーバーを用いて塗工し、未乾燥の塗膜を形成した。そして、この未乾燥の塗膜が形成された基材を、１００℃で１分間加熱することにより、未乾燥の塗膜を乾燥させた。その後、高圧水銀ランプにて積算光量３００ｍＪ／ｃｍ2の紫外線を照射し、塗膜を硬化処理して、塗膜層厚み５μｍの被着体（７）を得た。 [Production Example 28]: Production of Adherend (7) A biaxially stretched polyester film (manufactured by Mitsubishi Chemical Corporation, product name "T100C#38") was prepared as a substrate.
The coating liquid (6) produced in Production Example 21 was applied to the corona surface of the substrate using a wire bar to form a wet coating film. The substrate on which the wet coating film was formed was then heated at 100° C. for 1 minute to dry the wet coating film. The coating film was then cured by irradiating it with ultraviolet light from a high-pressure mercury lamp at an integrated light quantity of 300 mJ/cm 2 to obtain an adherend (7) with a coating film layer thickness of 5 μm.
［製造例２９］：被着体（８）の製造
　基材として、二軸延伸ポリエステルフィルム（三菱ケミカル社製、商品名「Ｔ１００Ｃ＃３８」）を準備した。
　基材のコロナ面に、製造例１６で製造した塗工液（１）を、ワイヤーバーを用いて塗工し、未乾燥の塗膜を形成した。そして、この未乾燥の塗膜が形成された基材を、１００℃で１分間加熱することにより、未乾燥の塗膜を乾燥させた。その後、高圧水銀ランプにて積算光量３００ｍＪ／ｃｍ2の紫外線を照射し、塗膜を硬化処理して、塗膜層厚み４．５μｍの被着体（８）を製造した。 [Production Example 29]: Production of Adherend (8) As a substrate, a biaxially stretched polyester film (manufactured by Mitsubishi Chemical Corporation, product name "T100C#38") was prepared.
The coating liquid (1) produced in Production Example 16 was applied to the corona surface of the substrate using a wire bar to form a wet coating film. The substrate on which the wet coating film was formed was then heated at 100° C. for 1 minute to dry the wet coating film. The coating film was then cured by irradiating it with ultraviolet light from a high-pressure mercury lamp at an integrated light quantity of 300 mJ/cm 2 to produce an adherend (8) with a coating film layer thickness of 4.5 μm.
［実施例１］：積層体（１）の製造
　はく離ライナー付きの表面保護フィルム（１）を幅２５ｍｍ、長さ１００ｍｍのサイズに切り出し、はく離ライナーを剥離後に、幅７０ｍｍ、長さ１００ｍｍのサイズに切り出した被着体（１）に、圧力０．２５ＭＰａ、送り速度０．３ｍ／分でロール圧着し、積層体（１）を得た。
　結果を表１に示した。 Example 1: Production of laminate (1) A surface protection film (1) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (1) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (1).
The results are shown in Table 1.
［実施例２］：積層体（２）の製造
　はく離ライナー付きの表面保護フィルム（２）を幅２５ｍｍ、長さ１００ｍｍのサイズに切り出し、はく離ライナーを剥離後に、幅７０ｍｍ、長さ１００ｍｍのサイズに切り出した被着体（１）に、圧力０．２５ＭＰａ、送り速度０．３ｍ／分でロール圧着し、積層体（２）を得た。
　結果を表１に示した。 [Example 2]: Production of laminate (2) A surface protection film (2) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (1) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (2).
The results are shown in Table 1.
［実施例３］：積層体（３）の製造
　はく離ライナー付きの表面保護フィルム（３）を幅２５ｍｍ、長さ１００ｍｍのサイズに切り出し、はく離ライナーを剥離後に、幅７０ｍｍ、長さ１００ｍｍのサイズに切り出した被着体（１）に、圧力０．２５ＭＰａ、送り速度０．３ｍ／分でロール圧着し、積層体（３）を得た。
　結果を表１に示した。 Example 3: Production of laminate (3) A surface protection film (3) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (1) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (3).
The results are shown in Table 1.
［実施例４］：積層体（４）の製造
　はく離ライナー付きの表面保護フィルム（４）を幅２５ｍｍ、長さ１００ｍｍのサイズに切り出し、はく離ライナーを剥離後に、幅７０ｍｍ、長さ１００ｍｍのサイズに切り出した被着体（１）に、圧力０．２５ＭＰａ、送り速度０．３ｍ／分でロール圧着し、積層体（４）を得た。
　結果を表１に示した。 Example 4: Production of laminate (4) A surface protection film (4) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (1) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (4).
The results are shown in Table 1.
［実施例５］：積層体（５）の製造
　はく離ライナー付きの表面保護フィルム（１）を幅２５ｍｍ、長さ１００ｍｍのサイズに切り出し、はく離ライナーを剥離後に、幅７０ｍｍ、長さ１００ｍｍのサイズに切り出した被着体（２）に、圧力０．２５ＭＰａ、送り速度０．３ｍ／分でロール圧着し、積層体（５）を得た。
　結果を表１に示した。 Example 5: Production of laminate (5) A surface protection film (1) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (2) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (5).
The results are shown in Table 1.
［実施例６］：積層体（６）の製造
　はく離ライナー付きの表面保護フィルム（４）を幅２５ｍｍ、長さ１００ｍｍのサイズに切り出し、はく離ライナーを剥離後に、幅７０ｍｍ、長さ１００ｍｍのサイズに切り出した被着体（２）に、圧力０．２５ＭＰａ、送り速度０．３ｍ／分でロール圧着し、積層体（６）を得た。
　結果を表１に示した。 [Example 6]: Production of laminate (6) A surface protection film (4) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (2) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (6).
The results are shown in Table 1.
［実施例７］：積層体（７）の製造
　はく離ライナー付きの表面保護フィルム（１）を幅２５ｍｍ、長さ１００ｍｍのサイズに切り出し、はく離ライナーを剥離後に、幅７０ｍｍ、長さ１００ｍｍのサイズに切り出した被着体（３）に、圧力０．２５ＭＰａ、送り速度０．３ｍ／分でロール圧着し、積層体（７）を得た。
　結果を表１に示した。 [Example 7]: Production of laminate (7) A surface protection film (1) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (3) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (7).
The results are shown in Table 1.
［実施例８］：積層体（８）の製造
　はく離ライナー付きの表面保護フィルム（４）を幅２５ｍｍ、長さ１００ｍｍのサイズに切り出し、はく離ライナーを剥離後に、幅７０ｍｍ、長さ１００ｍｍのサイズに切り出した被着体（３）に、圧力０．２５ＭＰａ、送り速度０．３ｍ／分でロール圧着し、積層体（８）を得た。
　結果を表１に示した。 [Example 8]: Production of laminate (8) A surface protection film (4) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (3) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (8).
The results are shown in Table 1.
［実施例９］：積層体（９）の製造
　はく離ライナー付きの表面保護フィルム（１）を幅２５ｍｍ、長さ１００ｍｍのサイズに切り出し、はく離ライナーを剥離後に、幅７０ｍｍ、長さ１００ｍｍのサイズに切り出した被着体（６）に、圧力０．２５ＭＰａ、送り速度０．３ｍ／分でロール圧着し、積層体（９）を得た。
　結果を表１に示した。 Example 9: Production of laminate (9) A surface protection film (1) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (6) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (9).
The results are shown in Table 1.
［実施例１０］：積層体（１０）の製造
　はく離ライナー付きの表面保護フィルム（１）を幅２５ｍｍ、長さ１００ｍｍのサイズに切り出し、はく離ライナーを剥離後に、幅７０ｍｍ、長さ１００ｍｍのサイズに切り出した被着体（７）に、圧力０．２５ＭＰａ、送り速度０．３ｍ／分でロール圧着し、積層体（１０）を得た。
　結果を表１に示した。 Example 10: Production of laminate (10) A surface protective film (1) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (7) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (10).
The results are shown in Table 1.
［実施例１１］：積層体（１１）の製造
　はく離ライナー付きの表面保護フィルム（１）を幅２５ｍｍ、長さ１００ｍｍのサイズに切り出し、はく離ライナーを剥離後に、幅７０ｍｍ、長さ１００ｍｍのサイズに切り出した被着体（８）に、圧力０．２５ＭＰａ、送り速度０．３ｍ／分でロール圧着し、積層体（１１）を得た。
　結果を表１に示した。 Example 11: Production of laminate (11) A surface protective film (1) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (8) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (11).
The results are shown in Table 1.
［比較例１］：積層体（Ｃ１）の製造
　はく離ライナー付きの表面保護フィルム（５）を幅２５ｍｍ、長さ１００ｍｍのサイズに切り出し、はく離ライナーを剥離後に、幅７０ｍｍ、長さ１００ｍｍのサイズに切り出した被着体（１）に、圧力０．２５ＭＰａ、送り速度０．３ｍ／分でロール圧着し、積層体（Ｃ１）を得た。
　結果を表１に示した。 Comparative Example 1: Production of Laminate (C1) A surface protective film (5) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (1) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (C1).
The results are shown in Table 1.
［比較例２］：積層体（Ｃ２）の製造
　はく離ライナー付きの表面保護フィルム（１）を幅２５ｍｍ、長さ１００ｍｍのサイズに切り出し、はく離ライナーを剥離後に、幅７０ｍｍ、長さ１００ｍｍのサイズに切り出した被着体（４）に、圧力０．２５ＭＰａ、送り速度０．３ｍ／分でロール圧着し、積層体（Ｃ２）を得た。
　結果を表１に示した。 [Comparative Example 2]: Production of Laminate (C2) A surface protection film (1) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (4) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (C2).
The results are shown in Table 1.
［比較例３］：積層体（Ｃ３）の製造
　はく離ライナー付きの表面保護フィルム（１）を幅２５ｍｍ、長さ１００ｍｍのサイズに切り出し、はく離ライナーを剥離後に、幅７０ｍｍ、長さ１００ｍｍのサイズに切り出した被着体（５）に、圧力０．２５ＭＰａ、送り速度０．３ｍ／分でロール圧着し、積層体（Ｃ３）を得た。
　結果を表１に示した。 [Comparative Example 3]: Production of Laminate (C3) A surface protection film (1) with a release liner was cut into a size of 25 mm in width and 100 mm in length, and after peeling off the release liner, the film was roll-pressed onto an adherend (5) cut into a size of 70 mm in width and 100 mm in length at a pressure of 0.25 MPa and a feed rate of 0.3 m/min to obtain a laminate (C3).
The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　本発明の積層体は、任意の適切な用途に用い得る。好ましくは、本発明の積層体は、光学部材や電子部材の分野において好ましく用いられる。 The laminate of the present invention can be used for any suitable application. Preferably, the laminate of the present invention is used in the fields of optical components and electronic components.

Claims (6)

  1. 　表面保護フィルムと被着体を含む積層体であって、
    　該表面保護フィルムは、基材と粘着剤層を有し、
    　該粘着剤層と該被着体が直接積層されてなり、
    　該被着体の該表面保護フィルム側の表面の水接触角が８５°以上であり、
    　該被着体の該表面保護フィルム側の表面の算術平均表面粗さＲａが０．６μｍ以下であり、
    　該粘着剤層のクリープリカバリー値が９６％以上である、
    　積層体。     A laminate including a surface protective film and an adherend,
    The surface protection film has a substrate and a pressure-sensitive adhesive layer,
    the pressure-sensitive adhesive layer and the adherend are directly laminated together,
    the water contact angle of the surface of the adherend on the side of the surface protective film is 85° or more;
    the arithmetic mean surface roughness Ra of the surface of the adherend facing the surface protective film is 0.6 μm or less;
    The creep recovery value of the pressure-sensitive adhesive layer is 96% or more.
    Laminate.
  2. 　表面保護フィルムと被着体を含む積層体であって、
    　該表面保護フィルムは、基材と粘着剤層を有し、
    　該粘着剤層と該被着体が直接積層されてなり、
    　該被着体の該表面保護フィルム側の表面の水接触角が８５°以上であり、
    　該被着体の該表面保護フィルム側の表面の算術平均表面粗さＲａが０．６μｍ以下であり、
    　該表面保護フィルムのせん断弾性係数Ｇが３９．０Ｎ／５０ｍｍ3以下である、
    　積層体。     A laminate including a surface protective film and an adherend,
    The surface protection film has a substrate and a pressure-sensitive adhesive layer,
    the pressure-sensitive adhesive layer and the adherend are directly laminated together,
    the water contact angle of the surface of the adherend on the side of the surface protective film is 85° or more;
    the arithmetic mean surface roughness Ra of the surface of the adherend facing the surface protective film is 0.6 μm or less;
    The shear modulus G of the surface protective film is 39.0 N/50 mm3 or less ;
    Laminate.
  3. 　前記水接触角が８５°～１０５°である、請求項１または２に記載の積層体。 The laminate according to claim 1 or 2, wherein the water contact angle is 85° to 105°.
  4. 　前記算術平均表面粗さＲａが０．１μｍ以下である、請求項１または２に記載の積層体。 The laminate according to claim 1 or 2, wherein the arithmetic mean surface roughness Ra is 0.1 μm or less.
  5. 　前記クリープリカバリー値が９９％以上である、請求項１に記載の積層体。 The laminate of claim 1, wherein the creep recovery value is 99% or more.
  6. 　前記せん断弾性係数Ｇが３０．０Ｎ／５０ｍｍ3以下である、請求項２に記載の積層体。 3. The laminate according to claim 2, wherein the shear modulus G is 30.0 N/50 mm3 or less .
PCT/JP2023/038599 2022-11-16 2023-10-25 Laminate WO2024106156A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070270062A1 (en) * 2006-05-19 2007-11-22 Steven Weber Process and System for Applying a Coating onto a Surface of a Lens Substrate
JP2008096734A (en) * 2006-10-12 2008-04-24 Fujifilm Corp Protection film for polarizing plate, polarizing plate and liquid crystal display apparatus
JP2011168751A (en) * 2010-02-22 2011-09-01 Nitto Denko Corp Surface protective film
JP2017160410A (en) * 2016-03-03 2017-09-14 東レフィルム加工株式会社 Laminate film
JP2020083955A (en) * 2018-11-19 2020-06-04 日本カーバイド工業株式会社 Adhesive composition for acrylic substrate protection film and acrylic substrate protection film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070270062A1 (en) * 2006-05-19 2007-11-22 Steven Weber Process and System for Applying a Coating onto a Surface of a Lens Substrate
JP2008096734A (en) * 2006-10-12 2008-04-24 Fujifilm Corp Protection film for polarizing plate, polarizing plate and liquid crystal display apparatus
JP2011168751A (en) * 2010-02-22 2011-09-01 Nitto Denko Corp Surface protective film
JP2017160410A (en) * 2016-03-03 2017-09-14 東レフィルム加工株式会社 Laminate film
JP2020083955A (en) * 2018-11-19 2020-06-04 日本カーバイド工業株式会社 Adhesive composition for acrylic substrate protection film and acrylic substrate protection film

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