WO2014069542A1 - Laminated body and display device - Google Patents

Laminated body and display device Download PDF

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Publication number
WO2014069542A1
WO2014069542A1 PCT/JP2013/079460 JP2013079460W WO2014069542A1 WO 2014069542 A1 WO2014069542 A1 WO 2014069542A1 JP 2013079460 W JP2013079460 W JP 2013079460W WO 2014069542 A1 WO2014069542 A1 WO 2014069542A1
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WO
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Prior art keywords
layer
base material
adhesive layer
adhesive
pressure
Prior art date
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PCT/JP2013/079460
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French (fr)
Japanese (ja)
Inventor
崇嗣 岡田
井上　政広
宏二 佐々木
Original Assignee
旭硝子株式会社
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Priority to JP2014544564A priority Critical patent/JPWO2014069542A1/en
Priority to CN201380056689.3A priority patent/CN104768752B/en
Publication of WO2014069542A1 publication Critical patent/WO2014069542A1/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
    • 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
    • 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
    • C08J5/128—Adhesives without diluent
    • 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
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/10—Esters of organic acids
    • C08J2301/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

  • the present invention relates to a laminate used by being bonded to an adherend, and a display device using the laminate.
  • a contrast-enhancement film As a display device used in electronic devices such as mobile phones, tablet PCs, car navigation systems, personal computers, ticket vending machines, bank terminals, etc., a contrast-enhancement film, reflection is provided on the front of display panels such as liquid crystal display panels and organic EL display panels.
  • An optical filter such as a prevention film bonded with an adhesive layer is known.
  • Such a display device is manufactured, for example, by providing an adhesive layer on one side of an optical filter and attaching the adhesive layer to the front surface of the display panel.
  • a high positional accuracy is required for bonding the display panel and the optical filter, and even if the positions are slightly shifted, it is regarded as a defective product.
  • the display panel and the optical filter are bonded to each other with a shift, the display panel is expensive. Therefore, the optical filter is removed from the display panel, and the display panel is reused. Therefore, the optical filter is required to be able to be peeled off from the display panel well, so-called reworkability. Specifically, it is required that the adhesive layer does not remain on the display panel, that is, so-called adhesive residue is small, and that the optical filter is partially damaged and does not remain.
  • the adhesive layer has a two-layer structure, and the initial adhesion of one adhesive layer to the soda glass plate is within a predetermined range while improving the reworkability and suppressing the mixing of bubbles at the time of bonding.
  • the adhesion force after 24 hours of both is adjusted within a predetermined range (see, for example, Patent Document 1).
  • a technique in which the adhesive force to a glass substrate is within a predetermined range and the breaking stress is within a predetermined range for example, see Patent Document 2.
  • the adhesion strength and the like are within a predetermined range.
  • different types of members are often arranged on both main surfaces of the pressure-sensitive adhesive layer, and the adhesion force varies greatly depending on the type of member, surface condition, and the like. For this reason, the reworkability cannot always be improved simply by specifying the adhesion.
  • Such a problem is not limited to a display device.
  • an optical filter such as a Low-E film in which a heat ray blocking film called a Low-E (Low-Emissivity) film is formed on a window glass of a building or an automobile is formed. It also occurs when pasting.
  • the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a laminate having good reworkability. Another object of the present invention is to provide a display device using such a laminate.
  • the laminate of the present invention relates to a laminate used by being bonded to an adherend.
  • the display device of the present invention includes an adherend having a display panel and a laminated body bonded to the adherend.
  • the laminate is the laminate of the present invention described above.
  • the present invention has the following gist.
  • a laminate used by being bonded to an adherend In order from the adherend side, a first adhesive layer, a first base material layer, a second adhesive layer, and a second base material layer are provided, and the laminate is attached to the adherend.
  • the adhesion between the adherend and the first pressure-sensitive adhesive layer when combined is A [N / 25 mm]
  • the adhesion between the first pressure-sensitive adhesive layer and the first base material layer is B [N / 25 mm]
  • the adhesive force between the first base material layer and the second adhesive layer is C [N / 25 mm]
  • the adhesive force between the second adhesive layer and the second base material layer is When D [N / 25 mm]
  • the laminated body is characterized in that all of the adhesion forces B, C, and D are larger than the adhesion force A by 5 [N / 25 mm] or more.
  • a laminate having good reworkability can be provided. Further, according to the present invention, it is possible to provide a display device having a laminate having good reworkability and good productivity.
  • Sectional drawing which shows typically one Embodiment of the display apparatus which has a laminated body. Sectional drawing which shows typically one Embodiment of a contrast improvement layer.
  • FIG. 1 is a cross-sectional view showing an embodiment of a display device using a laminate.
  • the display device 10 includes, for example, an adherend 11 having a display panel, and a laminated body 12 as an optical filter bonded to the front surface of the adherend 11.
  • the laminate 12 includes a first pressure-sensitive adhesive layer 13, a first base material layer 14, a second pressure-sensitive adhesive layer 15, and a second base material layer 16 in order from the adherend 11 side.
  • the laminate 12 has an adhesive force of A [N / 25 mm] between the adherend 11 and the first adhesive layer 13 when the laminate 12 is bonded to the adherend 11, and the first adhesive layer 13.
  • the adhesive strength between the first base material layer 14 and the first base material layer 14 is B [N / 25 mm]
  • the adhesive strength between the first base material layer 14 and the second adhesive layer 15 is C [N / 25 mm]
  • the second When the adhesive force between the adhesive layer 15 and the second base material layer 16 is D [N / 25 mm]
  • the adhesive force B, C, and D are all 5 [N / 25 mm] compared to the adhesive force A. Bigger than that.
  • adheresion strength is “conforms to the standard of JIS Z 0237”.
  • the second base material layer 16 in addition to the first base material layer 14, by increasing the adhesion forces B, C, and D by 5 [N / 25 mm] or more compared to the adhesion force A, The reworkability of the laminate 12 can be improved. Specifically, when the laminate 12 is peeled from the adherend 11, it is possible to suppress the first pressure-sensitive adhesive layer 13 and a part of the first base material layer 14 from remaining on the adherend 11. In particular, when the first base material layer 14 is easily damaged by tearing, such as a contrast enhancement film or a thin glass plate, the first base material layer 14 is reinforced by the second base material layer 16 and the damage It is possible to suppress the remaining on the adherend 11 by suppressing the above.
  • Examples of the display panel of the adherend 11 include display panels such as a liquid crystal display panel, a plasma display panel, and an organic EL display panel.
  • the adherend 11 is not necessarily limited to having only a single display panel, and a functional layer described later, for example, an electromagnetic wave shielding layer, a contrast improving layer, or the like is laminated on the front surface according to the type of the display panel. May be.
  • the first pressure-sensitive adhesive layer 13 is for bonding the adherend 11 and the first base material layer 14, and the adhesive force A [N / 25 mm] when bonded to the adherend 11 and the first The adhesive force difference (BA) with the adhesive force B [N / 25 mm] when bonded to the base material layer 14 is 5 [N / 25 mm] or more.
  • the 1st adhesive layer 13 has a single layer structure comprised entirely with the same material. That is, the first pressure-sensitive adhesive layer 13 does not include a multilayer structure.
  • the adhesion difference (BA) When the adhesion difference (BA) is less than 5 [N / 25 mm], the first pressure-sensitive adhesive layer 13 tends to remain on the surface of the adherend 11 when the laminate 12 is peeled from the adherend 11. .
  • the adhesion difference (BA) is preferably 5.5 [N / 25 mm] or more, and more preferably 8.0 [N / 25 mm] or more. Basically, the larger the difference in adhesion (BA) is, the better, but it is usually sufficient that the difference is about 10 [N / 25 mm].
  • the adjustment of the adhesion difference (BA) is, for example, an adhesion difference (BA) of 5 [N / 25 mm] depending on the adherend 11 and the first base material layer 14 to be deposited. This is performed by selecting an adhesive as described above. Specifically, for various pressure-sensitive adhesives that are considered to be applied to the first pressure-sensitive adhesive layer 13, the adhesive force A with the adherend 11 is measured and the first base material layer 14 is configured. The adhesion strength B with the material is measured, and a material having an adhesion strength difference (BA) of 5 [N / 25 mm] or more is selected and used.
  • BA adhesion difference
  • the adhesive force greatly varies depending on the constituent material of the pressure-sensitive adhesive, and also varies greatly depending on the constituent material to be deposited and the surface condition such as surface irregularities. Therefore, the adhesion force difference (B ⁇ A) can be reliably adjusted by actually measuring the adhesion forces A and B to the deposition target.
  • adhesion power A and B can be performed by adjustment of a composition, hardness, etc. of an adhesive, for example.
  • the values of the adhesion forces A and B themselves are not necessarily limited as long as the adhesion force difference (BA) is within a predetermined range.
  • the adhesion strength A is preferably 1 [N / 25 mm] or more from the viewpoint of adhesion to the adherend 11. Further, the adhesion A is preferably 15 [N / 25 mm] or less, more preferably 10 [N / 25 mm] or less from the viewpoint of facilitating peeling from the adherend 11.
  • the adhesion force B [N / 25 mm] is sufficient if the adhesion force difference (BA) is 5 [N / 25 mm] or more, and usually the adhesion force difference (BA) is about 10 [N / 25 mm]. It will be enough.
  • the difference in adhesion (BA) is obtained.
  • the characteristic that the adhesive force of the first pressure-sensitive adhesive layer changes (increases) with time can be used. That is, after the first adhesive layer is bonded to the thin glass plate as the first base material layer, it is allowed to stand for 24 hours or more, and then the glass plate as the adherend is bonded within 3 hours. By peeling, the adhesion difference (BA) can be made 5 [N / 25 mm] or more.
  • the first base material layer is peeled within one hour after bonding the thin glass plate.
  • the adhesion difference (BA) can be made 5 [N / 25 mm] or more, and the reworkability can be improved.
  • the thickness of the first pressure-sensitive adhesive layer 13 is not necessarily limited, but is preferably 10 ⁇ m or more. By setting the thickness to 10 ⁇ m or more, the adherend 11 and the first base material layer 14 can be bonded together reliably. As for the thickness of the 1st adhesive layer 13, 15 micrometers or more are more preferable, and 20 micrometers or more are further more preferable. Usually, the thickness of the first pressure-sensitive adhesive layer 13 is sufficient if it is 30 ⁇ m.
  • the second pressure-sensitive adhesive layer 15 is provided for bonding the first base material layer 14 and the second base material layer 16 together.
  • the second pressure-sensitive adhesive layer 15 has an adhesion force C [N / 25 mm] when bonded to the first substrate layer 14 and an adhesion force D [N / when bonded to the second substrate layer 16. 25 mm] is larger than the adhesion force A by 5 [N / 25 mm] or more. That is, both the adhesion force difference (CA) and the adhesion force difference (DA) are 5 [N / 25 mm] or more.
  • a desired peeled portion that is, the adherend 11 and the first It can be peeled between the pressure-sensitive adhesive layer 13, and other portions, that is, between the first base material layer 14 and the second pressure-sensitive adhesive layer 15 and between the second pressure-sensitive adhesive layer 15 and the second pressure-sensitive adhesive layer 15. Separation with the base material layer 16 can be suppressed. Thereby, even when the first base material layer 14 is easily damaged due to tearing or the like, the second base material layer 16 is effectively reinforced to suppress the damage to the adherend 11. Can be suppressed.
  • both the adhesion forces C and D with respect to the adhesion force A according to the first base material layer 14 and the second base material layer 16 to be attached Is performed by selecting an adhesive that increases 5 [N / 25 mm] or more.
  • the adhesive force C with the constituent material constituting the first base material layer 14 is measured, and the second Adhesive that measures adhesion D with the constituent material constituting the base material layer 16 and increases the adhesion C and D with respect to the adhesion A among these by 5 [N / 25 mm] or more. Select and use.
  • the adhesion forces C and D are preferably 7.0 [N / 25 mm] or more larger than the adhesion force A.
  • the magnitude relationship between the adhesion forces C and D is not particularly limited, and the adhesion force C may be large, the adhesion force D may be large, or may be the same. It is sufficient that the adhesion forces C and D are about 10 [N / 25 mm] larger than the adhesion force A.
  • the thickness of the second pressure-sensitive adhesive layer 15 is not necessarily limited, but is preferably 10 ⁇ m or more. By setting the thickness to 10 ⁇ m or more, the first base material layer 14 and the second base material layer 16 can be reliably bonded together.
  • the thickness of the second pressure-sensitive adhesive layer 15 is more preferably 15 ⁇ m or more, and further preferably 20 ⁇ m or more. Usually, it is sufficient that the thickness of the second pressure-sensitive adhesive layer 15 is 30 ⁇ m.
  • the constituent material of the first pressure-sensitive adhesive layer 13 and the second pressure-sensitive adhesive layer 15 is not necessarily limited as long as a predetermined difference in adhesion force is obtained.
  • acrylic pressure-sensitive adhesives are preferably used.
  • the acrylic pressure-sensitive adhesive is a polymer containing an acrylic monomer unit as a main component.
  • the acrylic monomer include (meth) acrylic acid, itaconic acid, (anhydrous) maleic acid, (anhydrous) fumaric acid, crotonic acid, and alkyl esters thereof.
  • (meth) acrylic acid is a general term for acrylic acid and methacrylic acid. The same applies to (meth) acrylate.
  • alkyl esters of (meth) acrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, and n-hexyl (meth) ) Acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, etc. .
  • Monomers other than acrylic monomers can also be used for the acrylic pressure-sensitive adhesive.
  • examples of other monomers used include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; styrene, ⁇ - Styrene monomers such as methylstyrene; Diene monomers such as butadiene, isoprene and chloroprene; Nitrile monomers such as acrylonitrile and methacrylonitrile; Acrylamide, N, N-dimethylacrylamide, N, N-dimethyl Examples include acrylamide monomers such as methacrylamide.
  • a monomer having a functional group for example, a hydroxy group, a glycidyl group, or the like
  • a crosslinking point examples include hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and the like.
  • crosslinking agent When using a monomer having a functional group that can be a crosslinking point, it is preferable to add a crosslinking agent. By adding a crosslinking agent, it is possible to ensure cohesion by reacting with the crosslinking point to crosslink the polymer.
  • cross-linking agents include melamine resins, urea resins, epoxy resins, metal oxides, metal salts, metal hydroxides, metal chelates, polyisocyanates, carboxy group-containing polymers, acid anhydrides, polyamines, and so on. It is suitably selected according to the type of functional group that can be obtained.
  • the acrylic pressure-sensitive adhesive can contain a silane coupling agent in order to adjust the adhesion.
  • a silane coupling agent an organosilicon compound having at least one alkoxysilyl group in the molecule can be preferably used.
  • an ultraviolet absorber a coloring pigment, and the like can be added to the acrylic adhesive.
  • UV absorber examples include UV absorbers such as benzotriazole, benzophenone, salicylate, cyanoacrylate, triazine, oxanilide, nickel complex, and inorganic.
  • Coloring dyes include color correction dyes and near infrared absorbing dyes.
  • the color tone correction dye absorbs a part of a specific wavelength range of visible light and improves the color tone of transmitted visible light.
  • Examples of color correction dyes include azo, condensed azo, diimonium, phthalocyanine, anthraquinone, indigo, perinone, perylene, dioxazine, quinacridone, methine, isoindolinone, and quinophthalone. , Pyrrole-based, thioindigo-based, metal complex-based, porphyrin-based, tetraazaporphyrin-based pigments.
  • near infrared absorbing dyes examples include polymethine, phthalocyanine, naphthalocyanine, aminium, imonium, diimonium, anthraquinone, dithiol metal complex, naphthoquinone, indolephenol, azo, triallylmethane And dyes such as those based on tungsten oxide.
  • the first pressure-sensitive adhesive layer 13 may be formed by applying a pressure-sensitive adhesive containing the above-described constituent components to the first base material layer 14, or a pressure-sensitive adhesive containing the above-described constituent components in advance.
  • a pressure-sensitive adhesive sheet formed into a sheet shape may be bonded to the first base material layer 14.
  • the second pressure-sensitive adhesive layer 15 may be formed by applying a pressure-sensitive adhesive to the first base material layer 14 or the second base material layer 16 or by bonding a pressure-sensitive adhesive sheet. May be.
  • Coating is, for example, dip coating method, spray coating method, spinner coating method, bead coating method, wire bar coating method, blade coating method, roller coating method, curtain coating method, slit die coater method, gravure coater method, slit reverse.
  • a coater method, a micro gravure method, a comma coater method, etc. can be applied.
  • non-carrier sheet is a film in which two base materials coated with silicone are laminated via an adhesive.
  • the 1st base material layer 14 and the 2nd base material layer 16 should just have a base material at least, for example, the functional layer which has a functional film on the surface of a base material besides a base material simple substance is mentioned. .
  • the single base material examples include a resin film and a thin glass plate.
  • the single base material can contain a coloring pigment, an ultraviolet absorber, and the like as necessary and to the extent possible.
  • the resin film examples include polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyolefins such as polyethylene and polypropylene; polyacrylates such as polymethyl methacrylate (PMMA); polycarbonates (PC); Polystyrenes; celluloses such as triacetyl cellulose, diacetyl cellulose, acetate butyrate cellulose; polyvinyl alcohol; polyvinyl chloride; polyvinylidene chloride; ethylene-vinyl acetate copolymer; polyvinyl butyral;
  • the thickness of the resin film is preferably 10 to 200 ⁇ m, more preferably 50 to 150 ⁇ m.
  • a thin glass plate is provided for enhancing the design by imparting the texture of glass or for protecting the surface.
  • Such a glass plate preferably has a thickness of 0.05 to 5 mm.
  • Examples of the functional layer include a contrast improving layer, an electromagnetic wave shielding layer, an antireflection layer, an antiglare layer, a colored layer, and an ultraviolet absorbing layer.
  • FIG. 2 is a cross-sectional view showing an example of the contrast improving layer.
  • FIG. 2 shows an example in which a contrast improving layer is applied to the first base material layer 14.
  • the contrast enhancement layer 14 ′ is provided to suppress a decrease in contrast due to external light, and has a contrast enhancement film 142 on one surface of the base material 141.
  • the substrate 141 examples include a resin film similar to a single substrate or a thin glass plate.
  • the contrast enhancement film 142 includes a plurality of light transmitting regions 142a that extend in the horizontal direction and are arranged in parallel to each other, and a dark color portion 142b that is disposed between the light transmitting regions 142a.
  • the dark portion 142b contains dark particles, and the cross-sectional shape thereof may be a square shape, a rectangular shape, a triangular shape, or the like in addition to a substantially trapezoidal shape.
  • the translucent region 142a and the dark portion 142b are made of a cured product of a composition containing, for example, an ultraviolet curable resin and a photopolymerization initiator.
  • the dark color portion 142b containing dark particles can absorb external light to improve the contrast of the display image, and the translucent region 142a does not contain dark particles. It is possible to suppress a decrease in visibility due to the darkness of the display image without reducing the light transmittance.
  • the contrast improving layer 14 ′ is disposed so that, for example, the contrast improving film 142, in particular, the translucent region 142 a and the dark portion 142 b are in contact with the first pressure-sensitive adhesive layer 13.
  • the laminate 12 when the laminate 12 is peeled off from the adherend 11, for example, damage is caused at a boundary portion between the translucent region 142a and the dark color portion 142b or a thin portion in the translucent region 142a. It is easy and the damaged part tends to remain on the adherend 11 together with the first pressure-sensitive adhesive layer 13.
  • the adhesion difference (BA) is set to 5 [N / 25 mm] or more, even if it is easily damaged like the contrast improving layer 14 ′, the adherend 11 Residue on the surface can be suppressed.
  • the constituent material of the translucent region 142a in the contrast enhancement layer 14 ′ is preferably a resin material because it is easy to form a groove for forming the dark color portion 142b, can be light and thin, and is excellent in flexibility.
  • resin materials such as ionizing radiation curable resins, thermosetting resins, and thermoplastic resins.
  • the ionizing radiation curable resin is cured by crosslinking or polymerization reaction by irradiation with electromagnetic waves or charged particle beams such as ultraviolet rays or electron beams.
  • electromagnetic waves or charged particle beams such as ultraviolet rays or electron beams.
  • Examples of such ionizing radiation curable resins include ionizing radiation polymerizable prepolymers and / or ionizing radiation polymerizable monomers.
  • ionizing radiation polymerizable prepolymers include polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyol (meth) acrylate, and silicon (meth) acrylate.
  • polymerizable prepolymers having a functional functional group may be used alone or in combination of two or more.
  • a polyfunctional (meth) acrylate which is a polymerizable monomer having a radical polymerizable functional group in the molecule is preferable, specifically, ethylene glycol di (meth) acrylate
  • examples include propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.
  • ionizing radiation polymerizable monomer examples include polymerizable monomers having a cationic polymerizable functional group in the molecule.
  • polymerizable monomers having a cationic polymerizable functional group in the molecule include polymerizable monomers having a cationic polymerizable functional group in the molecule.
  • alicyclic epoxides such as 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, glycidyl ethers such as bisphenol A diglycidyl ether, vinyl ethers such as 4-hydroxybutyl vinyl ether, And oxetanes such as 3-ethyl-3-hydroxymethyloxetane.
  • the ionizing radiation curable resin When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is preferable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the ionizing radiation curable resin.
  • the photopolymerization initiator can be appropriately selected from those conventionally used.
  • Examples of the polymerizable monomer or polymerizable prepolymer having a radical polymerizable functional group in the molecule include benzoin, benzoin methyl ether, acetophenone, dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 1-hydroxycyclohexyl phenyl ketone, benzophenone, p-phenylbenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal and the like are used.
  • aromatic sulfonium salts aromatic diazonium salts, aromatic iodonium salts, metallocene compounds, and benzoin sulfonic acid esters are used as polymerizable monomers and polymerizable prepolymers having a cationic polymerizable functional group in the molecule. It is done.
  • photosensitizer p-dimethylbenzoate, tertiary amines, thiol sensitizers and the like are used.
  • Thermosetting resins include phenolic resin, phenol-formalin resin, urea resin, urea-formalin resin, melamine resin, polyester-melamine resin, melamine-formalin resin, alkyd resin, epoxy resin, epoxy-melamine resin, unsaturated polyester Examples thereof include resins, polyimide resins, acrylic resins, polysiloxane resins, polyurethane resins, and general-purpose two-component curable acrylic resins (acrylic polyol cured products).
  • Thermoplastic resins include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), ethylene glycol-terephthalic acid-isophthalic acid copolymer, terephthalic acid-ethylene glycol-1,4 cyclohexanedimethanol copolymer, polyester heat Polyester resins such as plastic elastomers; Polyolefin resins such as polyethylene, polypropylene, cyclic polyolefin, and polymethylpentene; Halogen-containing resins such as polyvinyl chloride and polyvinylidene chloride; Styrene resins such as polystyrene and acrylonitrile-styrene copolymers; Cellulose resins such as acetyl cellulose, diacetyl cellulose, acetate butyrate cellulose; thermoplastic polyurethane resins; polycarbonate resins; polyamide resins It is.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthal
  • the dark color portion 142b in the contrast improving layer 14 ' is preferably a material in which dark particles are dispersed in a binder resin, and preferably a material that absorbs incident visible light (external light) at a high rate. According to such a configuration, even if the reflected external light is not conspicuous and the reflected light is mixed into the image light, a decrease in image contrast is suppressed.
  • black particles black pigments such as carbon black (black) and black iron oxide, and transparent particles such as acrylic are dyed with a black pigment such as carbon black.
  • black particles black pigments such as carbon black (black) and black iron oxide, and transparent particles such as acrylic are dyed with a black pigment such as carbon black.
  • resin particles examples thereof include resin particles.
  • the dark particles may be pigment particles that are achromatic by mixing various pigments such as blue, purple, yellow, and red, or may be resin particles that are dyed with these pigments.
  • Copper pigments such as copper phthalocyanine blue, indanthrene blue, cobalt blue, ultramarine blue, purple pigments such as dioxazine violet, yellow pigments such as disazo yellow, isoindolinone yellow, and yellow lead, red pigments such as chromophthal red
  • green pigments such as tiepel, quinacridone red, and petals include copper phthalocyanine green and patina.
  • the content of dark particles is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the binder resin.
  • the binder resin include the same resin materials as those of the translucent region 142a, and examples thereof include resin materials such as an ionizing radiation curable resin, a thermosetting resin, and a thermoplastic resin.
  • the contrast improving layer 14 ′ can be manufactured as follows, for example. First, a translucent region forming composition is applied on the substrate 141, and a groove portion or the like for forming the dark color portion 142b is formed on the surface thereof to form the translucent region 142a.
  • a composition for forming a translucent region is prepared by dissolving an ultraviolet curable resin and a photopolymerization initiator in an organic solvent, and then using this as a base material. It is applied to the surface of 141, and a roll-shaped mold (shaped forming roll) is pressed against the surface to form a groove for forming the dark portion 142b, and cured by irradiation with ultraviolet rays. .
  • the dark color part 142b can be formed by dissolving the dark color particles and the binder resin in an organic solvent to prepare a dark color part forming composition, and then applying this to the groove part between the translucent regions 142a and curing.
  • a dark color portion forming composition is prepared by dissolving dark particles, an ultraviolet curable resin, and a photopolymerization initiator in an organic solvent, and this is used as a light transmissive region 142a. After being applied to the grooves in between, it is cured by irradiating with ultraviolet rays.
  • the thickness of the translucent region 142a is preferably 20 to 200 ⁇ m, more preferably 30 to 150 ⁇ m, for example, from the viewpoint of forming the dark color portion 142b, and the thickness (depth) of the dark color portion 142b is 10 to 180 ⁇ m.
  • the width is preferably 20 to 130 ⁇ m, the width is preferably 5 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, and the pitch is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m.
  • the electromagnetic wave shielding layer has, for example, a metal mesh film as an electromagnetic wave shielding film on a base material.
  • a metal mesh film as an electromagnetic wave shielding film on a base material.
  • Such an electromagnetic wave shielding layer is usually formed by bonding a copper foil on a base material and then processing the copper foil into a mesh shape, or a conductive ink such as copper or silver on the base material. It is manufactured by printing on.
  • the base material a resin film similar to a single base material, a thin glass plate, or the like can be used.
  • the electromagnetic wave shielding layer may be formed by forming an electromagnetic wave shielding film on a base material by a sputtering method.
  • the electromagnetic wave shielding film is formed by alternately laminating metal oxide films and metal films, for example, where the number of metal films is n and the number of metal oxide films is n + 1 (where n is 1). It is an integer above.
  • the metal oxide film include an oxide of indium and tin, an oxide of titanium and zinc, an oxide of aluminum and zinc, an oxide of niobium, and the like.
  • what consists of silver, a silver alloy, etc. is mentioned as a metal film.
  • the antireflection layer is provided to suppress reflection of visible light (external light). By providing the antireflection layer, reflection can be suppressed and the contrast of the display image can be improved.
  • the antireflection layer has, for example, an antireflection film on a substrate.
  • the substrate a resin film similar to a single substrate or a thin glass plate can be used.
  • the antireflection film include a laminated film in which an inorganic compound having a low refractive index and an inorganic compound having a high refractive index are alternately laminated, a film made of an inorganic compound having a low refractive index, and a film made of a resin having a low refractive index. It is done.
  • the inorganic compound having a low refractive index include silicon dioxide.
  • the resin having a low refractive index include a fluororesin, a silicone resin, and a fluorosilicone resin.
  • the anti-glare layer has, for example, an anti-glare portion composed of uneven portions on the surface.
  • the anti-glare portion has an effect of blurring the outline by diffusing a reflected image reflected on the surface by the uneven portion on the surface.
  • the surface of the base material is coated with a solution in which inorganic fine particles such as silica or organic fine particles such as acrylic resin are dispersed in a binder, and the solvent is volatilized to form an antiglare portion composed of uneven portions. And those obtained by forming a glare-proof portion comprising uneven portions on the substrate itself by sandblasting, etching, or the like.
  • the base material a resin film similar to a single base material, a thin glass plate, or the like can be used.
  • the colored layer examples include those having a colored film which is a resin film containing a colored pigment on a substrate.
  • a resin film similar to a single substrate or a thin glass plate can be used.
  • the coloring dye examples include a color tone correction dye and a near-infrared absorbing dye, and those used for the first pressure-sensitive adhesive layer 13 and the second pressure-sensitive adhesive layer 15 can be used.
  • the ultraviolet absorbing layer examples include those having an ultraviolet absorbing film which is a resin film containing an ultraviolet absorbent on a substrate.
  • the substrate a resin film similar to a single substrate or a thin glass plate can be used.
  • the 1st adhesive layer 13 or the 2nd adhesive layer 15 can be used for an ultraviolet absorber.
  • the adherend 11 has a single display panel
  • the laminate 12 is an adhesive layer (first adhesive layer 13) made of an acrylic adhesive in order from the adherend 11 side. )
  • a contrast improving layer (first base layer 14) provided with a contrast improving film on the base an adhesive layer made of an acrylic adhesive (second adhesive layer 15), and the base Examples thereof include those having an antireflection layer (second base material layer 16) provided with an antireflection film.
  • the base material of the antireflection layer is preferably a polyethylene terephthalate film from the viewpoint of suppressing damage to the contrast improving layer.
  • the thickness of the polyethylene terephthalate film serving as the base material for such an antireflection layer is preferably 38 ⁇ m or more, and more preferably 75 ⁇ m or more.
  • the contrast improving layer when the laminate 12 is peeled from the adherend 11, the contrast improving layer is easily damaged and remains on the adherend 11.
  • an antireflection layer that should also be a reinforcing layer is provided, and the adhesive force B, C, and D are all increased by 5 [N / 25 mm] or more compared to the adhesive force A, whereby an adhesive layer In addition to the remaining (first pressure-sensitive adhesive layer 13), the remaining contrast enhancing layer due to damage can also be suppressed.
  • a polyethylene terephthalate film as the base material of the antireflection layer, it is possible to effectively suppress the remaining of the contrast improving layer due to damage.
  • Other display devices 10 include those in which the contrast enhancement layer (first base material layer) of the display device 10 is a triacetyl cellulose film. Since the triacetyl cellulose film is also easily damaged like the contrast improving layer, the same remarkable effect can be obtained.
  • an adherend 11 is obtained by sequentially laminating an adhesive layer, an electromagnetic wave shielding layer, an adhesive layer, and a contrast improving layer on a display panel.
  • an adhesive layer (first adhesive layer 13) made of an acrylic adhesive, a thin glass plate (first base material layer 14), and an adhesive layer made of an acrylic adhesive.
  • examples thereof include (second pressure-sensitive adhesive layer 15) and an antireflection layer (second base material layer 16) in which an antireflection film is provided on the base material.
  • the base material of the antireflection layer is preferably a polyethylene terephthalate film from the viewpoint of suppressing damage to the thin glass plate.
  • the thickness of the polyethylene terephthalate film serving as the base material for such an antireflection layer is preferably 38 ⁇ m or more, and more preferably 75 ⁇ m or more.
  • the adherend 11 is not necessarily limited to a single display panel, and functional layers such as an electromagnetic wave shielding layer and a contrast enhancement layer may be laminated on the front surface according to the type of the display panel.
  • functional layers such as an electromagnetic wave shielding layer and a contrast enhancement layer may be laminated on the front surface according to the type of the display panel.
  • the laminate 12 has a thin glass plate, when the laminate 12 is peeled from the adherend 11, the thin glass plate is easily damaged and remains on the adherend 11.
  • an anti-reflection layer that should serve as a reinforcing layer is provided, and the adhesive force B, C, and D are all increased by 5 [N / 25 mm] or more compared to the adhesive force A.
  • the agent layer first pressure-sensitive adhesive layer 13
  • the laminate 12 is not necessarily limited to one having two pressure-sensitive adhesive layers and two base material layers, and the pressure-sensitive adhesive layer and the base material layer may each be three or more layers.
  • the adhesive layer which is the third and subsequent layers counted only from the adhesive layer 11 side from the adherend 11 side has an adhesive force of 5 [ N / 25 mm] or more is preferable. By setting it as such, it can be made to peel between a desired peeling part, ie, the adherend 11 and the 1st adhesive layer (1st adhesive layer 13), and other parts. Can be prevented. Thereby, damage to the adherend 11 can be suppressed by suppressing damage to the first base layer (first base layer 14) and the like.
  • the first base material layer (first base material layer 14) and the second base material layer Like a layer (2nd base material layer 16), it can be set as the functional layer which has a functional film on the surface of a base material other than a base material single-piece
  • the laminated body of the present invention has been described by taking the optical filter for display device applied to the display device as an example, the laminated body of the present invention is not necessarily limited to the optical filter for display device.
  • the laminated body of the present invention may be a low-emissivity laminated body used by being attached to a window glass of a building or an automobile.
  • a base material alone or a heat ray blocking film called a Low-E (Low-Emissivity) film formed on the base material is used as the first base material layer and the second base material layer.
  • a base material alone or a heat ray blocking film called a Low-E (Low-Emissivity) film formed on the base material is used. Is mentioned.
  • Examples 1 to 3 and 7 are examples of the present invention, and Examples 4 to 6 are comparative examples of the present invention.
  • Example 1 A laminate having the structure shown in Table 1 was produced as the laminate of Example 1.
  • the 2nd adhesion layer was manufactured as follows. To 6 parts by mass of methyl ethyl ketone, 1.13 parts by mass of an ultraviolet absorber (trade name “TINUVIN 479” manufactured by Ciba) and 0.0150 part by mass of a porphyrin compound (manufactured by Yamada Chemical Co., TAP 18) are added and stirred for 10 minutes with a mixer. And dissolved.
  • an ultraviolet absorber trade name “TINUVIN 479” manufactured by Ciba
  • a porphyrin compound manufactured by Yamada Chemical Co., TAP 18
  • the second adhesive layer is bonded to an antireflection (AR) film (trade name “RL9900”, manufactured by NOF Corporation, base material: PET film, base material thickness 100 ⁇ m) to be the second base material layer.
  • AR antireflection
  • RLF contrast enhancing film
  • an acrylic adhesive (trade name “NCK101 adhesive” manufactured by Toyo Ink Co., Ltd.) serving as the first adhesive layer is formed on the side opposite to the PET film surface of the contrast improving film serving as the first base material layer with a thickness of 25 ⁇ m.
  • the optical filter as a laminated body was produced by applying to the above.
  • the contrast improvement film (CRF) used as a 1st base material layer was manufactured as follows.
  • a base material a 100 ⁇ m-thick polyethylene terephthalate belt-like sheet (product name: A4300, manufactured by Toyobo Co., Ltd.) that has been subjected to easy adhesion on both sides is prepared, and an ultraviolet curable resin made of urethane acrylate prepolymer is thickened thereon The film was applied to a thickness of 89 ⁇ m.
  • a metal capable of forming a plurality of groove-like recesses having a maximum bottom opening width of 10 ⁇ m, a minimum width of 7 ⁇ m on the upper bottom side, and a depth of 69 ⁇ m.
  • the shaping mold roll was pressed and the ultraviolet curable resin was cured by irradiating ultraviolet rays from the back side while engraving the groove-like concave shape.
  • a plurality of groove-shaped recesses having a pitch of 51 ⁇ m and groove-shaped recesses having an opening width on the lower base side of 10 ⁇ m, a minimum width on the upper base side of 7 ⁇ m, and a depth of 69 ⁇ m were formed.
  • the shaping-type roll has a groove-shaped convex portion corresponding to the groove-shaped concave portion of the contrast improving film in the circumferential direction (a reverse convex shape that is the same shape as the concave shape of the contrast improving film),
  • a groove-like recess can be formed so as to extend in the longitudinal direction of the sheet member by rotating the extension direction of the groove-like convex part in the longitudinal direction of the belt on the belt-like sheet member.
  • a liquid ultraviolet curable resin composition was prepared by mixing 2 parts by mass of xyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals). This liquid resin composition was applied to the groove-shaped recess forming surface side and then wiped with a doctor blade. In wiping, the liquid resin composition was cured by irradiating ultraviolet rays from the back at the same time. In wiping, the gap between the groove-shaped recess forming surface and the doctor blade was set to 1.5 ⁇ m, and the wiping was repeated twice.
  • the groove-shaped recess can form a dark part with a trapezoidal cross section filled with an ultraviolet curable resin, which is a transparent resin, and black spherical beads, which are dark particles, on the flat part between these dark parts.
  • an ultraviolet curable resin which is a transparent resin
  • black spherical beads which are dark particles
  • Example 2 The contrast-enhancement film, which is the first base material layer, is changed to a triacetyl cellulose film (manufactured by Fuji Film Co., Ltd., trade name: TAC film, thickness 80 ⁇ m), and the acrylic adhesive (Toyo Ink Co., Ltd.) which is the first adhesive layer
  • a triacetyl cellulose film manufactured by Fuji Film Co., Ltd., trade name: TAC film, thickness 80 ⁇ m
  • acrylic adhesive Toyo Ink Co., Ltd.
  • An optical filter as a laminate was prepared in the same manner as in Example 1 except that the product was manufactured and trade name: NCK101 adhesive was changed to an acrylic adhesive (manufactured by Lintec Corporation, trade name: SY adhesive).
  • Example 3 The acrylic adhesive (trade name: NCK101 adhesive manufactured by Toyo Ink Co., Ltd.), which is the first adhesive layer, was changed to an acrylic adhesive (trade name: SY adhesive manufactured by Lintec Corporation), and the second adhesive layer was acrylic.
  • An optical filter as a laminate was produced in the same manner as in Example 1 except that the adhesive was changed to a system adhesive (trade name: P0280 adhesive, manufactured by Lintec Corporation).
  • Example 4 Except that the acrylic adhesive (trade name: NCK101 adhesive manufactured by Toyo Ink Co., Ltd.), which is the first adhesive layer, was changed to an acrylic adhesive (trade name: P0280 adhesive manufactured by Lintec Co., Ltd.), the same as in Example 1 An optical filter as a laminate was produced.
  • the acrylic adhesive trade name: NCK101 adhesive manufactured by Toyo Ink Co., Ltd.
  • an acrylic adhesive trade name: P0280 adhesive manufactured by Lintec Co., Ltd.
  • Example 5 A laminate as in Example 1 except that the second adhesive layer and the antireflection film with an adhesive layer to be the second base material layer were not bonded onto the contrast-enhancing film as the first base material layer. An optical filter was prepared.
  • Example 6 Change the acrylic adhesive (product name: NCK101 adhesive, manufactured by Toyo Ink Co., Ltd.) to be the first adhesive layer to acrylic adhesive (product name: SY adhesive, manufactured by Lintec Corporation), and make the second adhesive layer non-
  • An optical filter as a laminate was produced in the same manner as in Example 1 except that the carrier sheet was changed to a carrier sheet (trade name: TX48A non-carrier sheet, thickness 25 ⁇ m, manufactured by TOMO EGAWA).
  • Example 7> The contrast improving film as the first base layer is changed to a 0.1 mm glass plate, the second adhesive layer is changed to an acrylic adhesive (trade name: P0280 adhesive), and the second adhesive layer is changed to the second adhesive layer.
  • An optical filter as a laminate was produced in the same manner as in Example 1 except that the base material layer was changed to a PET film (trade name: A4300, manufactured by Toyobo Co., Ltd.).
  • the adhesive strength between each substrate layer or the glass substrate as the adherend and each adhesive layer, adhesive residue and breakage at the time of peeling of the laminate were evaluated by the following methods.
  • the adhesion was measured as follows in accordance with the standard of JIS Z 0237.
  • Each adhesive layer (the first adhesive layer or the second adhesive layer) shown in Table 1 is formed on one side of a belt-like sheet made of polyethylene terephthalate (trade name: A4300, manufactured by Toyobo Co., Ltd.), and has an adhesive layer. A sheet was produced. Separately, each base material layer (first base material layer or second base material layer) shown in Table 1 is fixed to one side of a 2.5 mm thick soda lime glass plate with an adhesive (thickness 25 ⁇ m, width 25 mm). And the soda-lime glass plate which has a base material layer was manufactured.
  • the pressure-sensitive adhesive layer of the belt-like sheet and the base material layer of the soda lime glass plate were bonded together and pressure-bonded with a 2 kg rubber roll at room temperature to obtain a pressure-bonded body.
  • the pressure-bonded body was subjected to autoclave treatment (temperature 60 ° C., pressure 0.95 MPa, time 90 minutes) to prepare a test piece for measuring adhesion.
  • the adhesion strength 180 degree peel, tension rate 300 mm / min
  • the 1st adhesion layer of the laminated body (size: 200 mm x 300 mm) which has a structure shown in Table 1 was bonded together to the soda-lime glass plate as a to-be-adhered material. Then, it was left for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65%. After the standing, the laminate was peeled from the soda lime glass plate as the adherend, and the adhesive residue rate was calculated and evaluated based on the following formula.
  • Adhesive residue rate (%) (Area of adhesive layer transferred to soda lime glass / Area of adhesive layer bonded to soda lime glass) x 100 Moreover, the laminated body peeled off from soda-lime glass was observed visually, and the presence or absence of a fracture
  • the first base material layer is fixed to the soda lime glass plate with the first pressure-sensitive adhesive, and after the production of the soda lime glass plate having the base material layer, it is peeled off within 30 minutes and the adhesion strength is measured. The rate and the presence or absence of breakage were evaluated.
  • the adhesion force B was less than 5 [N / 25 mm] compared to the adhesion force A
  • adhesive residue was generated.
  • the laminate of Example 5 in which the second base material layer was not provided and the laminate of Example 6 in which the adhesion forces C and D were less than 5 [N / 25 mm] compared to the adhesion A were broken. did.
  • the laminate according to the present invention has good reworkability and can be applied to various display panels. Further, according to the present invention, it is possible to provide a display device having a laminate having good reworkability and good productivity.
  • the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2012-239313 filed on October 30, 2012 are cited herein as disclosure of the specification of the present invention. Incorporate.

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Abstract

A laminated body with good reworkability is provided. The laminated body is bonded to an adherend and used. The laminated body comprises, in order from an adherend side, a first adhesive layer, a first substrate layer, a second adhesive layer, and a second substrate layer. If the adhesive force between the adherend and the first adhesive layer when the laminated body has been bonded to an adherend is defined as A [N/25 mm], the adhesive force between the first adhesive layer and the first substrate layer is defined as B [N/25 mm], the adhesive force between the first substrate layer and the second adhesive layer is defined as C [N/25 mm], and the adhesive force between the second adhesive layer and the second substrate layer is defined as D [N/25 mm], the adhesive forces B, C and D are all 5 [N/25 mm] or higher than the adhesive force A.

Description

積層体および表示装置Laminated body and display device
　本発明は、被着材に貼り合わされて使用される積層体、および該積層体を用いた表示装置に関する。 The present invention relates to a laminate used by being bonded to an adherend, and a display device using the laminate.
　携帯電話、タブレットＰＣ、カーナビゲーション、パーソナルコンピュータ、券売機、銀行の端末等の電子機器に用いられる表示装置として、液晶表示パネル、有機ＥＬ表示パネル等の表示パネルの前面に、コントラスト向上フィルム、反射防止フィルム等の光学フィルタを粘着層によって貼り合わせたものが知られている。このような表示装置は、例えば、光学フィルタの片面に粘着層を設け、この粘着層によって表示パネルの前面に貼り合わせて製造している。 As a display device used in electronic devices such as mobile phones, tablet PCs, car navigation systems, personal computers, ticket vending machines, bank terminals, etc., a contrast-enhancement film, reflection is provided on the front of display panels such as liquid crystal display panels and organic EL display panels. An optical filter such as a prevention film bonded with an adhesive layer is known. Such a display device is manufactured, for example, by providing an adhesive layer on one side of an optical filter and attaching the adhesive layer to the front surface of the display panel.
　表示パネルと光学フィルタとの貼り合わせには高い位置精度が要求され、互いの位置が僅かでもずれると不良品と見なされる。表示パネルと光学フィルタとがずれて貼り合わされた場合、表示パネルが高価であることから、表示パネルから光学フィルタを剥離して、表示パネルを再利用する。従って、光学フィルタには、表示パネルから良好に剥離できること、いわゆるリワーク性が求められる。具体的には、表示パネルに粘着層が残留しないこと、いわゆる糊残りが少ないことが求められるとともに、光学フィルタの一部が損傷して残留しないことが求められる。 A high positional accuracy is required for bonding the display panel and the optical filter, and even if the positions are slightly shifted, it is regarded as a defective product. When the display panel and the optical filter are bonded to each other with a shift, the display panel is expensive. Therefore, the optical filter is removed from the display panel, and the display panel is reused. Therefore, the optical filter is required to be able to be peeled off from the display panel well, so-called reworkability. Specifically, it is required that the adhesive layer does not remain on the display panel, that is, so-called adhesive residue is small, and that the optical filter is partially damaged and does not remain.
　リワーク性を向上させるとともに、貼り合わせ時の気泡の混入を抑制するものとして、例えば、粘着層を２層構造とし、一方の粘着層のソーダガラス板に対する初期密着力を所定の範囲内とするとともに、両者の２４時間後の密着力を所定の範囲内に調整したものが知られている（例えば、特許文献１参照）。また、特に糊残りを抑制するものとして、ガラス基板に対する密着力を所定の範囲内とするとともに、破断点応力を所定の範囲内としたものが知られている（例えば、特許文献２参照）。 For example, the adhesive layer has a two-layer structure, and the initial adhesion of one adhesive layer to the soda glass plate is within a predetermined range while improving the reworkability and suppressing the mixing of bubbles at the time of bonding. In addition, there is known one in which the adhesion force after 24 hours of both is adjusted within a predetermined range (see, for example, Patent Document 1). In particular, as a means for suppressing adhesive residue, there is known a technique in which the adhesive force to a glass substrate is within a predetermined range and the breaking stress is within a predetermined range (for example, see Patent Document 2).
特開２０１２－１２１９７８号公報JP 2012-121978 A 特開２０１２－１１６９４０号公報JP 2012-116940 A
　リワーク性を向上させるために、密着力等を所定の範囲内とすることが知られている。しかしながら、粘着層の両主面には異なる種類の部材が配置されることが多く、密着力は部材の種類や表面状態等によって大きく異なる。このため単に密着力を規定しただけでは、必ずしもリワーク性を良好にできない。このような問題は表示装置に限らず、例えば、建築物や自動車等の窓ガラスに、Ｌｏｗ－Ｅ（Ｌｏｗ-Ｅｍｉｓｓｉｖｉｔｙ）膜とも呼ばれる熱線遮断膜が形成されたＬｏｗ－Ｅフィルム等の光学フィルタを貼り合わせる場合にも発生する。 In order to improve reworkability, it is known that the adhesion strength and the like are within a predetermined range. However, different types of members are often arranged on both main surfaces of the pressure-sensitive adhesive layer, and the adhesion force varies greatly depending on the type of member, surface condition, and the like. For this reason, the reworkability cannot always be improved simply by specifying the adhesion. Such a problem is not limited to a display device. For example, an optical filter such as a Low-E film in which a heat ray blocking film called a Low-E (Low-Emissivity) film is formed on a window glass of a building or an automobile is formed. It also occurs when pasting.
　本発明は、上記課題を解決するためになされたものであって、リワーク性が良好な積層体の提供を目的とする。また、本発明は、このような積層体を用いた表示装置の提供を目的とする。 The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a laminate having good reworkability. Another object of the present invention is to provide a display device using such a laminate.
　本発明の積層体は、被着材に貼り合わされて使用される積層体に関する。本発明の表示装置は、表示パネルを有する被着材と、該被着材に貼り合わされた積層体とを有する。該積層体は、上記した本発明の積層体である。 The laminate of the present invention relates to a laminate used by being bonded to an adherend. The display device of the present invention includes an adherend having a display panel and a laminated body bonded to the adherend. The laminate is the laminate of the present invention described above.
　本発明は、以下の要旨を有する。
（１）被着材に貼り合わされて使用される積層体であって、
　前記被着材側から順に、第１の粘着剤層、第１の基材層、第２の粘着剤層、および第２の基材層を有し、前記積層体が前記被着材に貼り合わされたときの前記被着材と前記第１の粘着剤層との密着力をＡ［Ｎ／２５ｍｍ］、前記第１の粘着剤層と第１の基材層との密着力をＢ［Ｎ／２５ｍｍ］、前記第１の基材層と前記第２の粘着剤層との密着力をＣ［Ｎ／２５ｍｍ］、前記第２の粘着剤層と第２の基材層との密着力をＤ［Ｎ／２５ｍｍ］としたとき、密着力Ａに比べて密着力Ｂ、Ｃ、およびＤはいずれも５［Ｎ／２５ｍｍ］以上大きいことを特徴とする積層体。
（２）前記密着力Ａは１～１５［Ｎ／２５ｍｍ］である上記（１）に記載の積層体。
（３）前記第１の基材層は、コントラスト向上層またはトリアセチルセルロースフィルムである上記（１）または（２）に記載の積層体。
（４）前記第２の基材層は、ポリエチレンテレフタレートフィルムを有する上記（１）乃至（３）のいずれかに記載の積層体。
（５）前記第１の粘着剤層および第２の粘着剤層のうち少なくとも１層は、アクリル系粘着剤を含む層である上記（１）乃至（４）のいずれかに記載の積層体。
（６）前記密着力ＣおよびＤは、いずれも密着力Ａに比べて７［Ｎ／２５ｍｍ］以上大きい上記（１）乃至（５）のいずれかに記載の積層体。
（７）前記第１の粘着剤層および第２の粘着剤層のうち少なくとも１層は、厚さが１０μｍ以上である上記（１）乃至（６）のいずれかに記載の積層体。
（８）前記第２の基材層は、反射防止層である上記（１）乃至（７）のいずれかに記載の積層体。
（９）前記積層体は表示装置用の光学フィルタである上記（１）乃至（８）のいずれかに記載の積層体。
（１０）表示パネルを有する被着材と、前記被着材に貼り合わされた積層体とを有する表示装置であって、前記積層体は上記（１）乃至（９）のいずれかに記載の積層体である表示装置。 The present invention has the following gist.
(1) A laminate used by being bonded to an adherend,
In order from the adherend side, a first adhesive layer, a first base material layer, a second adhesive layer, and a second base material layer are provided, and the laminate is attached to the adherend. The adhesion between the adherend and the first pressure-sensitive adhesive layer when combined is A [N / 25 mm], and the adhesion between the first pressure-sensitive adhesive layer and the first base material layer is B [N / 25 mm], the adhesive force between the first base material layer and the second adhesive layer is C [N / 25 mm], and the adhesive force between the second adhesive layer and the second base material layer is When D [N / 25 mm], the laminated body is characterized in that all of the adhesion forces B, C, and D are larger than the adhesion force A by 5 [N / 25 mm] or more.
(2) The laminate according to (1), wherein the adhesion A is 1 to 15 [N / 25 mm].
(3) The laminate according to (1) or (2), wherein the first base material layer is a contrast improving layer or a triacetyl cellulose film.
(4) The laminate according to any one of (1) to (3), wherein the second base material layer has a polyethylene terephthalate film.
(5) The laminate according to any one of (1) to (4), wherein at least one of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is a layer containing an acrylic pressure-sensitive adhesive.
(6) The laminated body according to any one of (1) to (5), wherein the adhesion strengths C and D are both greater than the adhesion strength A by 7 [N / 25 mm] or more.
(7) The laminate according to any one of (1) to (6), wherein at least one of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer has a thickness of 10 μm or more.
(8) The laminate according to any one of (1) to (7), wherein the second base material layer is an antireflection layer.
(9) The laminate according to any one of (1) to (8), wherein the laminate is an optical filter for a display device.
(10) A display device having an adherend having a display panel and a laminate bonded to the adherend, wherein the laminate is a laminate according to any one of (1) to (9). A display device that is a body.
　本発明によれば、リワーク性が良好な積層体を提供できる。また、本発明によれば、リワーク性が良好な積層体を有し、生産性の良好な表示装置を提供できる。 According to the present invention, a laminate having good reworkability can be provided. Further, according to the present invention, it is possible to provide a display device having a laminate having good reworkability and good productivity.
積層体を有する表示装置の一実施形態を模式的に示す断面図。Sectional drawing which shows typically one Embodiment of the display apparatus which has a laminated body. コントラスト向上層の一実施形態を模式的に示す断面図。Sectional drawing which shows typically one Embodiment of a contrast improvement layer.
　以下、本発明の実施形態について図面を参照して説明する。
　図１は、積層体を用いた表示装置の一実施形態を示す断面図である。 Embodiments of the present invention will be described below with reference to the drawings.
FIG. 1 is a cross-sectional view showing an embodiment of a display device using a laminate.
　表示装置１０は、例えば、表示パネルを有する被着材１１と、この被着材１１の前面に貼り合わされた光学フィルタとしての積層体１２とを有する。積層体１２は、被着材１１側から順に、第１の粘着剤層１３、第１の基材層１４、第２の粘着剤層１５、および第２の基材層１６を有する。 The display device 10 includes, for example, an adherend 11 having a display panel, and a laminated body 12 as an optical filter bonded to the front surface of the adherend 11. The laminate 12 includes a first pressure-sensitive adhesive layer 13, a first base material layer 14, a second pressure-sensitive adhesive layer 15, and a second base material layer 16 in order from the adherend 11 side.
　積層体１２は、積層体１２が被着材１１に貼り合わされたときの被着材１１と第１の粘着剤層１３との密着力をＡ［Ｎ／２５ｍｍ］、第１の粘着剤層１３と第１の基材層１４との密着力をＢ［Ｎ／２５ｍｍ］、第１の基材層１４と第２の粘着剤層１５との密着力をＣ［Ｎ／２５ｍｍ］、第２の粘着剤層１５と第２の基材層１６との密着力をＤ［Ｎ／２５ｍｍ］としたとき、密着力Ａに比べて密着力Ｂ、Ｃ、およびＤはいずれも５［Ｎ／２５ｍｍ］以上大きい。すなわち、Ｂ－Ａ≧５［Ｎ／２５ｍｍ］、Ｃ－Ａ≧５［Ｎ／２５ｍｍ］、およびＤ－Ａ≧５［Ｎ／２５ｍｍ］を満たす。なお、本明細書において「密着力」とは「ＪＩＳ　Ｚ　０２３７の規格に準拠」する。 The laminate 12 has an adhesive force of A [N / 25 mm] between the adherend 11 and the first adhesive layer 13 when the laminate 12 is bonded to the adherend 11, and the first adhesive layer 13. The adhesive strength between the first base material layer 14 and the first base material layer 14 is B [N / 25 mm], the adhesive strength between the first base material layer 14 and the second adhesive layer 15 is C [N / 25 mm], the second When the adhesive force between the adhesive layer 15 and the second base material layer 16 is D [N / 25 mm], the adhesive force B, C, and D are all 5 [N / 25 mm] compared to the adhesive force A. Bigger than that. That is, B−A ≧ 5 [N / 25 mm], C−A ≧ 5 [N / 25 mm], and D−A ≧ 5 [N / 25 mm] are satisfied. In this specification, “adhesion strength” is “conforms to the standard of JIS Z 0237”.
　第１の基材層１４に加えて第２の基材層１６を設けるとともに、密着力Ａに比べて密着力Ｂ、Ｃ、およびＤをいずれも５［Ｎ／２５ｍｍ］以上大きくすることで、積層体１２のリワーク性を良好にできる。具体的には、被着材１１から積層体１２を剥離する際、第１の粘着剤層１３や第１の基材層１４の一部が被着材１１に残留することを抑制できる。特に、第１の基材層１４が、コントラスト向上フィルム、薄板状のガラス板等のように、破れなどにより損傷しやすいものである場合、第２の基材層１６により補強して、その損傷を抑制して被着材１１への残留を抑制できる。 In addition to providing the second base material layer 16 in addition to the first base material layer 14, by increasing the adhesion forces B, C, and D by 5 [N / 25 mm] or more compared to the adhesion force A, The reworkability of the laminate 12 can be improved. Specifically, when the laminate 12 is peeled from the adherend 11, it is possible to suppress the first pressure-sensitive adhesive layer 13 and a part of the first base material layer 14 from remaining on the adherend 11. In particular, when the first base material layer 14 is easily damaged by tearing, such as a contrast enhancement film or a thin glass plate, the first base material layer 14 is reinforced by the second base material layer 16 and the damage It is possible to suppress the remaining on the adherend 11 by suppressing the above.
　被着材１１が有する表示パネルとしては、液晶表示パネル、プラズマディスプレイパネル、有機ＥＬ表示パネル等の表示パネルが挙げられる。なお、被着材１１は、必ずしも単体の表示パネルのみを有するに限られず、その前面には表示パネルの種類に応じて、後述の機能層、例えば、電磁波遮蔽層、コントラスト向上層等が積層されてもよい。 Examples of the display panel of the adherend 11 include display panels such as a liquid crystal display panel, a plasma display panel, and an organic EL display panel. The adherend 11 is not necessarily limited to having only a single display panel, and a functional layer described later, for example, an electromagnetic wave shielding layer, a contrast improving layer, or the like is laminated on the front surface according to the type of the display panel. May be.
　第１の粘着剤層１３は、被着材１１と第１の基材層１４とを貼り合わせるものであり、被着材１１に貼り合わされたときの密着力Ａ［Ｎ／２５ｍｍ］と第１の基材層１４に貼り合わされたときの密着力Ｂ［Ｎ／２５ｍｍ］との密着力差（Ｂ－Ａ)が５［Ｎ／２５ｍｍ］以上のものである。なお、第１の粘着剤層１３は、同一材料によって全体が構成される単層構造を有するものである。すなわち、第１の粘着剤層１３には、複層構造のものは含まれない。 The first pressure-sensitive adhesive layer 13 is for bonding the adherend 11 and the first base material layer 14, and the adhesive force A [N / 25 mm] when bonded to the adherend 11 and the first The adhesive force difference (BA) with the adhesive force B [N / 25 mm] when bonded to the base material layer 14 is 5 [N / 25 mm] or more. In addition, the 1st adhesive layer 13 has a single layer structure comprised entirely with the same material. That is, the first pressure-sensitive adhesive layer 13 does not include a multilayer structure.
　密着力差（Ｂ－Ａ)が５［Ｎ／２５ｍｍ］未満の場合、被着材１１から積層体１２を剥離する際、第１の粘着剤層１３が被着材１１の表面に残留しやすい。密着力差（Ｂ－Ａ)を５［Ｎ／２５ｍｍ］以上とすることで、被着材１１への第１の粘着剤層１３の残留を抑制できる。また、単層構造とすることで、生産性も良好とできる。密着力差（Ｂ－Ａ)は、５．５［Ｎ／２５ｍｍ］以上が好ましく、８．０［Ｎ／２５ｍｍ］以上がさらに好ましい。密着力差（Ｂ－Ａ)は、基本的には大きいほど好ましいが、通常は１０［Ｎ／２５ｍｍ］程度もあれば十分である。 When the adhesion difference (BA) is less than 5 [N / 25 mm], the first pressure-sensitive adhesive layer 13 tends to remain on the surface of the adherend 11 when the laminate 12 is peeled from the adherend 11. . By setting the adhesion difference (BA) to 5 [N / 25 mm] or more, it is possible to suppress the first adhesive layer 13 from remaining on the adherend 11. Moreover, productivity can also be made favorable by setting it as a single layer structure. The adhesion difference (BA) is preferably 5.5 [N / 25 mm] or more, and more preferably 8.0 [N / 25 mm] or more. Basically, the larger the difference in adhesion (BA) is, the better, but it is usually sufficient that the difference is about 10 [N / 25 mm].
　密着力差（Ｂ－Ａ)の調整は、例えば、被着対象である被着材１１および第１の基材層１４に応じて、密着力差（Ｂ－Ａ)が５［Ｎ／２５ｍｍ］以上となるような粘着剤を選択して行う。具体的には、第１の粘着剤層１３への適用が検討される各種の粘着剤について、被着材１１との密着力Ａを測定するとともに、第１の基材層１４を構成する構成材との密着力Ｂを測定し、これらの中から密着力差（Ｂ－Ａ)が５［Ｎ／２５ｍｍ］以上となるものを選択して使用する。密着力は、粘着剤の構成材料によって大きく変化する他、被着対象の構成材料および表面の凹凸等の表面状態によっても大きく変化する。従って、被着対象に対する密着力Ａ、Ｂを実際に測定することで、密着力差（Ｂ－Ａ)を確実に調整できる。なお、個々の密着力Ａ、Ｂの調整は、例えば、粘着剤の組成、硬さ等の調整により行うことができる。 The adjustment of the adhesion difference (BA) is, for example, an adhesion difference (BA) of 5 [N / 25 mm] depending on the adherend 11 and the first base material layer 14 to be deposited. This is performed by selecting an adhesive as described above. Specifically, for various pressure-sensitive adhesives that are considered to be applied to the first pressure-sensitive adhesive layer 13, the adhesive force A with the adherend 11 is measured and the first base material layer 14 is configured. The adhesion strength B with the material is measured, and a material having an adhesion strength difference (BA) of 5 [N / 25 mm] or more is selected and used. The adhesive force greatly varies depending on the constituent material of the pressure-sensitive adhesive, and also varies greatly depending on the constituent material to be deposited and the surface condition such as surface irregularities. Therefore, the adhesion force difference (B−A) can be reliably adjusted by actually measuring the adhesion forces A and B to the deposition target. In addition, adjustment of each contact | adhesion power A and B can be performed by adjustment of a composition, hardness, etc. of an adhesive, for example.
　密着力Ａ、Ｂ自体の値は、密着力差（Ｂ－Ａ)が所定の範囲内となれば必ずしも制限されない。密着力Ａは、被着材１１との密着性の観点から、１［Ｎ／２５ｍｍ］以上が好ましい。また、密着力Ａは、被着材１１との剥離を容易にする観点から、１５［Ｎ／２５ｍｍ］以下が好ましく、１０［Ｎ／２５ｍｍ］以下がより好ましい。密着力Ｂ［Ｎ／２５ｍｍ］は、密着力差（Ｂ－Ａ)が５［Ｎ／２５ｍｍ］以上となればよく、通常は密着力差（Ｂ－Ａ）が１０［Ｎ／２５ｍｍ］程度となれば十分である。
　なお、被着材１１の第１の粘着剤層に接する面がガラス板であり、かつ、第１の基材層が薄板状のガラス板である場合に、密着力差（Ｂ－Ａ）を５［Ｎ／２５ｍｍ］以上とするためには、第１の粘着剤層の密着力が経時で変化（増加）する特性を利用することができる。すなわち、第１の基材層である薄板状のガラス板に第１の粘着層を貼り合わせた後２４時間以上放置し、次いで被着材であるガラス板を貼り合わせた後、３時間以内に剥離することで、密着力差（Ｂ－Ａ)を５［Ｎ／２５ｍｍ］以上とすることができる。リワーク性を良好にする観点からは、第１の基材層である薄板状のガラス板を貼り合わせた後、１時間以内に剥離することが好ましい。該時間内に剥離することで、密着力差（Ｂ－Ａ)を５［Ｎ／２５ｍｍ］以上とすることができ、リワーク性を良好にできる。 The values of the adhesion forces A and B themselves are not necessarily limited as long as the adhesion force difference (BA) is within a predetermined range. The adhesion strength A is preferably 1 [N / 25 mm] or more from the viewpoint of adhesion to the adherend 11. Further, the adhesion A is preferably 15 [N / 25 mm] or less, more preferably 10 [N / 25 mm] or less from the viewpoint of facilitating peeling from the adherend 11. The adhesion force B [N / 25 mm] is sufficient if the adhesion force difference (BA) is 5 [N / 25 mm] or more, and usually the adhesion force difference (BA) is about 10 [N / 25 mm]. It will be enough.
When the surface of the adherend 11 that is in contact with the first pressure-sensitive adhesive layer is a glass plate, and the first base material layer is a thin glass plate, the difference in adhesion (BA) is obtained. In order to set it to 5 [N / 25 mm] or more, the characteristic that the adhesive force of the first pressure-sensitive adhesive layer changes (increases) with time can be used. That is, after the first adhesive layer is bonded to the thin glass plate as the first base material layer, it is allowed to stand for 24 hours or more, and then the glass plate as the adherend is bonded within 3 hours. By peeling, the adhesion difference (BA) can be made 5 [N / 25 mm] or more. From the viewpoint of improving the reworkability, it is preferable that the first base material layer is peeled within one hour after bonding the thin glass plate. By peeling within this time, the adhesion difference (BA) can be made 5 [N / 25 mm] or more, and the reworkability can be improved.
　第１の粘着剤層１３の厚さは、必ずしも制限されないが、１０μｍ以上が好ましい。厚さを１０μｍ以上とすることで、被着材１１と第１の基材層１４とを確実に貼り合わせることができる。第１の粘着剤層１３の厚さは、１５μｍ以上がより好ましく、２０μｍ以上がさらに好ましい。通常、第１の粘着剤層１３の厚さは、３０μｍもあれば十分である。 The thickness of the first pressure-sensitive adhesive layer 13 is not necessarily limited, but is preferably 10 μm or more. By setting the thickness to 10 μm or more, the adherend 11 and the first base material layer 14 can be bonded together reliably. As for the thickness of the 1st adhesive layer 13, 15 micrometers or more are more preferable, and 20 micrometers or more are further more preferable. Usually, the thickness of the first pressure-sensitive adhesive layer 13 is sufficient if it is 30 μm.
　第２の粘着剤層１５は、第１の基材層１４と第２の基材層１６とを貼り合わせるために設けられる。第２の粘着剤層１５は、第１の基材層１４に貼り合わされたときの密着力Ｃ［Ｎ／２５ｍｍ］および第２の基材層１６に貼り合わされたときの密着力Ｄ［Ｎ／２５ｍｍ］がいずれも密着力Ａよりも５［Ｎ／２５ｍｍ］以上大きいものである。すなわち、密着力差（Ｃ－Ａ）および密着力差（Ｄ－Ａ）がいずれも５［Ｎ／２５ｍｍ］以上である。 The second pressure-sensitive adhesive layer 15 is provided for bonding the first base material layer 14 and the second base material layer 16 together. The second pressure-sensitive adhesive layer 15 has an adhesion force C [N / 25 mm] when bonded to the first substrate layer 14 and an adhesion force D [N / when bonded to the second substrate layer 16. 25 mm] is larger than the adhesion force A by 5 [N / 25 mm] or more. That is, both the adhesion force difference (CA) and the adhesion force difference (DA) are 5 [N / 25 mm] or more.
　密着力Ｃ、Ｄを密着力Ａよりも５［Ｎ／２５ｍｍ］以上大きくすることで、被着材１１から積層体１２を剥離する際、所望の剥離部、すなわち被着材１１と第１の粘着剤層１３との間で剥離させることができ、その他の部分、すなわち第１の基材層１４と第２の粘着剤層１５との間、および第２の粘着剤層１５と第２の基材層１６との間における剥離を抑制できる。これにより、第１の基材層１４が破れなどにより損傷しやすいものである場合にも、第２の基材層１６により効果的に補強して、その損傷を抑制して被着材１１への残留を抑制できる。 By making the adhesion forces C and D larger than the adhesion force A by 5 [N / 25 mm] or more, when peeling the laminate 12 from the adherend 11, a desired peeled portion, that is, the adherend 11 and the first It can be peeled between the pressure-sensitive adhesive layer 13, and other portions, that is, between the first base material layer 14 and the second pressure-sensitive adhesive layer 15 and between the second pressure-sensitive adhesive layer 15 and the second pressure-sensitive adhesive layer 15. Separation with the base material layer 16 can be suppressed. Thereby, even when the first base material layer 14 is easily damaged due to tearing or the like, the second base material layer 16 is effectively reinforced to suppress the damage to the adherend 11. Can be suppressed.
　密着力Ｃ、Ｄの調整についても、例えば、被着対象である第１の基材層１４および第２の基材層１６に応じて、密着力Ａに対して密着力Ｃ、Ｄのいずれもが５［Ｎ／２５ｍｍ］以上大きくなるような粘着剤を選択して行う。具体的には、第２の粘着剤層１５への適用が検討される各種の粘着剤について、第１の基材層１４を構成する構成材との密着力Ｃを測定するとともに、第２の基材層１６を構成する構成材との密着力Ｄを測定し、これらの中から密着力Ａに対して密着力Ｃ、Ｄのいずれもが５［Ｎ／２５ｍｍ］以上大きくなるような粘着剤を選択して使用する。 Regarding the adjustment of the adhesion forces C and D, for example, both the adhesion forces C and D with respect to the adhesion force A according to the first base material layer 14 and the second base material layer 16 to be attached. Is performed by selecting an adhesive that increases 5 [N / 25 mm] or more. Specifically, for various pressure-sensitive adhesives that are considered to be applied to the second pressure-sensitive adhesive layer 15, the adhesive force C with the constituent material constituting the first base material layer 14 is measured, and the second Adhesive that measures adhesion D with the constituent material constituting the base material layer 16 and increases the adhesion C and D with respect to the adhesion A among these by 5 [N / 25 mm] or more. Select and use.
　密着力Ｃ、Ｄは、いずれも密着力Ａに対して７．０［Ｎ／２５ｍｍ］以上大きいことが好ましい。なお、密着力Ｃ、Ｄの互いの大小関係は特に制限されず、密着力Ｃが大きくてもよいし、密着力Ｄが大きくてもよいし、互いに同一であってもよい。密着力Ｃ、Ｄは、いずれも密着力Ａに対して１０［Ｎ／２５ｍｍ］程度大きければ十分である。 The adhesion forces C and D are preferably 7.0 [N / 25 mm] or more larger than the adhesion force A. The magnitude relationship between the adhesion forces C and D is not particularly limited, and the adhesion force C may be large, the adhesion force D may be large, or may be the same. It is sufficient that the adhesion forces C and D are about 10 [N / 25 mm] larger than the adhesion force A.
　第２の粘着剤層１５の厚さは、必ずしも制限されないが、１０μｍ以上が好ましい。厚さを１０μｍ以上とすることで、第１の基材層１４と第２の基材層１６とを確実に貼り合わせることができる。第２の粘着剤層１５の厚さは、１５μｍ以上がより好ましく、２０μｍ以上がさらに好ましい。通常、第２の粘着剤層１５の厚さは、３０μｍもあれば十分である。 The thickness of the second pressure-sensitive adhesive layer 15 is not necessarily limited, but is preferably 10 μm or more. By setting the thickness to 10 μm or more, the first base material layer 14 and the second base material layer 16 can be reliably bonded together. The thickness of the second pressure-sensitive adhesive layer 15 is more preferably 15 μm or more, and further preferably 20 μm or more. Usually, it is sufficient that the thickness of the second pressure-sensitive adhesive layer 15 is 30 μm.
　第１の粘着剤層１３および第２の粘着剤層１５の構成材料は、所定の密着力差等が得られれば必ずしも制限されず、例えば、アクリル系粘着剤、ウレタン系粘着剤、ポリエステル系粘着剤、シリコーン系粘着剤、ゴム系粘着剤等が挙げられ、これらの中でもアクリル系粘着剤が好適に用いられる。 The constituent material of the first pressure-sensitive adhesive layer 13 and the second pressure-sensitive adhesive layer 15 is not necessarily limited as long as a predetermined difference in adhesion force is obtained. For example, an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and a polyester-based pressure-sensitive adhesive Agents, silicone pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, and the like. Among these, acrylic pressure-sensitive adhesives are preferably used.
　アクリル系粘着剤は、アクリル系単量体単位を主成分として含む重合体である。アクリル系単量体としては、（メタ）アクリル酸、イタコン酸、（無水）マレイン酸、（無水）フマル酸、クロトン酸、これらのアルキルエステルが挙げられる。ここで、（メタ）アクリル酸とは、アクリル酸およびメタクリル酸の総称である。（メタ）アクリレートも同様である。 The acrylic pressure-sensitive adhesive is a polymer containing an acrylic monomer unit as a main component. Examples of the acrylic monomer include (meth) acrylic acid, itaconic acid, (anhydrous) maleic acid, (anhydrous) fumaric acid, crotonic acid, and alkyl esters thereof. Here, (meth) acrylic acid is a general term for acrylic acid and methacrylic acid. The same applies to (meth) acrylate.
　アクリル系単量体の中でも、（メタ）アクリル酸またはそのアルキルエステルを主成分とするものが好ましい。（メタ）アクリル酸のアルキルエステルとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ｎ－ヘプチル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｎ－デシル（メタ）アクリレート、イソデシル（メタ）アクリレート等が挙げられる。 Among the acrylic monomers, those having (meth) acrylic acid or an alkyl ester thereof as a main component are preferable. Examples of alkyl esters of (meth) acrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, and n-hexyl (meth) ) Acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, etc. .
　アクリル系粘着剤には、アクリル系単量体以外の単量体を用いることもできる。用いられる他の単量体の例としては、酢酸ビニル、プロピオン酸ビニル等のビニルエステル類；エチレン、プロピレン、イソブチレン等のオレフィン類；塩化ビニル、ビニリデンクロリド等のハロゲン化オレフィン類；スチレン、α－メチルスチレン等のスチレン系単量体；ブタジエン、イソプレン、クロロプレン等のジエン系単量体；アクリロニトリル、メタクリロニトリル等のニトリル系単量体；アクリルアミド、Ｎ,Ｎ－ジメチルアクリルアミド、Ｎ,Ｎ－ジメチルメタクリルアミド等のアクリルアミド系単量体等が挙げられる。 Monomers other than acrylic monomers can also be used for the acrylic pressure-sensitive adhesive. Examples of other monomers used include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; styrene, α- Styrene monomers such as methylstyrene; Diene monomers such as butadiene, isoprene and chloroprene; Nitrile monomers such as acrylonitrile and methacrylonitrile; Acrylamide, N, N-dimethylacrylamide, N, N-dimethyl Examples include acrylamide monomers such as methacrylamide.
　アクリル系粘着剤には、その凝集力を高めるために、架橋点となりうる官能基（例えば、ヒドロキシ基、グリシジル基等）を有する単量体を使用できる。架橋点となりうる官能基を有する単量体としては、例えばヒドロキシエチル（メタ）アクリレート、グリシジル（メタ）アクリレート等が挙げられる。 In the acrylic pressure-sensitive adhesive, a monomer having a functional group (for example, a hydroxy group, a glycidyl group, or the like) that can become a crosslinking point can be used in order to increase the cohesive force. Examples of the monomer having a functional group that can serve as a crosslinking point include hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and the like.
　架橋点となりうる官能基を有する単量体を使用する場合、架橋剤を添加することが好ましい。架橋剤を添加することで、架橋点に反応させてポリマーを架橋させることにより凝集力を確保できる。架橋剤としては、メラミン樹脂、尿素樹脂、エポキシ樹脂、金属酸化物、金属塩、金属水酸化物、金属キレート、ポリイソシアネート、カルボキシ基含有ポリマー、酸無水物、ポリアミン等が挙げられ、架橋点となりうる官能基の種類に応じて適宜選択される。 When using a monomer having a functional group that can be a crosslinking point, it is preferable to add a crosslinking agent. By adding a crosslinking agent, it is possible to ensure cohesion by reacting with the crosslinking point to crosslink the polymer. Examples of cross-linking agents include melamine resins, urea resins, epoxy resins, metal oxides, metal salts, metal hydroxides, metal chelates, polyisocyanates, carboxy group-containing polymers, acid anhydrides, polyamines, and so on. It is suitably selected according to the type of functional group that can be obtained.
　また、アクリル系粘着剤には、密着力を調整するためにシランカップリング剤を含有させることができる。シランカップリング剤としては、分子内にアルコキシシリル基を少なくとも１個有する有機ケイ素化合物を好ましく用いることができる。 Also, the acrylic pressure-sensitive adhesive can contain a silane coupling agent in order to adjust the adhesion. As the silane coupling agent, an organosilicon compound having at least one alkoxysilyl group in the molecule can be preferably used.
　さらに、アクリル系粘着剤には、紫外線吸収剤、着色色素等を添加できる。 Furthermore, an ultraviolet absorber, a coloring pigment, and the like can be added to the acrylic adhesive.
　紫外線吸収剤としては、例えば、ベンゾトリアゾール系、ベンゾフェノン系、サリシレート系、シアノアクリレート系、トリアジン系、オキザニリド系、ニッケル錯塩系、無機系等の紫外線吸収剤が挙げられる。 Examples of the UV absorber include UV absorbers such as benzotriazole, benzophenone, salicylate, cyanoacrylate, triazine, oxanilide, nickel complex, and inorganic.
　着色色素としては、色調補正色素、近赤外線吸収色素が挙げられる。色調補正色素は、可視光の特定波長域の一部を吸収し、透過可視光の色調を改善する。色調補正色素としては、例えば、アゾ系、縮合アゾ系、ジイモニウム系、フタロシアニン系、アンスラキノン系、インジゴ系、ペリノン系、ペリレン系、ジオキサジン系、キナクリドン系、メチン系、イソインドリノン系、キノフタロン系、ピロール系、チオインジゴ系、金属錯体系、ポルフィリン系、テトラアザポルフィリン系等の色素が挙げられる。 Coloring dyes include color correction dyes and near infrared absorbing dyes. The color tone correction dye absorbs a part of a specific wavelength range of visible light and improves the color tone of transmitted visible light. Examples of color correction dyes include azo, condensed azo, diimonium, phthalocyanine, anthraquinone, indigo, perinone, perylene, dioxazine, quinacridone, methine, isoindolinone, and quinophthalone. , Pyrrole-based, thioindigo-based, metal complex-based, porphyrin-based, tetraazaporphyrin-based pigments.
　近赤外線吸収色素としては、例えば、ポリメチン系、フタロシアニン系、ナフタロシアニン系、アミニウム系、イモニウム系、ジイモニウム系、アンスラキノン系、ジチオール金属錯体系、ナフトキノン系、インドールフェノール系、アゾ系、トリアリルメタン系、酸化タングステン系等の色素が挙げられる。 Examples of near infrared absorbing dyes include polymethine, phthalocyanine, naphthalocyanine, aminium, imonium, diimonium, anthraquinone, dithiol metal complex, naphthoquinone, indolephenol, azo, triallylmethane And dyes such as those based on tungsten oxide.
　第１の粘着剤層１３は、上記したような構成成分を含む粘着剤を第１の基材層１４に塗布して形成してもよいし、予め上記したような構成成分を含む粘着剤をシート状に成形した粘着シートを第１の基材層１４に貼り合わせて形成してもよい。同様に、第２の粘着剤層１５についても、第１の基材層１４または第２の基材層１６に粘着剤を塗布して形成してもよいし、粘着シートを貼り合わせて形成してもよい。塗工は、例えば、浸漬コーティング法、スプレーコーティング法、スピンナーコーティング法、ビードコーティング法、ワイヤーバーコーティング法、ブレードコーティング法、ローラーコーティング法、カーテンコーティング法、スリットダイコーター法、グラビアコーター法、スリットリバースコーター法、マイクログラビア法、コンマコーター法等を適用できる。 The first pressure-sensitive adhesive layer 13 may be formed by applying a pressure-sensitive adhesive containing the above-described constituent components to the first base material layer 14, or a pressure-sensitive adhesive containing the above-described constituent components in advance. A pressure-sensitive adhesive sheet formed into a sheet shape may be bonded to the first base material layer 14. Similarly, the second pressure-sensitive adhesive layer 15 may be formed by applying a pressure-sensitive adhesive to the first base material layer 14 or the second base material layer 16 or by bonding a pressure-sensitive adhesive sheet. May be. Coating is, for example, dip coating method, spray coating method, spinner coating method, bead coating method, wire bar coating method, blade coating method, roller coating method, curtain coating method, slit die coater method, gravure coater method, slit reverse. A coater method, a micro gravure method, a comma coater method, etc. can be applied.
　粘着剤および粘着シートには、市販品を使用することができる。例えば、粘着剤として、ＮＣＫ１０１粘着（東洋インキ社製、アクリル系粘着剤）、ＥＸＫ０４－４８８粘着（東洋インキ社製、アクリル系粘着剤）が挙げられる。また、粘着シートとして、ＴＸ４８Ａ粘着ノンキャリアシート（ＴＯＭＯＥＧＡＷＡ社製、アクリル系粘着剤）、Ｐ０２８０粘着ノンキャリアシート（リンテック社製、アクリル系粘着剤）が挙げられる。なお、上記した「ノンキャリアシート」とは、シリコーン塗布された二つの基材が粘着剤を介してラミネートされたフィルムのことである。 Commercial products can be used for the adhesive and the adhesive sheet. Examples of the adhesive include NCK101 adhesive (acrylic adhesive manufactured by Toyo Ink) and EXK04-488 adhesive (acrylic adhesive manufactured by Toyo Ink). Examples of the pressure-sensitive adhesive sheet include a TX48A pressure-sensitive non-carrier sheet (manufactured by TOMOEGAWA, acrylic pressure-sensitive adhesive) and a P0280 pressure-sensitive non-carrier sheet (manufactured by Lintec, acrylic pressure-sensitive adhesive). The above-mentioned “non-carrier sheet” is a film in which two base materials coated with silicone are laminated via an adhesive.
　第１の基材層１４、第２の基材層１６は、少なくとも基材を有するものであればよく、例えば、基材単体の他、基材の表面に機能膜を有する機能層が挙げられる。 The 1st base material layer 14 and the 2nd base material layer 16 should just have a base material at least, for example, the functional layer which has a functional film on the surface of a base material besides a base material simple substance is mentioned. .
　単体の基材としては、樹脂フィルム、薄板状のガラス板等が挙げられる。なお、単体の基材は、必要に応じて、かつ可能な限度において、着色色素、紫外線吸収剤等を含有できる。 Examples of the single base material include a resin film and a thin glass plate. The single base material can contain a coloring pigment, an ultraviolet absorber, and the like as necessary and to the extent possible.
　樹脂フィルムとしては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）等のポリエステル類；ポリエチレン、ポリプロピレン等のポリオレフィン類；ポリメチルメタクリレート（ＰＭＭＡ）等のポリアクリレート類；ポリカーボネート（ＰＣ）類；ポリスチレン類；トリアセチルセルロース、ジアセチルセルロース、アセテートブチレートセルロース等のセルロース類；ポリビニルアルコール；ポリ塩化ビニル；ポリ塩化ビニリデン；エチレン－酢酸ビニル共重合体；ポリビニルブチラール；ポリウレタン類等のフィルムが挙げられる。樹脂フィルムの厚さは、１０～２００μｍが好ましく、５０～１５０μｍがより好ましい。 Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyolefins such as polyethylene and polypropylene; polyacrylates such as polymethyl methacrylate (PMMA); polycarbonates (PC); Polystyrenes; celluloses such as triacetyl cellulose, diacetyl cellulose, acetate butyrate cellulose; polyvinyl alcohol; polyvinyl chloride; polyvinylidene chloride; ethylene-vinyl acetate copolymer; polyvinyl butyral; The thickness of the resin film is preferably 10 to 200 μm, more preferably 50 to 150 μm.
　薄板状のガラス板は、ガラスの質感を付与して意匠性を高めるために、または表面保護のために設けられる。このようなガラス板としては、厚さが０．０５～５ｍｍのものが好ましい。 A thin glass plate is provided for enhancing the design by imparting the texture of glass or for protecting the surface. Such a glass plate preferably has a thickness of 0.05 to 5 mm.
　機能層としては、コントラスト向上層、電磁波遮蔽層、反射防止層、防眩層、着色層、紫外線吸収層等が挙げられる。 Examples of the functional layer include a contrast improving layer, an electromagnetic wave shielding layer, an antireflection layer, an antiglare layer, a colored layer, and an ultraviolet absorbing layer.
　図２は、コントラスト向上層の一例を示す断面図である。なお、図２は、第１の基材層１４にコントラスト向上層を適用した例を示したものである。 FIG. 2 is a cross-sectional view showing an example of the contrast improving layer. FIG. 2 shows an example in which a contrast improving layer is applied to the first base material layer 14.
　コントラスト向上層１４’は、外光によるコントラストの低下を抑制するために設けられ、基材１４１の片面にコントラスト向上膜１４２を有するものである。 The contrast enhancement layer 14 ′ is provided to suppress a decrease in contrast due to external light, and has a contrast enhancement film 142 on one surface of the base material 141.
　基材１４１としては、単体の基材と同様な樹脂フィルムまたは薄板状のガラス板等が挙げられる。コントラスト向上膜１４２は、水平方向に延び、かつ互いに平行に配置される複数の透光性領域１４２ａと、これら透光性領域１４２ａ間に配置される暗色部１４２ｂとを有する。暗色部１４２ｂは、暗色粒子を含有するものであり、その断面形状は、略台形状の他、正方形状や長方形状、三角形状等であってもよい。透光性領域１４２ａおよび暗色部１４２ｂは、例えば、紫外線硬化性樹脂および光重合開始剤を含有する組成物の硬化物からなる。 Examples of the substrate 141 include a resin film similar to a single substrate or a thin glass plate. The contrast enhancement film 142 includes a plurality of light transmitting regions 142a that extend in the horizontal direction and are arranged in parallel to each other, and a dark color portion 142b that is disposed between the light transmitting regions 142a. The dark portion 142b contains dark particles, and the cross-sectional shape thereof may be a square shape, a rectangular shape, a triangular shape, or the like in addition to a substantially trapezoidal shape. The translucent region 142a and the dark portion 142b are made of a cured product of a composition containing, for example, an ultraviolet curable resin and a photopolymerization initiator.
　コントラスト向上層１４’によれば、暗色粒子を含有する暗色部１４２ｂによって外光を吸収して表示画像のコントラストを向上させることができ、また透光性領域１４２ａには暗色粒子が含有されないことから光透過性が低下せず、表示画像が暗くなることによる視認性の低下を抑制できる。 According to the contrast improving layer 14 ′, the dark color portion 142b containing dark particles can absorb external light to improve the contrast of the display image, and the translucent region 142a does not contain dark particles. It is possible to suppress a decrease in visibility due to the darkness of the display image without reducing the light transmittance.
　コントラスト向上層１４’は、例えば、コントラスト向上膜１４２、特に透光性領域１４２ａおよび暗色部１４２ｂが第１の粘着剤層１３に接触するように配置される。このような場合、被着材１１から積層体１２を剥離しようとすると、例えば、透光性領域１４２ａと暗色部１４２ｂとの境界部分、または透光性領域１４２ａにおける厚さの薄い部分において損傷しやすく、損傷部分が第１の粘着剤層１３とともに被着材１１に残留しやすい。第２の基材層１６を設けるとともに、密着力差（Ｂ－Ａ)を５［Ｎ／２５ｍｍ］以上とすることで、コントラスト向上層１４’のように損傷しやすいものでも、被着材１１への残留を抑制できる。 The contrast improving layer 14 ′ is disposed so that, for example, the contrast improving film 142, in particular, the translucent region 142 a and the dark portion 142 b are in contact with the first pressure-sensitive adhesive layer 13. In such a case, when the laminate 12 is peeled off from the adherend 11, for example, damage is caused at a boundary portion between the translucent region 142a and the dark color portion 142b or a thin portion in the translucent region 142a. It is easy and the damaged part tends to remain on the adherend 11 together with the first pressure-sensitive adhesive layer 13. Even when the second base material layer 16 is provided and the adhesion difference (BA) is set to 5 [N / 25 mm] or more, even if it is easily damaged like the contrast improving layer 14 ′, the adherend 11 Residue on the surface can be suppressed.
　コントラスト向上層１４’における透光性領域１４２ａの構成材料は、暗色部１４２ｂを形成するための溝部を形成しやすく、軽量で薄くすることができ、可撓性にも優れることから樹脂材料が好ましく、例えば、電離放射線硬化性樹脂、熱硬化性樹脂、熱可塑性樹脂等の樹脂材料が挙げられる。 The constituent material of the translucent region 142a in the contrast enhancement layer 14 ′ is preferably a resin material because it is easy to form a groove for forming the dark color portion 142b, can be light and thin, and is excellent in flexibility. Examples thereof include resin materials such as ionizing radiation curable resins, thermosetting resins, and thermoplastic resins.
　電離放射線硬化性樹脂は、電磁波または荷電粒子線、例えば紫外線または電子線等の照射により、架橋または重合反応にて硬化する。このような電離放射線硬化性樹脂としては、例えば電離放射線重合性プレポリマーおよび／または電離放射線重合性モノマーが挙げられる。 The ionizing radiation curable resin is cured by crosslinking or polymerization reaction by irradiation with electromagnetic waves or charged particle beams such as ultraviolet rays or electron beams. Examples of such ionizing radiation curable resins include ionizing radiation polymerizable prepolymers and / or ionizing radiation polymerizable monomers.
　電離放射線重合性プレポリマー（オリゴマーも包含する）としては、例えば、ポリエステル（メタ）アクリレート系、エポキシ（メタ）アクリレート系、ウレタン（メタ）アクリレート系、ポリオール（メタ）アクリレート系、シリコン（メタ）アクリレート、不飽和ポリエステル系等の分子中にラジカル重合性官能基を有する重合性プレポリマー；あるいはノボラック系型エポキシ樹脂プレポリマー、芳香族ビニルエーテル系樹脂プレポリマー等のエポキシ系樹脂等の分子中にカチオン重合性官能基を有する重合性プレポリマー等が挙げられる。これらの電離放射線重合性プレポリマーは、１種単独で、または２種以上を組み合わせて用いてもよい。 Examples of ionizing radiation polymerizable prepolymers (including oligomers) include polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyol (meth) acrylate, and silicon (meth) acrylate. Polymerizable prepolymer having a radical polymerizable functional group in a molecule such as an unsaturated polyester; or cationic polymerization in a molecule such as an epoxy resin such as a novolak epoxy resin prepolymer or an aromatic vinyl ether resin prepolymer And polymerizable prepolymers having a functional functional group. These ionizing radiation polymerizable prepolymers may be used alone or in combination of two or more.
　電離放射線重合性モノマー（単量体）としては、分子中にラジカル重合性官能基を有する重合性モノマーである多官能性（メタ）アクリレートが好ましく、具体的にはエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。 As the ionizing radiation polymerizable monomer (monomer), a polyfunctional (meth) acrylate which is a polymerizable monomer having a radical polymerizable functional group in the molecule is preferable, specifically, ethylene glycol di (meth) acrylate, Examples include propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.
　また、電離放射線重合性モノマーの他の例として、分子中にカチオン重合性官能基を有する重合性モノマーが挙げられる。例えば、３，４－エポキシシクロへキセニルメチル－３'，４'－エポキシシクロへキセンカルボキシレート等の脂環式エポキシド類、ビスフェノールＡジグリシジルエーテル等グリシジルエーテル類、４－ヒドロキシブチルビニルエーテル等ビニルエーテル類、３－エチル－３－ヒドロキシメチルオキセタン等オキセタン類等が挙げられる。 Also, other examples of the ionizing radiation polymerizable monomer include polymerizable monomers having a cationic polymerizable functional group in the molecule. For example, alicyclic epoxides such as 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, glycidyl ethers such as bisphenol A diglycidyl ether, vinyl ethers such as 4-hydroxybutyl vinyl ether, And oxetanes such as 3-ethyl-3-hydroxymethyloxetane.
　電離放射線硬化性樹脂として紫外線硬化性樹脂を用いる場合、光重合開始剤を電離放射線硬化性樹脂１００質量部に対して、０．１～５質量部程度添加することが好ましい。光重合開始剤としては、従来慣用されているものから適宜選択できる。 When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is preferable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the ionizing radiation curable resin. The photopolymerization initiator can be appropriately selected from those conventionally used.
　分子中にラジカル重合性官能基を有する重合性モノマーや重合性プレポリマーには、例えば、ベンゾイン、ベンゾインメチルエーテル、アセトフェノン、ジメチルアミノアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－ヒドロキシシクロへキシルフェニルケトン、ベンゾフェノン、ｐ－フェニルベンゾフェノン、２－メチルアントラキノン、２－エチルアントラキノン、２－メチルチオキサントン、２－エチルチオキサントン、ベンジルジメチルケタール、アセトフェノンジメチルケタール等が用いられる。また、分子中にカチオン重合性官能基を有する重合性モノマーや重合性プレポリマーには、例えば、芳香族スルホニウム塩、芳香族ジアゾニウム塩、芳香族ヨードニウム塩、メタロセン化合物、ベンゾインスルホン酸エステル等が用いられる。また、光増感剤として、ｐ－ジメチル安息香酸エステル、第三級アミン類、チオール系増感剤等が用いられる。 Examples of the polymerizable monomer or polymerizable prepolymer having a radical polymerizable functional group in the molecule include benzoin, benzoin methyl ether, acetophenone, dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 1-hydroxycyclohexyl phenyl ketone, benzophenone, p-phenylbenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal and the like are used. In addition, for example, aromatic sulfonium salts, aromatic diazonium salts, aromatic iodonium salts, metallocene compounds, and benzoin sulfonic acid esters are used as polymerizable monomers and polymerizable prepolymers having a cationic polymerizable functional group in the molecule. It is done. As the photosensitizer, p-dimethylbenzoate, tertiary amines, thiol sensitizers and the like are used.
　熱硬化性樹脂としては、フェノール樹脂、フェノール－ホルマリン樹脂、尿素樹脂、尿素－ホルマリン樹脂、メラミン樹脂、ポリエステル－メラミン樹脂、メラミン－ホルマリン樹脂、アルキッド樹脂、エポキシ樹脂、エポキシ－メラミン樹脂、不飽和ポリエステル樹脂、ポリイミド樹脂、アクリル樹脂、ポリシロキサン樹脂、ポリウレタン樹脂、汎用の２液硬化型アクリル樹脂（アクリルポリオール硬化物）等が挙げられる。 Thermosetting resins include phenolic resin, phenol-formalin resin, urea resin, urea-formalin resin, melamine resin, polyester-melamine resin, melamine-formalin resin, alkyd resin, epoxy resin, epoxy-melamine resin, unsaturated polyester Examples thereof include resins, polyimide resins, acrylic resins, polysiloxane resins, polyurethane resins, and general-purpose two-component curable acrylic resins (acrylic polyol cured products).
　熱可塑性樹脂としては、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）、エチレングリコール－テレフタル酸－イソフタル酸共重合体、テレフタル酸－エチレングリコール－１，４シクロヘキサンジメタノール共重合体、ポリエステル系熱可塑性エラストマー等のポリエステル樹脂；ポリエチレン、ポリプロピレン、環状ポリオレフィン、ポリメチルペンテン等のポリオレフィン樹脂；ポリ塩化ビニル、ポリ塩化ビニリデン等の含ハロゲン樹脂；ポリスチレン、アクリロニトリル－スチレン共重合体等のスチレン系樹脂；トリアセチルセルロース、ジアセチルセルロース、アセテートブチレートセルロース等のセルロース樹脂；熱可塑性ポリウレタン系樹脂；ポリカーボネート樹脂；ポリアミド樹脂等が挙げられる。 Thermoplastic resins include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), ethylene glycol-terephthalic acid-isophthalic acid copolymer, terephthalic acid-ethylene glycol-1,4 cyclohexanedimethanol copolymer, polyester heat Polyester resins such as plastic elastomers; Polyolefin resins such as polyethylene, polypropylene, cyclic polyolefin, and polymethylpentene; Halogen-containing resins such as polyvinyl chloride and polyvinylidene chloride; Styrene resins such as polystyrene and acrylonitrile-styrene copolymers; Cellulose resins such as acetyl cellulose, diacetyl cellulose, acetate butyrate cellulose; thermoplastic polyurethane resins; polycarbonate resins; polyamide resins It is.
　コントラスト向上層１４’における暗色部１４２ｂとしては、バインダー樹脂中に暗色粒子を分散させたものが好ましく、入射する可視光線（外光）を高い割合で吸収するものが好ましい。このようなものによれば、反射する外光が目立たず、その反射光が画像光に混入しても画像コントラストの低下が抑制される。 The dark color portion 142b in the contrast improving layer 14 'is preferably a material in which dark particles are dispersed in a binder resin, and preferably a material that absorbs incident visible light (external light) at a high rate. According to such a configuration, even if the reflected external light is not conspicuous and the reflected light is mixed into the image light, a decrease in image contrast is suppressed.
　暗色粒子としては、各色の粒子を用いることができ、例えば、黒色粒子として、カーボンブラック（墨）、黒色酸化鉄等の黒色顔料や、アクリル等の透明粒子をカーボンブラック等の黒色顔料で染色した樹脂粒子等が挙げられる。暗色粒子は、青色、紫色、黄色、赤色等の各種顔料を混合して無彩色化した顔料粒子でもよく、それらの顔料で染色した樹脂粒子でもよい。青色顔料として、銅フタロシアニンブルー、インダスレンブルー、コバルトブルー、群青等、紫色顔料として、ジオキサジンバイオレット等、黄色顔料として、ジスアゾイエロー、イソインドリノンイエロー、黄鉛等、赤色顔料として、クロモフタルレッドタイペル、キナクリドンレッド、弁柄等、緑色顔料として、銅フタロシアニングリーン、緑青等が挙げられる。暗色粒子の含有量は、バインダー樹脂１００質量部に対して、１０～１００質量部が好ましい。バインダー樹脂としては、透光性領域１４２ａの樹脂材料と同様のものが挙げられ、例えば、電離放射線硬化性樹脂、熱硬化性樹脂、熱可塑性樹脂等の樹脂材料が挙げられる。 As the dark particles, particles of each color can be used. For example, as black particles, black pigments such as carbon black (black) and black iron oxide, and transparent particles such as acrylic are dyed with a black pigment such as carbon black. Examples thereof include resin particles. The dark particles may be pigment particles that are achromatic by mixing various pigments such as blue, purple, yellow, and red, or may be resin particles that are dyed with these pigments. Copper pigments such as copper phthalocyanine blue, indanthrene blue, cobalt blue, ultramarine blue, purple pigments such as dioxazine violet, yellow pigments such as disazo yellow, isoindolinone yellow, and yellow lead, red pigments such as chromophthal red Examples of green pigments such as tiepel, quinacridone red, and petals include copper phthalocyanine green and patina. The content of dark particles is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the binder resin. Examples of the binder resin include the same resin materials as those of the translucent region 142a, and examples thereof include resin materials such as an ionizing radiation curable resin, a thermosetting resin, and a thermoplastic resin.
　コントラスト向上層１４’は、例えば以下のように製造できる。まず、基材１４１の上に透光性領域形成用組成物を塗布し、その表面に暗色部１４２ｂを形成するための溝部等を形成して透光性領域１４２ａを形成する。例えば、紫外線硬化性樹脂からなる透光性領域１４２ａの場合、紫外線硬化性樹脂と光重合開始剤とを有機溶剤に溶解させて透光性領域形成用組成物を調製した後、これを基材１４１の表面に塗布し、その表面にロール状の金型（賦形型ロール）を押し当てて暗色部１４２ｂを形成するための溝部を形成しつつ、紫外線を照射することにより硬化させて形成する。 The contrast improving layer 14 ′ can be manufactured as follows, for example. First, a translucent region forming composition is applied on the substrate 141, and a groove portion or the like for forming the dark color portion 142b is formed on the surface thereof to form the translucent region 142a. For example, in the case of the translucent region 142a made of an ultraviolet curable resin, a composition for forming a translucent region is prepared by dissolving an ultraviolet curable resin and a photopolymerization initiator in an organic solvent, and then using this as a base material. It is applied to the surface of 141, and a roll-shaped mold (shaped forming roll) is pressed against the surface to form a groove for forming the dark portion 142b, and cured by irradiation with ultraviolet rays. .
　暗色部１４２ｂは、暗色粒子とバインダー樹脂とを有機溶剤に溶解させて暗色部形成用組成物を調製した後、これを透光性領域１４２ａ間の溝部に塗布し、硬化させることにより形成できる。例えば、バインダー樹脂として紫外線硬化性樹脂を用いる場合、暗色粒子、紫外線硬化性樹脂、および光重合開始剤を有機溶剤に溶解させて暗色部形成用組成物を調製し、これを透光性領域１４２ａ間の溝部に塗布した後、紫外線を照射することにより硬化させて形成する。 The dark color part 142b can be formed by dissolving the dark color particles and the binder resin in an organic solvent to prepare a dark color part forming composition, and then applying this to the groove part between the translucent regions 142a and curing. For example, when an ultraviolet curable resin is used as the binder resin, a dark color portion forming composition is prepared by dissolving dark particles, an ultraviolet curable resin, and a photopolymerization initiator in an organic solvent, and this is used as a light transmissive region 142a. After being applied to the grooves in between, it is cured by irradiating with ultraviolet rays.
　透光性領域１４２ａの厚さは、例えば暗色部１４２ｂを形成する観点等から、２０～２００μｍが好ましく、３０～１５０μｍがより好ましく、暗色部１４２ｂの厚さ（深さ）は、１０～１８０μｍが好ましく、２０～１３０μｍがより好ましく、幅は５～１００μｍが好ましく、５～５０μｍがより好ましく、ピッチは１０～２００μｍが好ましく、２０～１５０μｍがより好ましい。 The thickness of the translucent region 142a is preferably 20 to 200 μm, more preferably 30 to 150 μm, for example, from the viewpoint of forming the dark color portion 142b, and the thickness (depth) of the dark color portion 142b is 10 to 180 μm. The width is preferably 20 to 130 μm, the width is preferably 5 to 100 μm, more preferably 5 to 50 μm, and the pitch is preferably 10 to 200 μm, more preferably 20 to 150 μm.
　電磁波遮蔽層は、例えば、基材上に電磁波遮蔽膜としての金属メッシュ膜を有するものである。このような電磁波遮蔽層は、通常、基材上に銅箔を貼りあわせた後、この銅箔をメッシュ状に加工することにより、または銅や銀などの導電性インクを基材上にメッシュ状に印刷することにより製造される。なお、基材は、単体の基材と同様な樹脂フィルムまたは薄板状のガラス板等を用いることができる。 The electromagnetic wave shielding layer has, for example, a metal mesh film as an electromagnetic wave shielding film on a base material. Such an electromagnetic wave shielding layer is usually formed by bonding a copper foil on a base material and then processing the copper foil into a mesh shape, or a conductive ink such as copper or silver on the base material. It is manufactured by printing on. As the base material, a resin film similar to a single base material, a thin glass plate, or the like can be used.
　電磁波遮蔽層は、基材上に、スパッタ法により電磁波遮蔽膜を形成したものでもよい。電磁波遮蔽膜は、例えば、金属酸化物膜と金属膜とを交互に積層したものであって、金属膜の層数がｎであり、金属酸化物膜の層数がｎ＋１（ただし、ｎは１以上の整数）である。金属酸化物膜は、例えば、インジウムとスズとの酸化物、チタンと亜鉛との酸化物、アルミニウムと亜鉛との酸化物、ニオブの酸化物等からなるものが挙げられる。また、金属膜は、銀、銀合金等からなるものが挙げられる。 The electromagnetic wave shielding layer may be formed by forming an electromagnetic wave shielding film on a base material by a sputtering method. The electromagnetic wave shielding film is formed by alternately laminating metal oxide films and metal films, for example, where the number of metal films is n and the number of metal oxide films is n + 1 (where n is 1). It is an integer above. Examples of the metal oxide film include an oxide of indium and tin, an oxide of titanium and zinc, an oxide of aluminum and zinc, an oxide of niobium, and the like. Moreover, what consists of silver, a silver alloy, etc. is mentioned as a metal film.
　反射防止層は、可視光線（外光）の反射を抑制するために設けられる。反射防止層を設けることで、映りこみを抑制でき、また表示画像のコントラストを向上できる。反射防止層は、例えば、基材上に反射防止膜を有するものである。基材は、単体の基材と同様な樹脂フィルムまたは薄板状のガラス板等を用いることができる。反射防止膜は、例えば、屈折率の低い無機化合物と屈折率の高い無機化合物とを交互に積層した積層膜、屈折率の低い無機化合物からなる膜、屈折率の低い樹脂からなる膜等が挙げられる。屈折率の低い無機化合物としては、例えば、二酸化珪素等が挙げられる。屈折率の低い樹脂としては、例えば、フッ素樹脂、シリコーン樹脂、フルオロシリコーン樹脂等が挙げられる。 The antireflection layer is provided to suppress reflection of visible light (external light). By providing the antireflection layer, reflection can be suppressed and the contrast of the display image can be improved. The antireflection layer has, for example, an antireflection film on a substrate. As the substrate, a resin film similar to a single substrate or a thin glass plate can be used. Examples of the antireflection film include a laminated film in which an inorganic compound having a low refractive index and an inorganic compound having a high refractive index are alternately laminated, a film made of an inorganic compound having a low refractive index, and a film made of a resin having a low refractive index. It is done. Examples of the inorganic compound having a low refractive index include silicon dioxide. Examples of the resin having a low refractive index include a fluororesin, a silicone resin, and a fluorosilicone resin.
　防眩層は、例えば、表面に凹凸部からなる防眩部を有するものである。防眩部は、表面の凹凸部によって、この表面に映る反射像を拡散させて輪郭をぼかす効果等を有する。防眩層としては、基材の表面に、シリカ等の無機微粒子、またはアクリル系樹脂等の有機微粒子をバインダ中に分散した溶液をコーティングし、溶媒を揮発させて凹凸部からなる防眩部としたものや、サンドブラスト、またはエッチング等により基材自身に凹凸部からなる防眩部を形成したものが挙げられる。なお、基材は、単体の基材と同様な樹脂フィルムまたは薄板状のガラス板等を用いることができる。 The anti-glare layer has, for example, an anti-glare portion composed of uneven portions on the surface. The anti-glare portion has an effect of blurring the outline by diffusing a reflected image reflected on the surface by the uneven portion on the surface. As the antiglare layer, the surface of the base material is coated with a solution in which inorganic fine particles such as silica or organic fine particles such as acrylic resin are dispersed in a binder, and the solvent is volatilized to form an antiglare portion composed of uneven portions. And those obtained by forming a glare-proof portion comprising uneven portions on the substrate itself by sandblasting, etching, or the like. As the base material, a resin film similar to a single base material, a thin glass plate, or the like can be used.
　着色層としては、基材上に着色色素を含有する樹脂膜である着色膜を有するものが挙げられる。基材は、単体の基材と同様な樹脂フィルムまたは薄板状のガラス板等を用いることができる。着色色素は、色調補正色素、近赤外線吸収色素が挙げられ、第１の粘着剤層１３や第２の粘着剤層１５に用いられるようなものを使用できる。 Examples of the colored layer include those having a colored film which is a resin film containing a colored pigment on a substrate. As the substrate, a resin film similar to a single substrate or a thin glass plate can be used. Examples of the coloring dye include a color tone correction dye and a near-infrared absorbing dye, and those used for the first pressure-sensitive adhesive layer 13 and the second pressure-sensitive adhesive layer 15 can be used.
　紫外線吸収層としては、基材上に紫外線吸収剤を含有する樹脂膜である紫外線吸収膜を有するものが挙げられる。基材は、単体の基材と同様な樹脂フィルムまたは薄板状のガラス板等を用いることができる。また、紫外線吸収剤は、第１の粘着剤層１３や第２の粘着剤層１５に用いられるようなものを使用できる。 Examples of the ultraviolet absorbing layer include those having an ultraviolet absorbing film which is a resin film containing an ultraviolet absorbent on a substrate. As the substrate, a resin film similar to a single substrate or a thin glass plate can be used. Moreover, what is used for the 1st adhesive layer 13 or the 2nd adhesive layer 15 can be used for an ultraviolet absorber.
　以下、表示装置１０の具体例について説明する。 Hereinafter, a specific example of the display device 10 will be described.
　表示装置１０としては、例えば、被着材１１が表示パネル単体を有し、積層体１２が、被着材１１側から順に、アクリル系粘着剤からなる粘着剤層（第１の粘着剤層１３）、基材上にコントラスト向上膜が設けられたコントラスト向上層（第１の基材層１４）、アクリル系粘着剤からなる粘着剤層（第２の粘着剤層１５）、および基材上に反射防止膜が設けられた反射防止層（第２の基材層１６）を有するものが挙げられる。反射防止層の基材は、コントラスト向上層の損傷を抑制する観点から、ポリエチレンテレフタレートフィルムが好ましい。また、このような反射防止層の基材となるポリエチレンテレフタレートフィルムの厚みは、３８μｍ以上が好ましく、７５μｍ以上がより好ましい。 As the display device 10, for example, the adherend 11 has a single display panel, and the laminate 12 is an adhesive layer (first adhesive layer 13) made of an acrylic adhesive in order from the adherend 11 side. ), A contrast improving layer (first base layer 14) provided with a contrast improving film on the base, an adhesive layer made of an acrylic adhesive (second adhesive layer 15), and the base Examples thereof include those having an antireflection layer (second base material layer 16) provided with an antireflection film. The base material of the antireflection layer is preferably a polyethylene terephthalate film from the viewpoint of suppressing damage to the contrast improving layer. In addition, the thickness of the polyethylene terephthalate film serving as the base material for such an antireflection layer is preferably 38 μm or more, and more preferably 75 μm or more.
　このように、コントラスト向上層を有する場合、被着材１１から積層体１２を剥離する際、コントラスト向上層が損傷して被着材１１に残留しやすい。コントラスト向上層に加えて補強層ともなるべき反射防止層を設けるとともに、密着力Ａに比べて密着力Ｂ、Ｃ、およびＤをいずれも５［Ｎ／２５ｍｍ］以上大きくすることで、粘着剤層（第１の粘着剤層１３）の残留は勿論のこと、損傷によるコントラスト向上層の残留も抑制できる。特に、反射防止層の基材として、ポリエチレンテレフタレートフィルムを用いることで、損傷によるコントラスト向上層の残留を効果的に抑制できる。 Thus, when having the contrast improving layer, when the laminate 12 is peeled from the adherend 11, the contrast improving layer is easily damaged and remains on the adherend 11. In addition to the contrast improving layer, an antireflection layer that should also be a reinforcing layer is provided, and the adhesive force B, C, and D are all increased by 5 [N / 25 mm] or more compared to the adhesive force A, whereby an adhesive layer In addition to the remaining (first pressure-sensitive adhesive layer 13), the remaining contrast enhancing layer due to damage can also be suppressed. In particular, by using a polyethylene terephthalate film as the base material of the antireflection layer, it is possible to effectively suppress the remaining of the contrast improving layer due to damage.
　他の表示装置１０としては、上記表示装置１０のコントラスト向上層（第１の基材層）をトリアセチルセルロースフィルムとしたものが挙げられる。トリアセチルセルロースフィルムについても、コントラスト向上層と同様に損傷しやすいことから、同様の顕著な効果を得ることができる。 Other display devices 10 include those in which the contrast enhancement layer (first base material layer) of the display device 10 is a triacetyl cellulose film. Since the triacetyl cellulose film is also easily damaged like the contrast improving layer, the same remarkable effect can be obtained.
　さらに他の表示装置１０としては、例えば、被着材１１が、表示パネルに、順に、粘着層、電磁波遮蔽層、粘着層、コントラスト向上層が積層されたものであり、積層体１２が、被着材１１側から順に、アクリル系粘着剤からなる粘着剤層（第１の粘着剤層１３）、薄板状のガラス板（第１の基材層１４）、アクリル系粘着剤からなる粘着剤層（第２の粘着剤層１５）、および基材上に反射防止膜が設けられた反射防止層（第２の基材層１６）を有するものが挙げられる。反射防止層の基材は、薄板状のガラス板の損傷を抑制する観点から、ポリエチレンテレフタレートフィルムが好ましい。また、このような反射防止層の基材となるポリエチレンテレフタレートフィルムの厚みは、３８μｍ以上が好ましく、７５μｍ以上がより好ましい。 As another display device 10, for example, an adherend 11 is obtained by sequentially laminating an adhesive layer, an electromagnetic wave shielding layer, an adhesive layer, and a contrast improving layer on a display panel. In order from the dressing 11 side, an adhesive layer (first adhesive layer 13) made of an acrylic adhesive, a thin glass plate (first base material layer 14), and an adhesive layer made of an acrylic adhesive. Examples thereof include (second pressure-sensitive adhesive layer 15) and an antireflection layer (second base material layer 16) in which an antireflection film is provided on the base material. The base material of the antireflection layer is preferably a polyethylene terephthalate film from the viewpoint of suppressing damage to the thin glass plate. In addition, the thickness of the polyethylene terephthalate film serving as the base material for such an antireflection layer is preferably 38 μm or more, and more preferably 75 μm or more.
　このように、被着材１１は、必ずしも単体の表示パネルに限られず、その前面には表示パネルの種類に応じて、電磁波遮蔽層、コントラスト向上層等の機能層が積層されてもよい。また、積層体１２が薄板状のガラス板を有する場合、被着材１１から積層体１２を剥離する際、薄板状のガラス板が損傷して被着材１１に残留しやすい。薄板状のガラス板に加えて補強層ともなるべき反射防止層を設けるとともに、密着力Ａに比べて密着力Ｂ、Ｃ、およびＤをいずれも５［Ｎ／２５ｍｍ］以上大きくすることで、粘着剤層（第１の粘着剤層１３）の残留は勿論のこと、損傷による薄板状のガラス板の残留も抑制できる。特に、反射防止層の基材として、ポリエチレンテレフタレートフィルムを用いることで、損傷による薄板状のガラス板の残留を効果的に抑制できる。 Thus, the adherend 11 is not necessarily limited to a single display panel, and functional layers such as an electromagnetic wave shielding layer and a contrast enhancement layer may be laminated on the front surface according to the type of the display panel. Further, when the laminate 12 has a thin glass plate, when the laminate 12 is peeled from the adherend 11, the thin glass plate is easily damaged and remains on the adherend 11. In addition to a thin glass plate, an anti-reflection layer that should serve as a reinforcing layer is provided, and the adhesive force B, C, and D are all increased by 5 [N / 25 mm] or more compared to the adhesive force A. Not only the agent layer (first pressure-sensitive adhesive layer 13) remains, but also a thin glass plate due to damage can be suppressed. In particular, by using a polyethylene terephthalate film as the base material of the antireflection layer, it is possible to effectively suppress the remaining of a thin glass plate due to damage.
　なお、積層体１２は必ずしも粘着剤層および基材層をそれぞれ２層ずつ有するものに限られず、粘着剤層および基材層はそれぞれ３層以上でもよい。この場合、被着材１１側から粘着剤層のみで数えて３層目以降となる粘着剤層は、その両面に隣接する基材層との密着力がいずれも密着力Ａに比べて５［Ｎ／２５ｍｍ］以上大きいことが好ましい。このようなものとすることで、所望の剥離部、すなわち被着材１１と１層目の粘着剤層（第１の粘着剤層１３）との間で剥離させることができ、その他の部分での剥離を抑制できる。これにより、１層目の基材層（第１の基材層１４）等の損傷を抑制して被着材１１への残留を抑制できる。なお、被着材１１側から基材層のみで数えて３層目以降となる基材層については、１層目の基材層（第１の基材層１４）、２層目の基材層（第２の基材層１６）のように、基材単体の他、基材の表面に機能膜を有する機能層とできる。 The laminate 12 is not necessarily limited to one having two pressure-sensitive adhesive layers and two base material layers, and the pressure-sensitive adhesive layer and the base material layer may each be three or more layers. In this case, the adhesive layer which is the third and subsequent layers counted only from the adhesive layer 11 side from the adherend 11 side has an adhesive force of 5 [ N / 25 mm] or more is preferable. By setting it as such, it can be made to peel between a desired peeling part, ie, the adherend 11 and the 1st adhesive layer (1st adhesive layer 13), and other parts. Can be prevented. Thereby, damage to the adherend 11 can be suppressed by suppressing damage to the first base layer (first base layer 14) and the like. In addition, about the base material layer which becomes only the base material layer from the adherend 11 side and becomes the third and subsequent layers, the first base material layer (first base material layer 14) and the second base material layer Like a layer (2nd base material layer 16), it can be set as the functional layer which has a functional film on the surface of a base material other than a base material single-piece | unit.
　以上、本発明の積層体について、表示装置に適用される表示装置用の光学フィルタを例に挙げて説明したが、本発明の積層体は、必ずしも表示装置用の光学フィルタに限られない。本発明の積層体は、建築物や自動車等の窓ガラスに貼り合わせて使用する低放射率の積層体等であってもよい。この場合、第１の基材層、第２の基材層としては、例えば、基材単体、または基材上にＬｏｗ－Ｅ（Ｌｏｗ-Ｅｍｉｓｓｉｖｉｔｙ）膜とも呼ばれる熱線遮断膜が形成されたものなどが挙げられる。 As mentioned above, although the laminated body of the present invention has been described by taking the optical filter for display device applied to the display device as an example, the laminated body of the present invention is not necessarily limited to the optical filter for display device. The laminated body of the present invention may be a low-emissivity laminated body used by being attached to a window glass of a building or an automobile. In this case, as the first base material layer and the second base material layer, for example, a base material alone or a heat ray blocking film called a Low-E (Low-Emissivity) film formed on the base material is used. Is mentioned.
　以上、本発明について幾つかの実施形態を説明したが、これらの実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これらの実施形態は、その他の様々な形態で実施でき、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これら実施形態やその変形は、発明の範囲や要旨に含まれるとともに、特許請求の範囲に記載された発明とその均等の範囲に含まれる。 As mentioned above, although several embodiment was described about this invention, these embodiment is shown as an example and is not intending limiting the range of invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.
　以下、本発明について実施例を参照して具体的に説明する。
　なお、以下の例１～３、７が本発明の実施例、例４～６が本発明の比較例である。 Hereinafter, the present invention will be specifically described with reference to examples.
The following Examples 1 to 3 and 7 are examples of the present invention, and Examples 4 to 6 are comparative examples of the present invention.
＜例１＞
　例１の積層体として、表１に示すような構成を有するものを製造した。
　まず、第２の粘着層を以下のようにして製造した。メチルエチルケトン６質量部に紫外線吸収剤（Ｃｉｂａ社製、商品名「ＴＩＮＵＶＩＮ　４７９」）１．１３質量部、ポルフィリン化合物（山田化学社製、ＴＡＰ１８）０．０１５０質量部を添加し、ミキサーで１０分撹拌して溶解させた。この溶液にアクリル系粘着剤（東洋インキ社製、商品名「ＮＣＫ１０１粘着」）３０質量部および架橋剤（日本ポリウレタン社製、商品名「コロネートＨＬ」）０．２４質量部を添加し、さらにミキサーで１０分撹拌して溶解させた。ＰＥＴフィルム上にシリコーン層が形成されたセパレーター上に、この溶液をアプリケーターを用いて塗布し、１００℃のオーブンで５分乾燥させて、厚み２５μｍの第２の粘着層を形成した。 <Example 1>
A laminate having the structure shown in Table 1 was produced as the laminate of Example 1.
First, the 2nd adhesion layer was manufactured as follows. To 6 parts by mass of methyl ethyl ketone, 1.13 parts by mass of an ultraviolet absorber (trade name “TINUVIN 479” manufactured by Ciba) and 0.0150 part by mass of a porphyrin compound (manufactured by Yamada Chemical Co., TAP 18) are added and stirred for 10 minutes with a mixer. And dissolved. To this solution was added 30 parts by mass of an acrylic adhesive (trade name “NCK101 adhesive” manufactured by Toyo Ink Co., Ltd.) and 0.24 parts by mass of a crosslinking agent (trade name “Coronate HL” manufactured by Nippon Polyurethane Co., Ltd.), and a mixer. And stirred for 10 minutes to dissolve. This solution was applied onto a separator having a silicone layer formed on a PET film using an applicator and dried in an oven at 100 ° C. for 5 minutes to form a second adhesive layer having a thickness of 25 μm.
　次に、上記第２の粘着層を第２の基材層となる反射防止（ＡＲ）フィルム（日油社製、商品名「ＲＬ９９００」、基材：ＰＥＴフィルム、基材厚み１００μｍ）に貼り合わせて、第２の粘着層と第２の基材層とが積層された粘着層付き反射防止フィルムを得た。この粘着層付き反射防止フィルムの第２の粘着層からセパレーターを剥がして、第１の基材層となるコントラスト向上フィルム（ＣＲＦ）のＰＥＴフィルム面に貼り合わせた。さらに、第１の基材層となるコントラスト向上フィルムのＰＥＴフィルム面とは反対側に、第１の粘着層となるアクリル系粘着剤（東洋インキ社製、商品名「ＮＣＫ１０１粘着」）を厚み２５μｍに塗布して積層体としての光学フィルタを作製した。 Next, the second adhesive layer is bonded to an antireflection (AR) film (trade name “RL9900”, manufactured by NOF Corporation, base material: PET film, base material thickness 100 μm) to be the second base material layer. Thus, an antireflection film with an adhesive layer in which the second adhesive layer and the second base material layer were laminated was obtained. The separator was peeled off from the second adhesive layer of the antireflection film with an adhesive layer, and bonded to the PET film surface of the contrast enhancing film (CRF) to be the first base material layer. Further, an acrylic adhesive (trade name “NCK101 adhesive” manufactured by Toyo Ink Co., Ltd.) serving as the first adhesive layer is formed on the side opposite to the PET film surface of the contrast improving film serving as the first base material layer with a thickness of 25 μm. The optical filter as a laminated body was produced by applying to the above.
　なお、第１の基材層となるコントラスト向上フィルム（ＣＲＦ）は以下のように製造した。基材として、両面易接着処理された厚さ１００μｍのポリエチレンテレフタレートの帯状シート（東洋紡績社製、商品名：Ａ４３００）を準備し、その上に、ウレタンアクリレートプレポリマーからなる紫外線硬化性樹脂を厚さ８９μｍとなるように塗布した。この塗布面に、ピッチが５１μｍで溝状凹部を形成した下底側の最大幅の開口幅が１０μｍ、上底側の最小幅が７μｍで深さが６９μｍの複数の溝状凹部を形成できる金属製賦形型ロールを押し当て、溝状凹部形状を刻設しながら背面から紫外線を照射して紫外線硬化樹脂を硬化させた。こうして、ピッチが５１μｍで溝状凹部を形成した下底側の開口幅が１０μｍで上底側の最小幅が７μｍ、且つ深さが６９μｍの複数の溝状凹部を形成した。 In addition, the contrast improvement film (CRF) used as a 1st base material layer was manufactured as follows. As a base material, a 100 μm-thick polyethylene terephthalate belt-like sheet (product name: A4300, manufactured by Toyobo Co., Ltd.) that has been subjected to easy adhesion on both sides is prepared, and an ultraviolet curable resin made of urethane acrylate prepolymer is thickened thereon The film was applied to a thickness of 89 μm. A metal capable of forming a plurality of groove-like recesses having a maximum bottom opening width of 10 μm, a minimum width of 7 μm on the upper bottom side, and a depth of 69 μm. The shaping mold roll was pressed and the ultraviolet curable resin was cured by irradiating ultraviolet rays from the back side while engraving the groove-like concave shape. In this way, a plurality of groove-shaped recesses having a pitch of 51 μm and groove-shaped recesses having an opening width on the lower base side of 10 μm, a minimum width on the upper base side of 7 μm, and a depth of 69 μm were formed.
　なお、賦形型ロールは、その円周方向にコントラスト向上フィルムの溝状凹部に対応した溝状凸部（コントラスト向上フィルムの凹形状と同形状の逆凸形状）が賦形されているので、帯状シート部材上で該帯の長手方向に溝状凸部の延長方向が揃って回転させることにより、シート部材の長手方向に延びるように溝状凹部を形成することができる。 In addition, since the shaping-type roll has a groove-shaped convex portion corresponding to the groove-shaped concave portion of the contrast improving film in the circumferential direction (a reverse convex shape that is the same shape as the concave shape of the contrast improving film), A groove-like recess can be formed so as to extend in the longitudinal direction of the sheet member by rotating the extension direction of the groove-like convex part in the longitudinal direction of the belt on the belt-like sheet member.
　次に、透明アクリル系の紫外線硬化性プレポリマー１００質量部中に、最小粒径が２μｍで最大粒径が３μｍの黒い球状ビーズ状粒子５０質量部、光重合開始剤として１－ヒドロキシ－シクロへキシル－フェニル－ケトン（チバスペシャリティケミカルズ社製、商品名：イルガキュア１８４）２質量部を混合して液状の紫外線硬化性樹脂組成物を調製した。この液状の樹脂組成物を、上記溝状凹部形成面側に塗工した後、ドクターブレードでワイピングした。ワイピングに際しては、同時に背面から紫外線を照射して液状の樹脂組成物を硬化させた。ワイピングでは、上記溝状凹部形成面とドクターブレードとの隙間を１．５μｍとして行い、そのワイピングを２回繰り返した。 Next, in 100 parts by mass of a transparent acrylic UV curable prepolymer, 50 parts by mass of black spherical bead-shaped particles having a minimum particle size of 2 μm and a maximum particle size of 3 μm, and 1-hydroxy-cyclohexane as a photopolymerization initiator. A liquid ultraviolet curable resin composition was prepared by mixing 2 parts by mass of xyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals). This liquid resin composition was applied to the groove-shaped recess forming surface side and then wiped with a doctor blade. In wiping, the liquid resin composition was cured by irradiating ultraviolet rays from the back at the same time. In wiping, the gap between the groove-shaped recess forming surface and the doctor blade was set to 1.5 μm, and the wiping was repeated twice.
　その結果、溝状凹部には、透明樹脂である紫外線硬化性樹脂と暗色粒子である黒い球状ビーズとが充填された断面が台形状の暗色部を形成でき、これら暗色部間の平坦部上には透明樹脂である紫外線硬化性樹脂のみを厚さ１．５μｍで残留させることができ、同時に行った紫外線照射によりその透明樹脂である紫外線硬化性樹脂を硬化させて厚さ１μｍの透明保護層を形成できた。こうして、コントラスト向上フィルム（マイクロルーバ層）を得た。なお、上記において、［透明樹脂の屈折率］－［球状ビーズの屈折率］＝－０．００３であった。また、該溝状の暗色部の表面（下底側）には透明保護層表面からの深さが３μｍの凹陥部が形成されていた。
　なお、以上のように製造した第１の基材層となるコントラスト向上フィルム（ＣＲＦ）全体の厚みは１９０．５μｍであった。 As a result, the groove-shaped recess can form a dark part with a trapezoidal cross section filled with an ultraviolet curable resin, which is a transparent resin, and black spherical beads, which are dark particles, on the flat part between these dark parts. Can leave only the UV curable resin, which is a transparent resin, at a thickness of 1.5 μm, and at the same time, the UV curable resin, which is a transparent resin, is cured by UV irradiation, thereby forming a transparent protective layer having a thickness of 1 μm. I was able to form. In this way, a contrast enhancement film (microlouver layer) was obtained. In the above, [refractive index of transparent resin] − [refractive index of spherical beads] = − 0.003. Further, a concave portion having a depth of 3 μm from the surface of the transparent protective layer was formed on the surface (lower bottom side) of the groove-like dark color portion.
In addition, the thickness of the whole contrast improvement film (CRF) used as the 1st base material layer manufactured as mentioned above was 190.5 micrometers.
＜例２＞
　第１の基材層であるコントラスト向上フィルムをトリアセチルセルロースフィルム（富士フィルム社製、商品名：ＴＡＣフィルム、厚み８０μｍ）に変更し、第１の粘着層であるアクリル系粘着剤（東洋インキ社製、商品名：ＮＣＫ１０１粘着）をアクリル系粘着剤（リンテック社製、商品名：ＳＹ粘着に変更した以外は例１と同様にして積層体としての光学フィルタを作製した。 <Example 2>
The contrast-enhancement film, which is the first base material layer, is changed to a triacetyl cellulose film (manufactured by Fuji Film Co., Ltd., trade name: TAC film, thickness 80 μm), and the acrylic adhesive (Toyo Ink Co., Ltd.) which is the first adhesive layer An optical filter as a laminate was prepared in the same manner as in Example 1 except that the product was manufactured and trade name: NCK101 adhesive was changed to an acrylic adhesive (manufactured by Lintec Corporation, trade name: SY adhesive).
＜例３＞
　第１の粘着層であるアクリル系粘着剤（東洋インキ社製、商品名：ＮＣＫ１０１粘着）をアクリル系粘着剤（リンテック社製、商品名：ＳＹ粘着）に変更し、第２の粘着層をアクリル系粘着剤（リンテック社製、商品名：Ｐ０２８０粘着）に変更した以外は例１と同様にして積層体としての光学フィルタを作製した。 <Example 3>
The acrylic adhesive (trade name: NCK101 adhesive manufactured by Toyo Ink Co., Ltd.), which is the first adhesive layer, was changed to an acrylic adhesive (trade name: SY adhesive manufactured by Lintec Corporation), and the second adhesive layer was acrylic. An optical filter as a laminate was produced in the same manner as in Example 1 except that the adhesive was changed to a system adhesive (trade name: P0280 adhesive, manufactured by Lintec Corporation).
＜例４＞
　第１の粘着層であるアクリル系粘着剤（東洋インキ社製、商品名：ＮＣＫ１０１粘着）をアクリル系粘着剤（リンテック社製、商品名：Ｐ０２８０粘着）に変更した以外は例１と同様にして積層体としての光学フィルタを作製した。 <Example 4>
Except that the acrylic adhesive (trade name: NCK101 adhesive manufactured by Toyo Ink Co., Ltd.), which is the first adhesive layer, was changed to an acrylic adhesive (trade name: P0280 adhesive manufactured by Lintec Co., Ltd.), the same as in Example 1 An optical filter as a laminate was produced.
＜例５＞
　第１の基材層であるコントラスト向上フィルム上に、第２の粘着層および第２の基材層となる粘着層付き反射防止フィルムを貼り合わせなかった以外は例１と同様にして積層体としての光学フィルタを作製した。 <Example 5>
A laminate as in Example 1 except that the second adhesive layer and the antireflection film with an adhesive layer to be the second base material layer were not bonded onto the contrast-enhancing film as the first base material layer. An optical filter was prepared.
＜例６＞
　第１の粘着層となるアクリル系粘着剤（東洋インキ社製、商品名：ＮＣＫ１０１粘着）をアクリル系粘着剤（リンテック社製、商品名：ＳＹ粘着）に変更し、第２の粘着層をノンキャリアシート（ＴＯＭＯＥＧＡＷＡ社製、商品名：ＴＸ４８Ａノンキャリアシート、厚み２５μｍ）に変更した以外は例１と同様にして積層体としての光学フィルタを作製した。
＜例７＞
　第１の基材層であるコントラスト向上フィルムを０．１ｍｍのガラス板に変更し、第２の粘着層をアクリル系粘着剤（リンテック社製、商品名：Ｐ０２８０粘着）に変更し、第２の基材層をＰＥＴフィルム（東洋紡績社製、商品名：Ａ４３００）に変更した以外は例１と同様にして積層体としての光学フィルタを作製した。 <Example 6>
Change the acrylic adhesive (product name: NCK101 adhesive, manufactured by Toyo Ink Co., Ltd.) to be the first adhesive layer to acrylic adhesive (product name: SY adhesive, manufactured by Lintec Corporation), and make the second adhesive layer non- An optical filter as a laminate was produced in the same manner as in Example 1 except that the carrier sheet was changed to a carrier sheet (trade name: TX48A non-carrier sheet, thickness 25 μm, manufactured by TOMO EGAWA).
<Example 7>
The contrast improving film as the first base layer is changed to a 0.1 mm glass plate, the second adhesive layer is changed to an acrylic adhesive (trade name: P0280 adhesive), and the second adhesive layer is changed to the second adhesive layer. An optical filter as a laminate was produced in the same manner as in Example 1 except that the base material layer was changed to a PET film (trade name: A4300, manufactured by Toyobo Co., Ltd.).
　ここで、各基材層または被着材としてのガラス基板と各粘着層との密着力、積層体の剥離時の粘着剤の糊残りおよび破断を下記方法で評価した。密着力は、ＪＩＳ　Ｚ　０２３７の規格に準拠して下記の通りに測定した。 Here, the adhesive strength between each substrate layer or the glass substrate as the adherend and each adhesive layer, adhesive residue and breakage at the time of peeling of the laminate were evaluated by the following methods. The adhesion was measured as follows in accordance with the standard of JIS Z 0237.
（密着力）
　ポリエチレンテレフタレートからなる帯状シート（東洋紡績社製、商品名：Ａ４３００）の片面に表１に示す各粘着層（第１の粘着層または第２の粘着層）を形成して、粘着層を有する帯状シートを製造した。別途、厚さ２．５ｍｍのソーダライムガラス板の片面に表１に示す各基材層（第１の基材層または第２の基材層）を粘着剤（厚み２５μｍ、幅２５ｍｍ）により固定して、基材層を有するソーダライムガラス板を製造した。その後、上記帯状シートの粘着層と上記ソーダライムガラス板の基材層とを貼り合わせて、室温下で２ｋｇのゴムロールにより圧着して圧着体とした。この圧着体に対して、オートクレーブ処理（温度６０℃、圧力０．９５ＭＰａ、時間９０分）を実施して、密着力測定用の試験片を作製した。この試験片について、引張り試験機（島津製作所社製、ＡＧＳ－Ｘ　５００ＮＸ）を用いて、粘着層と基材層との密着強度（１８０度ピール、引張り速度３００ｍｍ／分）を測定した。 (Adhesion)
Each adhesive layer (the first adhesive layer or the second adhesive layer) shown in Table 1 is formed on one side of a belt-like sheet made of polyethylene terephthalate (trade name: A4300, manufactured by Toyobo Co., Ltd.), and has an adhesive layer. A sheet was produced. Separately, each base material layer (first base material layer or second base material layer) shown in Table 1 is fixed to one side of a 2.5 mm thick soda lime glass plate with an adhesive (thickness 25 μm, width 25 mm). And the soda-lime glass plate which has a base material layer was manufactured. Thereafter, the pressure-sensitive adhesive layer of the belt-like sheet and the base material layer of the soda lime glass plate were bonded together and pressure-bonded with a 2 kg rubber roll at room temperature to obtain a pressure-bonded body. The pressure-bonded body was subjected to autoclave treatment (temperature 60 ° C., pressure 0.95 MPa, time 90 minutes) to prepare a test piece for measuring adhesion. With respect to this test piece, the adhesion strength (180 degree peel, tension rate 300 mm / min) between the adhesive layer and the base material layer was measured using a tensile tester (manufactured by Shimadzu Corporation, AGS-X 500NX).
（糊残りおよび破断）
　表１に示す構成を有する積層体（大きさ：２００ｍｍ×３００ｍｍ）の第１の粘着層を被着材としてのソーダライムガラス板に貼り合わせた。その後、温度２３℃かつ相対湿度６５％の条件で７日間放置した。放置終了後、被着材としてのソーダライムガラス板から積層体を剥離して、糊残り率を下記数式に基づいて計算して評価した。
　糊残り率（％）＝（ソーダライムガラスへ移行した粘着層の面積／
　　　　　　ソーダライムガラスに貼り合わせた粘着層の面積）×１００
　また、ソーダライムガラスから剥離した積層体を目視により観察して、破断の有無を評価した。評価は、破断の大小にかかわらず、何らかの破断が観察されたものを破断有りとした。
　なお、例７のＡの密着強度ならびに糊残りおよび破断の測定においては、第１の基材層に第１の粘着層を貼り合わせ、常温・常圧の環境下で２４時間以上放置し、上記ソーダライムガラス板に第１の基材層を第１の粘着剤により固定して、基材層を有するソーダライムガラス板を製造した後３０分以内に剥離して密着強度を測定し、糊残り率および破断の有無を評価した。 (Adhesive residue and breakage)
The 1st adhesion layer of the laminated body (size: 200 mm x 300 mm) which has a structure shown in Table 1 was bonded together to the soda-lime glass plate as a to-be-adhered material. Then, it was left for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65%. After the standing, the laminate was peeled from the soda lime glass plate as the adherend, and the adhesive residue rate was calculated and evaluated based on the following formula.
Adhesive residue rate (%) = (Area of adhesive layer transferred to soda lime glass /
Area of adhesive layer bonded to soda lime glass) x 100
Moreover, the laminated body peeled off from soda-lime glass was observed visually, and the presence or absence of a fracture | rupture was evaluated. In the evaluation, a case where some breakage was observed regardless of the size of the breakage was regarded as having a breakage.
In the measurement of the adhesion strength and adhesive residue and breakage of A in Example 7, the first adhesive layer was bonded to the first base material layer, and the mixture was allowed to stand for 24 hours or more in a normal temperature / normal pressure environment. The first base material layer is fixed to the soda lime glass plate with the first pressure-sensitive adhesive, and after the production of the soda lime glass plate having the base material layer, it is peeled off within 30 minutes and the adhesion strength is measured. The rate and the presence or absence of breakage were evaluated.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から明らかなように、第２の基材層を設けるとともに、密着力Ａに比べて密着力Ｂ、Ｃ、およびＤをいずれも５［Ｎ／２５ｍｍ］以上大きくした例１～３、７の積層体は、いずれも糊残りおよび破断が抑制され、リワーク性が良好なことが認められた。一方、密着力Ａに比べて密着力Ｂを５［Ｎ／２５ｍｍ］未満の大きさとした例４の積層体は、糊残りが発生した。また、第２の基材層を設けなかった例５の積層体、および密着力Ａに比べて密着力Ｃ、Ｄを５［Ｎ／２５ｍｍ］未満とした例６の積層体は、破断が発生した。 As is clear from Table 1, Examples 1 to 3, 7 in which the second base material layer is provided and the adhesion forces B, C, and D are all increased by 5 [N / 25 mm] or more compared to the adhesion force A. In each of the laminates, it was confirmed that adhesive residue and breakage were suppressed and reworkability was good. On the other hand, in the laminate of Example 4 in which the adhesion force B was less than 5 [N / 25 mm] compared to the adhesion force A, adhesive residue was generated. In addition, the laminate of Example 5 in which the second base material layer was not provided and the laminate of Example 6 in which the adhesion forces C and D were less than 5 [N / 25 mm] compared to the adhesion A were broken. did.
　本発明による積層体はリワーク性が良好であり、様々な表示パネルに適用可能である。また、本発明によれば、リワーク性が良好な積層体を有し、生産性の良好な表示装置を提供できる。
　なお、２０１２年１０月３０日に出願された日本特許出願２０１２－２３９３１３号の明細書、特許請求の範囲、図面、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The laminate according to the present invention has good reworkability and can be applied to various display panels. Further, according to the present invention, it is possible to provide a display device having a laminate having good reworkability and good productivity.
The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2012-239313 filed on October 30, 2012 are cited herein as disclosure of the specification of the present invention. Incorporate.
　１０…表示装置、１１…被着材、１２…積層体、１３…第１の粘着剤層、１４…第１の基材層、１４’…コントラスト向上層、１５…第２の粘着剤層、１６…第２の基材層、１４１…基材、１４２…コントラスト向上膜、１４２ａ…透光性領域、１４２ｂ…暗色部 DESCRIPTION OF SYMBOLS 10 ... Display apparatus, 11 ... Adhering material, 12 ... Laminated body, 13 ... 1st adhesive layer, 14 ... 1st base material layer, 14 '... Contrast improvement layer, 15 ... 2nd adhesive layer, 16 ... 2nd base material layer, 141 ... Base material, 142 ... Contrast improvement film | membrane, 142a ... Translucent area | region, 142b ... Dark color part

Claims (10)

  1. 　被着材に貼り合わされて使用される積層体であって、
    　前記被着材側から順に、第１の粘着剤層、第１の基材層、第２の粘着剤層、および第２の基材層を有し、前記積層体が前記被着材に貼り合わされたときの前記被着材と前記第１の粘着剤層との密着力をＡ［Ｎ／２５ｍｍ］、前記第１の粘着剤層と第１の基材層との密着力をＢ［Ｎ／２５ｍｍ］、前記第１の基材層と前記第２の粘着剤層との密着力をＣ［Ｎ／２５ｍｍ］、前記第２の粘着剤層と第２の基材層との密着力をＤ［Ｎ／２５ｍｍ］としたとき、密着力Ａに比べて密着力Ｂ、Ｃ、およびＤはいずれも５［Ｎ／２５ｍｍ］以上大きいことを特徴とする積層体。     A laminated body used by being bonded to an adherend,
    In order from the adherend side, a first adhesive layer, a first base material layer, a second adhesive layer, and a second base material layer are provided, and the laminate is attached to the adherend. The adhesion between the adherend and the first pressure-sensitive adhesive layer when combined is A [N / 25 mm], and the adhesion between the first pressure-sensitive adhesive layer and the first base material layer is B [N / 25 mm], the adhesive force between the first base material layer and the second adhesive layer is C [N / 25 mm], and the adhesive force between the second adhesive layer and the second base material layer is When D [N / 25 mm], the laminated body is characterized in that all of the adhesion forces B, C, and D are larger than the adhesion force A by 5 [N / 25 mm] or more.
  2. 　前記密着力Ａは１～１５［Ｎ／２５ｍｍ］である請求項１に記載の積層体。 The laminate according to claim 1, wherein the adhesion A is 1 to 15 [N / 25 mm].
  3. 　前記第１の基材層は、コントラスト向上層またはトリアセチルセルロースフィルムである請求項１または２に記載の積層体。 The laminate according to claim 1 or 2, wherein the first base material layer is a contrast improving layer or a triacetyl cellulose film.
  4. 　前記第２の基材層は、ポリエチレンテレフタレートフィルムを有する請求項１乃至３のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 3, wherein the second base material layer has a polyethylene terephthalate film.
  5. 　前記第１の粘着剤層および第２の粘着剤層のうち少なくとも１層は、アクリル系粘着剤を含む層である請求項１乃至４のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 4, wherein at least one of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is a layer containing an acrylic pressure-sensitive adhesive.
  6. 　前記密着力ＣおよびＤは、いずれも密着力Ａに比べて７［Ｎ／２５ｍｍ］以上大きい請求項１乃至５のいずれか１項に記載の積層体。 The laminated body according to any one of claims 1 to 5, wherein both of the adhesion forces C and D are larger than the adhesion force A by 7 [N / 25mm] or more.
  7. 　前記第１の粘着剤層および第２の粘着剤層のうち少なくとも１層は、厚さが１０μｍ以上である請求項１乃至６のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 6, wherein at least one of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer has a thickness of 10 µm or more.
  8. 　前記第２の基材層は、反射防止層である請求項１乃至７のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 7, wherein the second base material layer is an antireflection layer.
  9. 　前記積層体は表示装置用の光学フィルタである請求項１乃至８のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 8, wherein the laminate is an optical filter for a display device.
  10. 　表示パネルを有する被着材と、前記被着材に貼り合わされた積層体とを有する表示装置であって、
    　前記積層体は請求項１乃至９のいずれか１項に記載の積層体である表示装置。     A display device comprising an adherend having a display panel, and a laminate bonded to the adherend,
    The said laminated body is a display apparatus which is a laminated body of any one of Claims 1 thru | or 9.
PCT/JP2013/079460 2012-10-30 2013-10-30 Laminated body and display device WO2014069542A1 (en)

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