WO2024106155A1 - Corps stratifié - Google Patents

Corps stratifié Download PDF

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Publication number
WO2024106155A1
WO2024106155A1 PCT/JP2023/038598 JP2023038598W WO2024106155A1 WO 2024106155 A1 WO2024106155 A1 WO 2024106155A1 JP 2023038598 W JP2023038598 W JP 2023038598W WO 2024106155 A1 WO2024106155 A1 WO 2024106155A1
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Prior art keywords
weight
adherend
acrylate
meth
film
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PCT/JP2023/038598
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English (en)
Japanese (ja)
Inventor
圭太 小川
和也 浦上
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 WO2024106155A1 publication Critical patent/WO2024106155A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—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.
  • a laminate according to an 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 surface of the adherend facing the surface protection film having a water contact angle of 85° or more, the surface of the adherend facing the surface protection film having an arithmetic mean surface roughness Ra of 0.6 ⁇ m or less, and the pressure-sensitive adhesive layer having a thickness of 15 ⁇ m or more.
  • the pressure-sensitive adhesive layer may be composed of an acrylic pressure-sensitive adhesive formed from an acrylic pressure-sensitive adhesive composition, and the acrylic pressure-sensitive adhesive composition may contain an acrylic polymer as a base polymer.
  • the acrylic polymer may have a glass transition temperature Tg of ⁇ 45° C. or lower.
  • the water contact angle may be 85° to 105°.
  • the arithmetic mean surface roughness Ra may be 0.1 ⁇ m 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.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of a laminate of the present invention.
  • FIG. 2 is a schematic diagram illustrating a method for evaluating deformation of a laminate.
  • 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 91° to 100°, and most preferably 91° 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 thickness of the adhesive layer of the surface protection film is preferably 15 ⁇ m or more, more preferably 16 ⁇ m or more, even more preferably 17 ⁇ m or more, particularly preferably 18 ⁇ m or more, and most preferably 19 ⁇ 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, and even more preferably 400,000 to 1,000,000, in order to better demonstrate the effects of the present invention.
  • 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 -20°C or lower, even more preferably -30°C or lower, particularly preferably -40°C or lower, and most preferably -45°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 1% by weight to 50% by weight, even more preferably 1% by weight to 40% by weight, particularly preferably 1% by weight to 30% by weight, and most preferably 1% by weight to 20% 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) which essentially contains hydroxyl group-containing monomer (b1) and embodiment (II) which does not contain hydroxyl group-containing monomer (b1).
  • Embodiment (II) which does not contain hydroxyl group-containing monomer (b1) essentially contains monomer (b2) which has a polar group other than a hydroxyl group. Note that the "hydroxyl group” referred to here does not include the -OH group contained in 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.
  • vinyl esters examples include vinyl acetate (VAc), vinyl propionate, and vinyl laurate.
  • 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 (b2-2) 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 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 more effectively manifest 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 such that the water contact angle of the surface on which the surface protective film is laminated and the arithmetic mean surface roughness Ra of the surface on which the surface protective film is laminated are within the preferred ranges described above, and any appropriate material may be used for the surface.
  • a representative example of such a material is a resin, and 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.
  • 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 7 hours to produce a solution of acrylic polymer (2) (concentration 40% by weight).
  • the weight average molecular weight of the acrylic polymer (2) was 460,000.
  • Production of Surface Protective Film (1) The acrylic pressure-sensitive adhesive composition (1) obtained in Production Example 3 was applied to the corona surface of a biaxially oriented 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 (4) The acrylic pressure-sensitive adhesive composition (1) obtained in Production Example 3 was applied to the corona surface of a biaxially oriented 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 Coating Liquid (4) [0213] The same procedure as in Production Example 11 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 (4).
  • the leveling agent manufactured by DIC Corporation, product name "GRANDIC PC4100", solid content 10%
  • KY-1203 solid content 20%
  • Coating solution (5) was produced in the same manner as in Production Example 11, 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.
  • Production of Coating Solution (6) [0213] The same procedure as in Production Example 11 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 (6).
  • a leveling agent manufactured by DIC Corporation, product name "GRANDIC PC4100", solid content 10%
  • Production of Coating Solution (7) [0213] The same procedure as in Production Example 11 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 0.05 part by weight, to produce a coating solution (7).
  • a leveling agent manufactured by DIC Corporation, product name "GRANDIC PC4100", solid content 10%
  • Production of Coating Solution (8) [0223] The same procedure as in Production Example 11 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 0.15 part by weight, to produce a coating solution (8).
  • a leveling agent manufactured by DIC Corporation, product name "GRANDIC PC4100", solid content 10%
  • a biaxially stretched polyester film (manufactured by Mitsubishi Chemical Corporation, product name "T100C#38") was prepared as a substrate.
  • the coating liquid (1) produced in Production Example 9 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 3 ⁇ m.
  • 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 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 (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 (2).
  • the results are shown in Table 1.
  • Example 3 Production of laminate (3) 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 (3).
  • the results are shown in Table 1.
  • Example 4 Production of laminate (4) 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 (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 (4).
  • the results are shown in Table 1.
  • Example 5 Production of laminate (5) 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 (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 (5).
  • the results are shown in Table 1.
  • Example 6 Production of laminate (6) 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 (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 (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 (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 (7).
  • the results are shown in Table 1.
  • Example 8 Production of laminate (8) 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 (9) 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 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 (10) 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.
  • Comparative Example 1 Production of Laminate (C1) 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 (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 (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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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne un corps stratifié qui comprend un film de protection de surface et une partie collée, des marques de déformation n'étant pas facilement laissées par déformation en raison d'une force externe, la force de pelage initiale du film de protection de surface à partir de la partie collée étant à un niveau approprié, et les changements au fil du temps de la force de pelage du film de protection de surface à partir de la partie collée étant petits.　Un corps stratifié selon un mode de réalisation de la présente invention comprend un film de protection de surface et une partie collée, le film de protection de surface présentant un substrat et une couche d'agent adhésif, le corps stratifié étant obtenu par la couche d'agent adhésif et la partie collée étant stratifiée en contact direct, l'angle de contact avec l'eau de la surface côté film de protection de surface de la partie collée étant supérieur ou égal à 85°, la rugosité de surface moyenne arithmétique Ra de la surface côté film de protection de surface de la partie collée étant inférieure ou égale à 0,6 µm, et l'épaisseur de la couche d'agent adhésif étant supérieure ou égale à 15 µm.
PCT/JP2023/038598 2022-11-16 2023-10-25 Corps stratifié WO2024106155A1 (fr)

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JP2022-183526 2022-11-16
JP2022183526 2022-11-16

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WO2024106155A1 true WO2024106155A1 (fr) 2024-05-23

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001049206A (ja) * 1999-08-04 2001-02-20 Nitto Denko Corp 表面保護フィルム及び光学部材
JP2002060707A (ja) * 2000-08-17 2002-02-26 Teijin Ltd 表面保護フィルムおよびその積層体
WO2014103885A1 (fr) * 2012-12-27 2014-07-03 日本カーバイド工業株式会社 Composition adhésive et film protecteur de surface d'un élément optique
WO2017150430A1 (fr) * 2016-03-03 2017-09-08 東レフィルム加工株式会社 Film stratifié
JP2019094508A (ja) * 2017-11-20 2019-06-20 日東電工株式会社 補強フィルム
JP2019133049A (ja) * 2018-02-01 2019-08-08 日東電工株式会社 表面保護フィルム付光学積層体
WO2019221148A1 (fr) * 2018-05-15 2019-11-21 富士フイルム株式会社 Plaque de polarisation et son procédé de fabrication
JP2020056001A (ja) * 2018-10-01 2020-04-09 日本カーバイド工業株式会社 偏光板用粘着剤組成物及び粘着剤層付偏光板

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001049206A (ja) * 1999-08-04 2001-02-20 Nitto Denko Corp 表面保護フィルム及び光学部材
JP2002060707A (ja) * 2000-08-17 2002-02-26 Teijin Ltd 表面保護フィルムおよびその積層体
WO2014103885A1 (fr) * 2012-12-27 2014-07-03 日本カーバイド工業株式会社 Composition adhésive et film protecteur de surface d'un élément optique
WO2017150430A1 (fr) * 2016-03-03 2017-09-08 東レフィルム加工株式会社 Film stratifié
JP2019094508A (ja) * 2017-11-20 2019-06-20 日東電工株式会社 補強フィルム
JP2019133049A (ja) * 2018-02-01 2019-08-08 日東電工株式会社 表面保護フィルム付光学積層体
WO2019221148A1 (fr) * 2018-05-15 2019-11-21 富士フイルム株式会社 Plaque de polarisation et son procédé de fabrication
JP2020056001A (ja) * 2018-10-01 2020-04-09 日本カーバイド工業株式会社 偏光板用粘着剤組成物及び粘着剤層付偏光板

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