WO2019026760A1 - Corps stratifié pour dispositif d'affichage d'image souple, et dispositif d'affichage d'image souple - Google Patents

Corps stratifié pour dispositif d'affichage d'image souple, et dispositif d'affichage d'image souple Download PDF

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Publication number
WO2019026760A1
WO2019026760A1 PCT/JP2018/028091 JP2018028091W WO2019026760A1 WO 2019026760 A1 WO2019026760 A1 WO 2019026760A1 JP 2018028091 W JP2018028091 W JP 2018028091W WO 2019026760 A1 WO2019026760 A1 WO 2019026760A1
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Prior art keywords
meth
sensitive adhesive
pressure
image display
laminate
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PCT/JP2018/028091
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English (en)
Japanese (ja)
Inventor
昌邦 藤田
雄祐 外山
大器 下栗
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日東電工株式会社
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Priority to JP2019534451A priority Critical patent/JPWO2019026760A1/ja
Publication of WO2019026760A1 publication Critical patent/WO2019026760A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details

Definitions

  • the present invention relates to a laminate for a flexible image display including an adhesive layer and an optical film including at least a polarizing film, and a flexible image display in which the laminate for a flexible image display is disposed.
  • the optical laminate 20 is provided on the viewing side of the organic EL display panel 10, and the touch panel 30 is provided on the viewing side of the optical laminate 20.
  • the optical laminated body 20 includes the polarizing film 1 and the retardation film 3 in which the protective films 2-1 and 2-2 are joined on both surfaces, and the polarizing film 1 is provided on the viewing side of the retardation film 3.
  • the transparent conductive films 4-1 and 4-2 having a structure in which the base films 5-1 and 5-2 and the transparent conductive layers 6-1 and 6-2 are laminated via the spacer 7. It has the structure arrange
  • the conventional organic EL display device as shown in Patent Document 1 is not designed with bending in mind.
  • the organic EL display panel can be provided with flexibility.
  • the organic EL display panel can be provided with flexibility.
  • an optical film including a conventional polarizing film or the like, which is laminated on an organic EL display panel inhibits the flexibility of the organic EL display device.
  • the present invention is a laminate for a flexible image display including a pressure-sensitive adhesive layer and an optical film including at least a polarizing film, wherein the laminate is bent 180 ° and then returned to be flat.
  • the laminate does not peel or break even in repeated bending, and a laminate for a flexible image display device excellent in bending resistance and adhesion, and the flexible image
  • An object of the present invention is to provide a flexible image display device in which a laminate for a display device is disposed.
  • the laminate for a flexible image display according to the present invention is a laminate for a flexible image display including an adhesive layer and an optical film including at least a polarizing film, and is flat after bending the laminate by 180 °. It is characterized in that the bending angle remaining when returned to is 0 ° to 60 °.
  • the storage elastic modulus G ′ at 25 ° C. of the pressure-sensitive adhesive layer is 1 ⁇ 10 5 Pa or less, and tan ⁇ indicating the glass transition temperature (Tg) of the pressure-sensitive adhesive layer.
  • the peak value of is preferably 3 or less.
  • the loss elastic modulus G ′ ′ at 25 ° C. of the pressure-sensitive adhesive layer is preferably 1 ⁇ 10 5 Pa or less.
  • the laminate for a flexible image display device of the present invention preferably has the pressure-sensitive adhesive layer in two or more and five or less layers.
  • the pressure-sensitive adhesive layer is preferably formed of a pressure-sensitive adhesive composition containing a (meth) acrylic polymer.
  • the flexible image display device of the present invention includes the laminate for the flexible image display device and an organic EL display panel, and the laminate for the flexible image display device is disposed on the viewing side with respect to the organic EL display panel. Preferably.
  • a window is disposed on the viewing side with respect to the laminate for a flexible image display device.
  • a laminate for a flexible image display including an adhesive layer and an optical film including at least a polarizing film, wherein the laminate is bent 180 ° and then returned to be flat
  • the laminate does not peel or break even in repeated bending, and a laminate for a flexible image display device excellent in bending resistance and adhesion can be obtained.
  • FIG. 1 is a cross-sectional view of a flexible image display according to an embodiment of the present invention.
  • FIG. 7 is a cross-sectional view of a flexible image display according to another embodiment of the present invention.
  • FIG. 7 is a cross-sectional view of a flexible image display according to another embodiment of the present invention. It is a figure which shows a bending test ((A) bending angle 0 degree, (B) bending angle 180 degree). It is sectional drawing which shows the sample for evaluation used in an Example. It is a figure which shows the manufacturing method of the phase difference used in an Example.
  • the laminate for a flexible image display according to the present invention is characterized by including an adhesive layer and an optical film.
  • the laminate for a flexible image display according to the present invention is characterized by including an optical film containing at least a polarizing film, and as the optical film, a protective film formed of, for example, a transparent resin material in addition to the polarizing film. And films including films such as retardation films.
  • a protective film of a transparent resin material provided on the first surface of the polarizing film, and the first surface of the polarizing film.
  • a configuration including the retardation film of the present invention is referred to as an optical laminate.
  • adhesive layers such as a 1st adhesive layer mentioned later, are not contained in the said optical film.
  • the thickness of the optical film is preferably 92 ⁇ m or less, more preferably 60 ⁇ m or less, and still more preferably 10 to 50 ⁇ m. If it is in the said range, it will become a preferable aspect, without inhibiting bending.
  • a protective film may be bonded with an adhesive (layer) on at least one side, as long as the characteristics of the present invention are not impaired (not shown by the drawings).
  • An adhesive can be used for the adhesion process of a polarizing film and a protective film.
  • the adhesive include isocyanate adhesive, polyvinyl alcohol adhesive, gelatin adhesive, vinyl latex, water-based polyester and the like.
  • the adhesive is generally used as an adhesive consisting of an aqueous solution, and usually contains 0.5 to 60% by weight of solid content.
  • an ultraviolet curable adhesive, an electron beam curable adhesive and the like can be mentioned.
  • the adhesive for electron beam-curable polarizing film exhibits suitable adhesion to the various protective films described above.
  • the adhesive used in the present invention can contain a metal compound filler.
  • polarizing film polarizing plate
  • the polarizing film (also referred to as a polarizer) contained in the optical film of the present invention is an iodine-oriented polyvinyl alcohol (PVA) drawn by a drawing process such as air drawing (dry drawing) or a drawing process in boric acid water. Based resins can be used.
  • PVA polyvinyl alcohol
  • a production method including a step of dyeing a single layer of a PVA-based resin and a step of drawing typically as described in JP-A-2004-341515 (single-layer drawing method ).
  • the manufacturing method including the process of extending
  • the manufacturing method including the step of stretching in the state of the laminate and the step of dyeing is as described in the above-mentioned JP-A-51-069644, JP-A-2000-338329, and JP-A-2001-343521.
  • the process of stretching in a boric acid aqueous solution as described in WO 2010/100917 and JP-A No. 2012-073563 is performed in that it can be stretched at a high magnification to improve the polarization performance.
  • the production method is preferable, and in particular, the production method (two-step stretching method) including the step of performing air-assisted stretching before stretching in a boric acid aqueous solution as described in JP-A-2012-073563 is preferable. Moreover, after extending
  • the polarizing film contained in the optical film of the present invention is made of a polyvinyl alcohol-based resin in which iodine is oriented as described above, and the polarizing film is drawn in a two-step drawing process consisting of air-assisted drawing and drawing in boric acid water. can do.
  • the polarizing film is made of a polyvinyl alcohol-based resin in which iodine is oriented as described above, and the laminate of the stretched PVA-based resin layer and the resin base for stretching is excessively dyed and then decolored. It can be set as the produced polarizing film.
  • the thickness of the polarizing film is 20 ⁇ m or less, preferably 12 ⁇ m or less, more preferably 9 ⁇ m or less, still more preferably 1 to 8 ⁇ m, particularly preferably 3 to 6 ⁇ m. If it is in the said range, it will become a preferable aspect, without inhibiting bending.
  • the optical film used in the present invention may include a retardation film, and the retardation film (also referred to as retardation film) may be obtained by stretching a polymer film, or may be used to align or fix a liquid crystal material. It is possible to use one that has been In the present specification, the retardation film refers to one having birefringence in the in-plane direction and / or in the thickness direction.
  • retardation films As retardation films, retardation films for antireflection (refer to JP 2012-133303 [0221], [0222], [0228]), retardation films for view angle compensation (JP 2012-133303 [0225] And [0226], and a tilt alignment retardation film for viewing angle compensation (refer to JP 2012-133303 [0227]) and the like.
  • retardation film for example, retardation value, arrangement angle, three-dimensional birefringence, single layer or multilayer, etc. are not particularly limited as long as the retardation film substantially has the above-mentioned function, and known retardation films Can be used.
  • the thickness of the retardation film is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 1 to 9 ⁇ m, and particularly preferably 3 to 8 ⁇ m. If it is in the said range, it will become a preferable aspect, without inhibiting bending.
  • the optical film used in the present invention can include a protective film formed of a transparent resin material, and the protective film (also referred to as a transparent protective film) is a cycloolefin resin such as a norbornene resin, polyethylene, An olefin resin such as polypropylene, a polyester resin, a (meth) acrylic resin or the like can be used.
  • a transparent protective film is a cycloolefin resin such as a norbornene resin, polyethylene, An olefin resin such as polypropylene, a polyester resin, a (meth) acrylic resin or the like can be used.
  • the thickness of the protective film is preferably 5 to 60 ⁇ m, more preferably 10 to 40 ⁇ m, still more preferably 10 to 30 ⁇ m, and appropriately providing a surface treatment layer such as an antiglare layer or an antireflective layer. Can. If it is in the said range, it will become a preferable aspect, without inhibiting bending.
  • the laminate for a flexible image display according to the present invention is characterized in that it is a laminate for a flexible image display including an adhesive layer and an optical film containing at least a polarizing film.
  • the pressure-sensitive adhesive layer may be a single layer, but in addition to the optical film, for lamination of a transparent conductive film, an organic EL display panel, a window, a decorative print film, a retardation layer, a protective film, etc.
  • a plurality of pressure-sensitive adhesive layers in a laminate for a flexible image display device such as a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer, as shown in FIG. See etc.).
  • the thickness of the entire laminate becomes large, so the difference in strain between the outermost layer and the innermost layer in the bent portion of the laminate becomes large, and peeling and breakage easily occur, which is not preferable.
  • the first pressure-sensitive adhesive layer is disposed on the side opposite to the surface in contact with the polarizing film with respect to the protective film. Is preferred (see FIG. 2).
  • the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive layer used for the laminate for a flexible image display device of the present invention comprises an acrylic pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, a vinyl alkyl ether pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, and a polyester type.
  • a pressure-sensitive adhesive, a polyamide-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a fluorine-based pressure-sensitive adhesive, an epoxy-based pressure-sensitive adhesive, a polyether-based pressure-sensitive adhesive and the like can be mentioned.
  • the adhesive which comprises the said adhesive layer is used individually or in combination of 2 or more types. However, from the viewpoint of transparency, processability, durability, adhesion, flexibility and the like, it is preferable to use an acrylic pressure-sensitive adhesive (composition) containing a (meth) acrylic polymer alone.
  • a (meth) acrylic-based monomer having a linear or branched alkyl group having 1 to 30 carbon atoms as a monomer unit. It is preferable to contain a system polymer.
  • the linear or branched (meth) acrylic monomer having an alkyl group having 1 to 30 carbon atoms a pressure-sensitive adhesive layer having excellent flexibility can be obtained.
  • the (meth) acrylic polymer refers to an acrylic polymer and / or a methacrylic polymer
  • the (meth) acrylate refers to an acrylate and / or a methacrylate.
  • (meth) acrylic monomers having a linear or branched alkyl group having 1 to 30 carbon atoms constituting the main skeleton of the (meth) acrylic polymer include methyl (meth) acrylate and ethyl (Meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n -Hexyl (meth) acrylate, isohexyl (meth) acrylate, isoheptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth)
  • a (meth) acrylic monomer having a linear or branched alkyl group having 6 to 30 carbon atoms (hereinafter, “a (meth) acrylic monomer having a long chain alkyl group”) Is preferred, and n-dodecyl (meth) acrylate (lauryl (meth) acrylate) is more preferred.
  • Tg glass transition temperature
  • an acrylate As said (meth) acrylic-type monomer, 1 type (s) or 2 or more types can be used.
  • “minor strain” refers to, for example, a strain of about ⁇ 0 to 10% with respect to a bending direction of 3 mm centered on the apex of the bending portion in the laminate for a flexible image display device, and "+” Indicates strain in the tensile direction, and "-” indicates strain in the compressive direction.
  • a tensile direction strain of "+” is applied to the bending outer side (convex side)
  • a compression direction strain of "-” is applied to the bending inner side (concave side)
  • any of the inside of the laminate to be bent There is a neutral axis where the strain stress is zero.
  • the linear or branched (meth) acrylic monomer having an alkyl group having 1 to 30 carbon atoms is a main component in all the monomers constituting the (meth) acrylic polymer.
  • the main component means that 50 to 100 weight of (meth) acrylic monomers having linear or branched alkyl group having 1 to 30 carbon atoms in all monomers constituting the (meth) acrylic polymer % Is preferable, 80 to 100% by weight is more preferable, 90 to 99.9% by weight is further preferable, and 94 to 99.9 is particularly preferable.
  • the monomer component constituting the (meth) acrylic polymer is a copolymerizable monomer (in addition to the (meth) acrylic monomer having the linear or branched alkyl group having 1 to 30 carbon atoms) (Copolymerizable monomer) may be contained.
  • a copolymerizable monomer may be used individually or in combination of 2 or more types.
  • the copolymerizable monomer is not particularly limited, but it is preferable to contain a (meth) acrylic polymer containing a hydroxyl group-containing monomer having a reactive functional group.
  • a pressure-sensitive adhesive layer having excellent adhesion and flexibility can be obtained.
  • the hydroxyl group-containing monomer is a compound containing a hydroxyl group in the structure and containing a polymerizable unsaturated double bond such as (meth) acryloyl group or vinyl group.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxy
  • hydroxyalkyl (meth) acrylates such as octyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate and 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) -methyl acrylate.
  • hydroxyl group-containing monomers 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable from the viewpoint of durability and adhesion.
  • hydroxyl group containing monomer 1 type (s) or 2 or more types can be used.
  • monomers such as a carboxyl group-containing monomer which has a reactive functional group, an amino group-containing monomer, and an amide group-containing monomer, as said copolymerizable monomer.
  • Use of these monomers is preferable from the viewpoint of adhesion under humidification and high temperature environment.
  • a (meth) acrylic polymer containing a carboxyl group-containing monomer having a reactive functional group can be contained as a monomer unit.
  • the carboxyl group-containing monomer is a compound containing a carboxyl group in the structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
  • carboxyl group-containing monomer examples include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like.
  • a (meth) acrylic polymer containing an amino group-containing monomer having a reactive functional group can be contained as a monomer unit.
  • the amino group-containing monomer is a compound containing an amino group in the structure and containing a polymerizable unsaturated double bond such as (meth) acryloyl group or vinyl group.
  • amino group-containing monomer examples include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate and the like.
  • a (meth) acrylic-based polymer containing an amide group-containing monomer having a reactive functional group can be contained as a monomer unit.
  • the amide group-containing monomer is a compound containing an amide group in the structure and containing a polymerizable unsaturated double bond such as (meth) acryloyl group or vinyl group.
  • the amide group-containing monomer examples include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropylacrylamide, N-methyl (meth) acrylamide, N -Butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylol-N-propane (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, mercapto Acrylamide-based monomers such as methyl (meth) acrylamide and mercaptoethyl (meth) acrylamide; N such as N- (meth) acryloyl morpholine, N- (meth) acryloyl piperidine and N- (meth) acryloyl pyrrolidine Acryloyl heterocyclic monomers; N such
  • polyfunctional monomers polyfunctional monomers
  • a crosslinking effect can be obtained by polymerization, and adjustment of gel fraction and improvement of cohesive strength can be easily performed. For this reason, cutting becomes easy, and processability is likely to be improved. Furthermore, it is possible to prevent peeling of the pressure-sensitive adhesive layer due to cohesive failure during bending (particularly under a high temperature environment).
  • the polyfunctional monomer is not particularly limited.
  • hexanediol di (meth) acrylate (1,6-hexanediol di (meth) acrylate), butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) ) Acrylate, (Poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylol Propane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, epoxy acrylate, polyester acrylate Or polyfunctional acrylates such as urethane acrylate, divinyl benzen
  • the polyfunctional acrylate 1,6-hexanediol diacrylate, dipentaerythritol hexa (meth) acrylate.
  • a polyfunctional monomer may be used individually or in combination of 2 or more types.
  • the mixing ratio (total amount) of the monomer having the reactive functional group and the polyfunctional monomer is all the monomers constituting the (meth) acrylic polymer Among them, 20% by weight or less is preferable, 10% by weight or less is more preferable, 0.01 to 8% by weight is more preferable, 0.01 to 5% by weight is particularly preferable, and 0.05 to 3% by weight is most preferable. If it exceeds 20% by weight, the crosslinking point increases and the flexibility of the pressure-sensitive adhesive (layer) is lost, so that the stress relaxation tends to be poor.
  • (meth) acrylic acid alkoxy alkyl ester For example, 2-methoxyethyl (meth) acrylic acid, 2-ethoxyethyl (meth) acrylic acid, methoxy triethyl (meth) acrylate] Ethylene glycol, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate, etc .; epoxy group-containing monomers [ For example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, etc.]; sulfonic acid group-containing monomer [eg, sodium vinylsulfonate etc.]; phosphoric acid group-containing monomer; having an alicyclic hydrocarbon group (meth ) Acrylic esters [eg (meth)
  • the proportion of the other copolymerizable monomer is not particularly limited, but is preferably 30% by weight or less, more preferably 10% by weight or less, and still more preferably not included, in all the monomers constituting the (meth) acrylic polymer. . If it exceeds 30% by weight, the reaction point between the pressure-sensitive adhesive layer and the other layers (films and substrates) tends to be reduced particularly when other than (meth) acrylic monomers are used, and the adhesion tends to be lowered.
  • the pressure-sensitive adhesive layer may be formed of a pressure-sensitive adhesive composition
  • the pressure-sensitive adhesive composition may be any pressure-sensitive adhesive composition, for example, an emulsion type, a solvent type (solution type). Active energy ray curable type, heat melting type (hot melt type) and the like.
  • preferred examples of the pressure-sensitive adhesive composition include solvent-type pressure-sensitive adhesive compositions and active energy ray-curable pressure-sensitive adhesive compositions.
  • a pressure-sensitive adhesive composition containing the (meth) acrylic polymer as an essential component is preferably mentioned.
  • a pressure-sensitive adhesive composition containing a mixture of monomer components (monomer mixture) constituting the (meth) acrylic polymer or a partial polymer thereof as an essential component is preferable. It can be mentioned.
  • the term "partially polymerized product” means a composition in which one or two or more components of the monomer components contained in the monomer mixture are partially polymerized.
  • the “monomer mixture” includes the case where there is only one monomer component.
  • the pressure-sensitive adhesive composition is a mixture of monomer components constituting a (meth) acrylic polymer from the viewpoints of productivity, environmental impact, and ease of obtaining a thick adhesive layer ( It is preferable that it is an active energy ray-curable pressure-sensitive adhesive composition containing a monomer mixture) or a partially polymerized product thereof as an essential component.
  • the (meth) acrylic polymer is obtained by polymerizing the monomer component. More specifically, it can be obtained by polymerizing the above-mentioned monomer component, the above-mentioned monomer mixture or a partial polymer thereof by a known method.
  • the polymerization method include solution polymerization, emulsion polymerization, bulk polymerization, polymerization by heat and active energy ray irradiation (thermal polymerization, active energy ray polymerization), and the like.
  • solution polymerization and active energy ray polymerization are preferable in terms of transparency, water resistance, cost and the like.
  • it is preferable that polymerization is performed avoiding contact with oxygen from the point which suppresses the polymerization inhibition by oxygen.
  • the (meth) acrylic polymer to be obtained may be any of a random copolymer, a block copolymer, a graft copolymer and the like.
  • Examples of the active energy ray irradiated at the time of the above-mentioned active energy ray polymerization (photopolymerization) include ionizing radiation such as alpha rays, beta rays, gamma rays, neutron rays and electron rays, and ultraviolet rays, and in particular, ultraviolet rays. Is preferred. Further, the irradiation energy of the active energy ray, the irradiation time, the irradiation method and the like are not particularly limited, as long as the photopolymerization initiator can be activated to cause the reaction of the monomer component.
  • solvents for example, esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane, methyl Alicyclic hydrocarbons such as cyclohexane; and organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • esters such as ethyl acetate and n-butyl acetate
  • aromatic hydrocarbons such as toluene and benzene
  • aliphatic hydrocarbons such as n-hexane and n-heptane
  • cyclohexane methyl Alicyclic hydrocarbons
  • organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • the solvents may be used
  • a polymerization initiator such as a photopolymerization initiator (photoinitiator) or a thermal polymerization initiator may be used according to the type of polymerization reaction.
  • a polymerization initiator may be used individually or in combination of 2 or more types.
  • the photopolymerization initiator is not particularly limited.
  • benzoin ether photopolymerization initiator acetophenone photopolymerization initiator, ⁇ -ketol photopolymerization initiator, aromatic sulfonyl chloride photopolymerization initiator, light Active oxime type photoinitiators, benzoin type photoinitiators, benzyl type photoinitiators, benzophenone type photoinitiators, ketal type photoinitiators, thioxanthone type photoinitiators may be mentioned.
  • benzoin ether photopolymerization initiators examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, Anisole methyl ether etc. are mentioned.
  • acetophenone photopolymerization initiators include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, 4- (t-butyl) ) Dichloroacetophenone and the like.
  • Examples of the ⁇ -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one and the like.
  • Be Examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalene sulfonyl chloride and the like.
  • Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime and the like.
  • Examples of the benzoin photopolymerization initiator include benzoin. As said benzyl type photoinitiator, a benzyl etc.
  • benzophenone-based photopolymerization initiators examples include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinyl benzophenone, ⁇ -hydroxycyclohexyl phenyl ketone and the like.
  • ketal type photoinitiator a benzyl dimethyl ketal etc. are mentioned, for example.
  • thioxanthone photopolymerization initiators examples include thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, and dodecyl thioxanthone.
  • the amount of the photopolymerization initiator used is not particularly limited, but is preferably 0.01 to 1 part by weight, and more preferably 0.05 to 0.5 parts by weight with respect to 100 parts by weight of the total amount of monomer components.
  • Examples of the polymerization initiator used in the solution polymerization include an azo polymerization initiator, a peroxide polymerization initiator (eg, dibenzoyl peroxide, tert-butyl permaleate, etc.), a redox polymerization initiator, etc. Can be mentioned. Among them, an azo polymerization initiator disclosed in JP-A-2002-69411 is preferable. As the above-mentioned azo polymerization initiator, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis (2-methylpropionic acid) And dimethyl), 4,4'-azobis-4-cyanovaleric acid and the like.
  • AIBN 2,2'-azobisisobutyronitrile
  • 2,2'-azobis-2-methylbutyronitrile 2,2'-azobis (2-methylpropionic acid) And dimethyl
  • the use amount of the azo polymerization initiator is not particularly limited, but preferably 0.05 to 0.5 parts by weight, more preferably 0.1 to 0.3 parts by weight with respect to 100 parts by weight of the total amount of monomer components. It is.
  • the polyfunctional monomer (polyfunctional acrylate) used as the said copolymerization monomer can also be used also for a solvent type or the adhesive composition of an active energy ray curing type,
  • the said solvent type adhesive composition When mixing and using a polyfunctional monomer (polyfunctional acrylate) and the said photoinitiator, active energy ray curing will be performed after heat drying.
  • the (meth) acrylic polymer used for the solvent-type pressure-sensitive adhesive composition when used, one having a weight average molecular weight (Mw) in the range of 1,000,000 to 2,000,000 is usually used. In consideration of durability, particularly heat resistance and flexibility, it is preferably 1.2 million to 2 million, and more preferably 1.4 million to 1.8 million.
  • the weight average molecular weight is less than 1,000,000, when crosslinking polymer chains to ensure durability, the crosslinking point is increased compared to the one having a weight average molecular weight of 1,000,000 or more, and the pressure-sensitive adhesive (layer Since the flexibility of the above is lost, the distortions on the outside (convex side) and the inside (concave side) of bending occurring between layers (each film) can not be relieved, and breakage of each layer tends to occur.
  • the weight average molecular weight is larger than 2.5 million, a large amount of dilution solvent is required to adjust the viscosity for coating, which is not preferable because the cost is increased, and (meth) acrylic resin is obtained.
  • Mw weight average molecular weight
  • the pressure-sensitive adhesive composition can contain (meth) acrylic oligomers.
  • the (meth) acrylic oligomer preferably uses a polymer having a weight average molecular weight (Mw) smaller than that of the (meth) acrylic polymer, and by using such (meth) acrylic oligomer, )
  • Mw weight average molecular weight
  • the (meth) acrylic oligomer intervenes between the acrylic polymers to reduce the entanglement of the (meth) acrylic polymer, which makes it easy to be deformed against a minute strain, and a preferable embodiment with respect to flexibility Become.
  • Examples of the monomer constituting the (meth) acrylic oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate and isobutyl (meth) Acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, Octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (
  • Examples of the (meth) acrylic oligomers include alkyl (meth) acrylates having an alkyl group having a branched structure such as isobutyl (meth) acrylate and t-butyl (meth) acrylate; cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate ) Esters of (meth) acrylic acid with a cycloaliphatic alcohol such as acrylate dicyclopentanyl (meth) acrylate; cyclic structures such as aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate It is preferable to contain as a monomer unit an acrylic monomer having a relatively bulky structure, represented by (meth) acrylate having By providing such a bulky structure to the (meth) acrylic oligomer, the adhesion of the pressure-sensitive adhesive layer can be further improved.
  • those having a cyclic structure in terms of bulkiness are highly effective, and those containing a plurality of rings are even more effective.
  • those having a saturated bond are preferable in that they are unlikely to cause polymerization inhibition, and alkyl groups are preferred.
  • An alkyl (meth) acrylate having a branched structure or an ester with an alicyclic alcohol can be suitably used as a monomer constituting a (meth) acrylic oligomer.
  • acrylic oligomers for example, copolymers of butyl acrylate (BA), methyl acrylate (MA) and acrylic acid (AA), cyclohexyl methacrylate (CHMA) and isobutyl methacrylate ( Copolymer of IBM A), copolymer of cyclohexyl methacrylate (CHMA) and isobornyl methacrylate (IBXMA), copolymer of cyclohexyl methacrylate (CHMA) and acryloyl morpholine (ACMO), cyclohexyl methacrylate (CHMA) and diethyl acrylamide Copolymer of DEAA), copolymer of 1-adamantyl acrylate (ADA) and methyl methacrylate (MMA), dicyclopentanyl methacrylate (DCPMA) and isobornyl methacrylate (IBXMA) copolymer, dicyclopentanyl methacrylate, dicyclopentanyl methacryl
  • the (meth) acrylic oligomer As the polymerization method of the (meth) acrylic oligomer, similar to the (meth) acrylic polymer, solution polymerization, emulsion polymerization, bulk polymerization, emulsion polymerization, polymerization by heat or active energy ray irradiation (thermal polymerization, active energy Linear polymerization) and the like. Among them, solution polymerization and active energy ray polymerization are preferable in terms of transparency, water resistance, cost and the like.
  • the (meth) acrylic oligomer to be obtained may be any of a random copolymer, a block copolymer, a graft copolymer and the like.
  • the (meth) acrylic oligomer can be used in the solvent-based pressure-sensitive adhesive composition or the active energy ray-curable pressure-sensitive adhesive composition, as in the case of the (meth) acrylic-based polymer.
  • the active energy ray-curable pressure-sensitive adhesive composition the (meth) acrylic oligomer is further added to a mixture (monomer mixture) of monomer components constituting the (meth) acrylic polymer or a partial polymer thereof. It can be mixed and used.
  • the active energy ray curing can be completed to obtain the pressure-sensitive adhesive layer.
  • the weight average molecular weight (Mw) of the (meth) acrylic oligomer used in the solvent type pressure-sensitive adhesive composition is preferably 1000 or more, more preferably 2000 or more, still more preferably 3000 or more, and particularly preferably 4000 or more.
  • the weight average molecular weight (Mw) of the (meth) acrylic oligomer is preferably 30000 or less, more preferably 15000 or less, still more preferably 10000 or less, and particularly preferably 7000 or less.
  • the weight-average molecular weight (Mw) of the (meth) acrylic oligomer within the above range, for example, when using in combination with the (meth) acrylic polymer, it is possible to ) An acrylic oligomer intervenes, the entanglement of the (meth) acrylic polymer is reduced, the pressure-sensitive adhesive layer is easily deformed to a minute strain, the strain applied to other layers can be reduced, and cracking or adhesion of each layer Peeling or the like between the agent layer and the other layers can be suppressed, which is a preferred embodiment.
  • the weight average molecular weight (Mw) of the said (meth) acrylic-type oligomer is measured by GPC (gel permeation chromatography) like the said (meth) acrylic-type polymer, and the value calculated by polystyrene conversion is Say.
  • the amount thereof is not particularly limited, but is preferably 70 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer, More preferably, it is 1 to 70 parts by weight, more preferably 2 to 50 parts by weight, and still more preferably 3 to 40 parts by weight.
  • the (meth) acrylic oligomer By adjusting the compounding amount of the (meth) acrylic oligomer within the above range, the (meth) acrylic oligomer appropriately intervenes between the (meth) acrylic polymer, and entanglement of the (meth) acrylic polymer
  • the pressure-sensitive adhesive layer is easily deformed to a minute strain, and the strain applied to the other layers can be reduced, and cracking of each layer and peeling between the pressure-sensitive adhesive layer and the other layers can be suppressed. It becomes an aspect.
  • the pressure-sensitive adhesive composition of the present invention can contain a crosslinking agent.
  • a crosslinking agent an organic crosslinking agent or a polyfunctional metal chelate can be used in any of the solvent-type or active energy ray-curable pressure-sensitive adhesive composition.
  • an organic type crosslinking agent an isocyanate type crosslinking agent, a peroxide type crosslinking agent, an epoxy type crosslinking agent, an imine type crosslinking agent etc. are mentioned.
  • a polyfunctional metal chelate is one in which a polyvalent metal is covalently bonded or coordinated with an organic compound.
  • polyvalent metal atoms examples include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, etc. It can be mentioned.
  • An oxygen atom etc. are mentioned as an atom in the organic compound which carries out covalent bond or coordinate bond,
  • An alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, a ketone compound etc. are mentioned as an organic compound.
  • peroxide-based crosslinking agents and isocyanate crosslinking agents are preferable, and among these, peroxide-based crosslinking agents are preferably used.
  • the peroxide-based crosslinking agent generates a radical by, for example, extracting hydrogen of the side chain of the (meth) acrylic polymer, and causes the cross-linking between the side chains of the (meth) acrylic polymer to proceed, so an isocyanate-based crosslinking agent
  • a crosslinking agent e.g., a polyfunctional isocyanate-based crosslinking agent
  • a crosslinking agent e.g., a polyfunctional isocyanate-based crosslinking agent
  • an isocyanate-based crosslinking agent in particular, a trifunctional isocyanate-based crosslinking agent
  • a peroxide-based crosslinking agent and an isocyanate-based crosslinking agent Is preferred in terms of flexibility.
  • peroxide-based crosslinking agents and bifunctional isocyanate-based crosslinking agents both form flexible two-dimensional crosslinking
  • trifunctional isocyanate-based crosslinking agents form stronger three-dimensional crosslinking.
  • two-dimensional crosslinking which is a more flexible crosslinking, is advantageous.
  • a crosslinking agent is mixed with a mixture of monomer components (monomer mixture) constituting the (meth) acrylic polymer or a partial polymer thereof, and the adhesive composition is thermally dried and crosslinked before and after active energy ray curing.
  • the reaction of the agent can be completed.
  • the amount of the crosslinking agent used is, for example, preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, and more preferably 0.3 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. Parts by weight are more preferred. If it is in the said range, it is excellent in bending resistance and it becomes a preferable aspect.
  • the peroxide crosslinking agent When used alone, it is preferably 0.5 to 5 parts by weight, and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. Within the above range, the cohesion can be sufficiently enhanced while maintaining the ease of deformation due to a minute strain, and the durability and the bending resistance can be improved, which is a preferable embodiment.
  • the lower limit value of the weight ratio of the peroxide type crosslinking agent to the isocyanate type crosslinking agent is preferably 1.2 or more, more preferably 1.5 or more, and still more preferably 3 or more.
  • the upper limit value of the weight ratio is preferably 500 or less, more preferably 300 or less, and still more preferably 200 or less.
  • the pressure-sensitive adhesive composition in the present invention may contain other known additives.
  • various silane coupling agents, polyether compounds of polyalkylene glycols such as polypropylene glycol, colorants, pigments, etc. Powders, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, light stabilizers, UV absorbers, polymerization inhibitors, antistatics Additives (alkali metal salts, ionic liquids, ionic solids, etc. which are ionic compounds), inorganic or organic fillers, metal powders, particles, foils, etc. can be added as appropriate depending on the use. Moreover, you may employ
  • the method for preparing the pressure-sensitive adhesive composition is not particularly limited, but any known method can be used.
  • the solvent-based acrylic pressure-sensitive adhesive composition is a (meth) acrylic polymer, It is produced by mixing the component (For example, the said (meth) acrylic-type oligomer, a crosslinking agent, a silane coupling agent, a solvent, an additive etc.) added as needed.
  • the active energy ray-curable acrylic pressure-sensitive adhesive composition may be a monomer mixture or a partial polymer thereof, a component to be added if necessary (for example, the photopolymerization initiator, polyfunctional monomer, (Meth) acrylic oligomers, crosslinking agents, silane coupling agents, solvents, additives, etc. are mixed to prepare.
  • a component to be added if necessary for example, the photopolymerization initiator, polyfunctional monomer, (Meth) acrylic oligomers, crosslinking agents, silane coupling agents, solvents, additives, etc. are mixed to prepare.
  • the pressure-sensitive adhesive composition preferably has a viscosity suitable for handling and coating. For this reason, it is preferable that the active energy ray-curable acrylic pressure-sensitive adhesive composition contains a partially polymerized product of a monomer mixture.
  • the polymerization rate of the partially polymerized product is not particularly limited, but is preferably 5 to 20% by weight, more preferably 5 to 15% by weight.
  • the polymerization rate of the said partial polymer is calculated
  • a portion of the partially polymerized product is sampled to give a sample.
  • the sample is precisely weighed to determine its weight, which is the "weight of partially polymerized product before drying”.
  • the sample is dried at 130 ° C. for 2 hours, and the dried sample is precisely weighed to determine its weight, which is the “weight of partially polymerized product after drying”.
  • the weight of the sample reduced by drying at 130 ° C. for 2 hours is determined from “weight of partial polymer before drying” and “weight of partial polymer after drying”, “weight loss” (volatilized, Unreacted monomer weight).
  • the second pressure-sensitive adhesive layer may be disposed on the side of the retardation film opposite to the side in contact with the polarizing film. Yes (see Figure 2).
  • the third pressure-sensitive adhesive layer is in contact with the second pressure-sensitive adhesive layer with respect to the transparent conductive layer constituting the touch sensor.
  • a third adhesive layer can be arranged (see FIG. 2).
  • the third pressure-sensitive adhesive layer is in contact with the first pressure-sensitive adhesive layer with respect to the transparent conductive layer constituting the touch sensor. It can be placed on the opposite side of the surface (see FIG. 3).
  • these pressure-sensitive adhesive layers are identical.
  • the composition the same pressure-sensitive adhesive composition
  • the same characteristics or the different characteristics, but all pressure-sensitive adhesives from the viewpoint of workability, economy, and flexibility.
  • the layers be pressure-sensitive adhesive layers having substantially the same composition and the same characteristics.
  • a method of forming the pressure-sensitive adhesive layer for example, a method of forming a pressure-sensitive adhesive layer by applying the solvent type pressure-sensitive adhesive composition to a release-treated separator (release film) and removing the polymerization solvent and the like by drying.
  • coats to the said separator etc., and the method etc. of forming by irradiating an active energy ray are mentioned. In addition to the active energy ray irradiation, heating and drying may be performed as necessary.
  • one or more solvents other than the polymerization solvent may be added as appropriate.
  • a silicone release liner is preferably used as the release-treated separator.
  • an appropriate method may be appropriately adopted as a method of drying the pressure-sensitive adhesive depending on the purpose. .
  • the method of heat-drying the said coating film is used.
  • the heating and drying temperature is, for example, preferably 40 to 200 ° C., more preferably 50 to 180 ° C., particularly preferably 70 to 200 ° C., when preparing an acrylic pressure-sensitive adhesive using a (meth) acrylic polymer. It is 170 ° C. By making heating temperature into said range, the adhesive which has the outstanding adhesion characteristic can be obtained.
  • the drying time any appropriate time may be employed.
  • the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, particularly preferably 10 seconds to 5 minutes, for example, when preparing an acrylic adhesive using a (meth) acrylic polymer. It is a minute.
  • Various methods can be used as a method of applying the pressure-sensitive adhesive composition. Specifically, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater etc. Methods such as extrusion coating may be mentioned.
  • the thickness of the pressure-sensitive adhesive layer used in the laminate for a flexible image display according to the present invention is preferably 1 to 200 ⁇ m, more preferably 5 to 150 ⁇ m, and still more preferably 10 to 100 ⁇ m.
  • the pressure-sensitive adhesive layer may be a single layer or may have a laminated structure. If it is in the said range, it will become a preferable aspect, also from the point of adhesiveness (holding resistance), without inhibiting a bending
  • the storage elastic modulus G ′ at 25 ° C. of the pressure-sensitive adhesive layer is 1 ⁇ 10 5 Pa or less, and tan ⁇ indicating the glass transition temperature (Tg) of the pressure-sensitive adhesive layer.
  • the peak value of (loss tangent) is preferably 3 or less.
  • the storage elastic modulus G ′ is more preferably 8 ⁇ 10 4 Pa or less, still more preferably 6 ⁇ 10 4 Pa or less, particularly preferably 4 ⁇ 10 4 Pa or less, 3 Most preferably, it is 10 4 Pa or less.
  • the tan ⁇ is more preferably 2.5 or less, still more preferably 2 or less, particularly preferably 1.5 or less, and most preferably 1 or less.
  • the storage elastic modulus G 'at 25 ° C. and the peak value of tan ⁇ indicating Tg are within the above range, that is, the storage elastic modulus G' is kept low to distort the adhesive layer at the time of bending. Makes it easy to diffuse strain stress by suppressing tan ⁇ to a low level, and by making the pressure-sensitive adhesive layer easy to strain, the laminate for a flexible image display device is bent or opened even with a light force (load). It becomes possible, and becomes a desirable mode.
  • strain stress generated at the time of bending becomes energy at the time of returning from the bending state to the flat state, it becomes easy to return from the bending state to the flat state, and it is estimated that the remaining bending angle is reduced. Be done.
  • the following methods are mentioned as an adhesive composition used for formation of an agent layer.
  • a solvent type pressure-sensitive adhesive composition a (meth) acrylic polymer copolymerized with a (meth) acrylic monomer having the long chain alkyl group is used.
  • the solvent type first method it is preferable to set the (meth) acrylic monomer having the long chain alkyl group to 40% by weight or more and 99% by weight with respect to all the monomers.
  • the peroxide-based crosslinking agent is used alone as the crosslinking agent, and 0.5 parts by weight or more and 5 parts by weight or less relative to 100 parts by weight of the (meth) acrylic polymer Added.
  • a peroxide type crosslinking agent and an isocyanate type crosslinking agent are used in combination as a crosslinking agent, and the weight ratio of the peroxide type crosslinking agent to the isocyanate type crosslinking agent (peroxide type crosslinking agent / The isocyanate crosslinking agent is 1.2 or more and 500 or less, and the addition amount of the peroxide crosslinking agent is 0.2 parts by weight or more with respect to 100 parts by weight of the (meth) acrylic polymer.
  • the (meth) acrylic oligomer is further added to 100 parts by weight of the (meth) acrylic polymer. 1 part by weight or more and 70 parts by weight or less.
  • the (meth) acrylic monomer having the long chain alkyl group is mainly contained, It polymerizes with a polyfunctional monomer using the mixture (monomer mixture) containing the monomer which has a C1-C5 alkyl group or a functional group, or a functional group, or the partial polymerization thing of the said mixture.
  • the (meth) acrylic monomer having the long chain alkyl group has 10 to 30 carbon atoms.
  • a mixture (monomer mixture) of a (meth) acrylic monomer having an alkyl group and a (meth) acrylic monomer having an alkyl group having 6 to 9 carbon atoms is used or a partially polymerized product of the mixture.
  • the content of the (meth) acrylic monomer having the long chain alkyl group in all monomers is preferably 60% by weight or more.
  • the loss elastic modulus G ′ ′ at 25 ° C. of the pressure-sensitive adhesive layer is preferably 1 ⁇ 10 5 Pa or less, and 8 ⁇ 10 4 Pa or less More preferably, it is 4 ⁇ 10 4 Pa or less.
  • the loss elastic modulus G ′ ′ at 25 ° C. of the pressure-sensitive adhesive layer is in the above range, that is, by suppressing the loss elastic modulus G ′ ′ low, the pressure-sensitive adhesive layer hardly conforms to a bent state and returns to flat. It is possible to reduce the remaining of the bending angle, which is a preferable embodiment.
  • the upper limit of the glass transition temperature (Tg) of the pressure-sensitive adhesive layer used in the laminate for a flexible image display according to the present invention is preferably 5 ° C. or less. In consideration of the flexibility in a low temperature environment or a high speed region, it is more preferably ⁇ 20 ° C. or less, still more preferably ⁇ 25 ° C. or less. If the Tg of the pressure-sensitive adhesive layer is in such a range, the pressure-sensitive adhesive layer does not become hard easily even in bending in a low temperature environment or a high speed region where the bending speed exceeds 1 second / time, and has excellent stress relaxation properties It is possible to realize a flexible image display device in which the flexible image display device laminate can be bent or folded and the flexible image display device laminate is disposed.
  • the total light transmittance (according to JIS K7136) in the visible light wavelength region of the pressure-sensitive adhesive layer used in the laminate for a flexible image display according to the present invention is preferably 85% or more, more preferably 90% or more.
  • the member having the transparent conductive layer is not particularly limited, and a known member can be used, but a member having a transparent conductive layer on a transparent substrate such as a transparent film, a transparent conductive layer and a liquid crystal The member which has a cell can be mentioned.
  • a transparent base material what is necessary is just to have transparency, for example, a base material (for example, sheet-like, film-like, plate-like base material etc.) etc. which consist of resin films etc. are mentioned.
  • the thickness of the transparent substrate is not particularly limited, but is preferably about 10 to 200 ⁇ m, and more preferably about 15 to 150 ⁇ m.
  • the material of the resin film is not particularly limited, and various plastic materials having transparency may be mentioned.
  • polyester resin such as polyethylene terephthalate and polyethylene naphthalate, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin
  • Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin and the like can be mentioned.
  • polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.
  • the transparent base material is previously subjected to an etching process such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical formation, oxidation or undercoating on the surface, and the transparent conductive layer provided thereon
  • an etching process such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical formation, oxidation or undercoating on the surface, and the transparent conductive layer provided thereon
  • the adhesion to the transparent substrate may be improved.
  • the constituent material of the transparent conductive layer is not particularly limited, and is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, tungsten and molybdenum Or at least one metal or metal oxide, or an organic conductive polymer such as polythiophene.
  • the said metal oxide may contain the metal atom further shown by the said group as needed.
  • indium oxide (ITO) containing tin oxide, tin oxide containing antimony, etc. are preferably used, and ITO is particularly preferably used.
  • the ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.
  • Crystalline ITO can be obtained by applying a high temperature at the time of sputtering or by further heating amorphous ITO.
  • the thickness of the transparent conductive layer of the present invention is preferably 0.005 to 10 ⁇ m, more preferably 0.01 to 3 ⁇ m, and still more preferably 0.01 to 1 ⁇ m.
  • the thickness of the transparent conductive layer is less than 0.005 ⁇ m, the change in the electrical resistance value of the transparent conductive layer tends to be large.
  • it exceeds 10 ⁇ m the productivity of the transparent conductive layer is lowered, the cost is also increased, and the optical characteristics are also tended to be lowered.
  • the total light transmittance of the transparent conductive layer of the present invention is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more.
  • the density of the transparent conductive layer of the present invention is preferably 1.0 to 10.5 g / cm 3 , more preferably 1.3 to 3.0 g / cm 3 .
  • the surface resistance value of the transparent conductive layer of the present invention is preferably 0.1 to 1000 ⁇ / ⁇ , more preferably 0.5 to 500 ⁇ / ⁇ , and still more preferably 1 to 250 ⁇ / ⁇ .
  • a conventionally well-known method is employable. Specifically, for example, a vacuum evaporation method, a sputtering method, and an ion plating method can be exemplified. In addition, an appropriate method can be adopted according to the required film thickness.
  • an undercoat layer, an oligomer prevention layer, etc. can be provided as needed between a transparent conductive layer and a transparent base material.
  • the transparent conductive layer is required to constitute a touch sensor and be configured to be bendable.
  • the transparent conductive layer constituting the touch sensor is disposed on the second pressure-sensitive adhesive layer on the side opposite to the surface in contact with the retardation film. Can be done (see Figure 2).
  • the transparent conductive layer constituting the touch sensor may be disposed on the side opposite to the surface in contact with the protective film with respect to the first pressure-sensitive adhesive layer. Yes (see Figure 3).
  • the transparent conductive layer constituting the touch sensor can be disposed between the protective film and the window film (OCA) (see FIG. 3).
  • the transparent conductive layer can be suitably applied to a liquid crystal display device incorporating a touch sensor such as an in-cell type or an on-cell type as used in a flexible image display device, and in particular, a touch sensor is incorporated in an organic EL display panel It may be (built in).
  • a touch sensor such as an in-cell type or an on-cell type as used in a flexible image display device, and in particular, a touch sensor is incorporated in an organic EL display panel It may be (built in).
  • the laminate for a flexible image display device of the present invention may have a conductive layer (conductive layer, antistatic layer).
  • the laminate for a flexible image display device has a bending function and has a very thin thickness configuration, so it has high reactivity to weak static electricity generated in manufacturing processes and the like, and is easily damaged.
  • the conductive layer By providing the conductive layer, the load due to static electricity in the manufacturing process and the like is greatly reduced, which is a preferable embodiment.
  • the flexible image display including the laminate has one of the major features of having a bending function, but in the case of continuous bending, static electricity is generated due to contraction between films (substrates) of the bending portion. There is a case. Therefore, when conductivity is imparted to the laminate, generated static electricity can be removed quickly, and damage to the image display device due to static electricity can be reduced, which is a preferable embodiment.
  • the conductive layer may be a subbing layer having a conductive function, a pressure-sensitive adhesive containing a conductive component, or a surface treatment layer containing a conductive component.
  • a method of forming a conductive layer between the polarizing film and the pressure-sensitive adhesive layer can be adopted using an antistatic agent composition containing a conductive polymer such as polythiophene and a binder.
  • a pressure sensitive adhesive containing an ionic compound which is an antistatic agent can also be used.
  • the conductive layer preferably has one or more layers, and may contain two or more layers.
  • the laminate for a flexible image display according to the present invention is a laminate for a flexible image display including an adhesive layer and an optical film including at least a polarizing film, and is flat after bending the laminate by 180 °. It is characterized in that the bending angle which remains when it is returned to 0 ° is 0 ° to 60 °, and the bending angle is preferably 0 ° to 50 °, more preferably 0 ° to 40 °. It is more preferably 0 ° to 30 °, particularly preferably 0 ° to 25 °, and most preferably 0 ° to 20 °. That is, the closer the bending angle is to 0 °, the more preferable the embodiment.
  • the remaining bending angle is in the above-mentioned range, so that the layer between the pressure-sensitive adhesive layer and the layer thereof, and in each layer also for repeated bending. It is possible to obtain a laminate for a flexible image display device which is free from peeling and breakage and is excellent in bending resistance and adhesion, which is a preferable embodiment.
  • 1000 micrometers or less are preferable, as for whole thickness of the laminated body for flexible image displays of this invention, 800 micrometers or less are more preferable, and 500 micrometers or less are more preferable. Moreover, as said whole thickness, 20 micrometers or more are preferable, and 100 micrometers or more are more preferable.
  • the total thickness is greater than 1000 ⁇ m, the difference in the amount of strain applied to the outermost layer and the innermost layer of the bent portion becomes large, and cracking or peeling is likely to occur at the time of bending. If the total thickness is greater than 1000 ⁇ m, the amount of distortion of the pressure-sensitive adhesive layer is also increased, plastic deformation is likely to occur, and when it is attempted to return to a flat state from a bent state, the remaining bending angle increases. .
  • the flexible image display device of the present invention includes the above-described laminate for a flexible image display device and an organic EL display panel, and the laminate for a flexible image display device is disposed on the viewing side with respect to the organic EL display panel It is configured to be possible. Although optional, a window can be disposed on the viewing side with respect to the laminate for a flexible image display (see FIGS. 2 to 4).
  • FIG. 2 is a cross-sectional view of one embodiment of a flexible image display according to the present invention.
  • the flexible image display device 100 includes a laminate 11 for flexible image display device and an organic EL display panel 10 configured to be foldable. Then, the laminate 11 for flexible image display device is disposed on the viewing side with respect to the organic EL display panel 10, and the flexible image display device 100 is configured to be bendable.
  • a transparent window 40 can be disposed on the viewing side with respect to the flexible image display device laminate 11 via the first pressure-sensitive adhesive layer 12-1.
  • the laminate 11 for flexible image display device further includes an optical laminate 20, and a pressure-sensitive adhesive layer constituting a second pressure-sensitive adhesive layer 12-2 and a third pressure-sensitive adhesive layer 12-3.
  • the optical laminate 20 includes a polarizing film 1, a protective film 2 of a transparent resin material, and a retardation film 3.
  • the protective film 2 made of a transparent resin material is bonded to the first surface on the viewing side of the polarizing film 1.
  • the retardation film 3 is bonded to a second surface different from the first surface of the polarizing film 1.
  • the polarizing film 1 and the retardation film 3 generate circularly polarized light, for example, in order to prevent internal reflection of light entering from the viewing side of the polarizing film 1 and being emitted to the viewing side, or viewing angle To compensate for
  • the protective film is provided on both sides of the conventional polarizing film, whereas the protective film is provided on only one side, and the polarizing film itself is also used in the conventional organic EL display device.
  • the thickness of the optical laminate 20 can be reduced by using a very thin (20 ⁇ m or less) polarizing film as compared to the existing polarizing film.
  • the polarizing film 1 is very thin compared with the polarizing film used for the conventional organic electroluminescence display, the stress by the expansion-contraction generate
  • the possibility that the stress generated by the shrinkage of the polarizing film causes the deformation such as warping in the adjacent organic EL display panel 10 is greatly reduced, and the display quality deterioration due to the deformation and the breakage of the panel sealing material are significantly reduced. It is possible to In addition, the use of a thin polarizing film does not inhibit bending, which is a preferred embodiment.
  • the thickness (for example, 92 ⁇ m or less) of the optical laminated body 20 is reduced, and the first pressure-sensitive adhesive layer 12-1 as described above is formed.
  • the second film By placing the second film on the side opposite to the retardation film 3 with respect to the protective film 2, it becomes possible to reduce the bending angle remaining in the optical laminate 20, whereby the optical laminate 20 can be bent, and It is possible to suppress cracking of each layer and peeling of the pressure-sensitive adhesive layer at the bent portion, and finally, the laminate 11 for a flexible image display device can be made bendable. Therefore, the range of the remaining bending angle may be set appropriately in accordance with the environmental temperature at which the flexible image display device is used.
  • a foldable transparent conductive layer 6 constituting a touch sensor can be further disposed on the side of the retardation film 3 opposite to the protective film 2, a foldable transparent conductive layer 6 constituting a touch sensor can be further disposed.
  • the transparent conductive layer 6 is directly bonded to the retardation film 3 by a manufacturing method as disclosed in JP-A-2014-219667, whereby the thickness of the optical laminate 20 is reduced, and the optical laminate 20 is obtained. The stress applied to the optical laminated body 20 when bending is further reduced.
  • a pressure-sensitive adhesive layer constituting the third pressure-sensitive adhesive layer 12-3 can be further disposed on the side opposite to the retardation film 3 with respect to the transparent conductive layer 6.
  • the second pressure-sensitive adhesive layer 12-2 is directly bonded to the transparent conductive layer 6.
  • the flexible image display device shown in FIG. 3 is substantially the same as that shown in FIG. 2, but in the flexible image display device of FIG. 2, the touch sensor is on the opposite side to the protective film 2 with respect to the retardation film 3
  • the side opposite to the protective film 2 is disposed with respect to the first pressure-sensitive adhesive layer 12-1 while the foldable transparent conductive layer 6 constituting the second embodiment is disposed.
  • the foldable transparent conductive layer 6 which comprises a touch sensor is arrange
  • the third pressure-sensitive adhesive layer 12-3 is disposed on the opposite side to the retardation film 3 with respect to the transparent conductive layer 2;
  • the flexible image display device is different in that a second pressure-sensitive adhesive layer 12-2 is disposed on the opposite side of the retardation film 3 to the protective film 2.
  • the third pressure-sensitive adhesive layer 12-3 can be disposed when the window 40 is disposed on the viewing side with respect to the laminate 11 for flexible image display device.
  • the flexible image display device of the present invention can be suitably used as an image display device such as a flexible liquid crystal display device, an organic EL (electroluminescence) display device, and electronic paper. Moreover, it can be used irrespective of methods, such as a resistive film type and a capacitive type, such as a touch panel.
  • the flexible image display device of the present invention as shown in FIG. 4, it is also used as an in-cell flexible image display device in which the transparent conductive layer 6 constituting the touch sensor is incorporated in the organic EL display panel 10-1. It is possible.
  • the numerical values in the table are the blending amount (addition amount), and indicate the solid content or the solid content ratio (based on weight).
  • the contents of the formulation and the evaluation results are shown in Tables 1 to 5.
  • Example 1 [Polarizing film] Amorphous polyethylene terephthalate (hereinafter, also referred to as “PET”) (IPA copolymerized PET) film (thickness: 100 ⁇ m) having 7 mol% of isophthalic acid unit is prepared as a thermoplastic resin base material, and the surface is corona treated ( 58 W / m 2 / min) was applied.
  • PET polyethylene terephthalate
  • acetoacetyl-modified PVA manufactured by Japan Synthetic Chemical Industry Co., Ltd., trade name: GOCEFIMER Z 200 (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%)
  • GOCEFIMER Z 200 average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%
  • a 1 wt% added PVA degree of polymerization 4200, degree of saponification 99.2%
  • prepare a coating solution of a PVA aqueous solution of 5.5 wt% PVA resin and dry the film thickness And dried for 10 minutes by hot-air drying in an atmosphere of 60 ° C. to produce a laminate having a layer of PVA resin on the substrate.
  • this laminate was first subjected to free end stretching at a temperature of 130 ° C. in air at 1.8 times (air-assisted stretching) to form a stretched laminate.
  • a step of insolubilizing the PVA layer in which the PVA molecules contained in the stretched laminate were oriented was performed by immersing the stretched laminate in a boric acid insolubilizing aqueous solution at a liquid temperature of 30 ° C. for 30 seconds.
  • the boric acid insolubilizing aqueous solution of this step had a boric acid content of 3 parts by weight with respect to 100 parts by weight of water.
  • a colored laminate was produced by dyeing this stretched laminate.
  • the single layer transmittance of the PVA layer constituting the polarizing film to be finally produced is 40 to 44% in a dye solution containing iodine and potassium iodide at a liquid temperature of 30 ° C.
  • the PVA layer contained in the stretched laminate is dyed with iodine by immersion for an arbitrary time.
  • the staining solution contains water as a solvent, an iodine concentration of 0.1 to 0.4% by weight, and a potassium iodide concentration of 0.7 to 2.8% by weight.
  • the ratio of the concentration of iodine to potassium iodide is 1 to 7.
  • a step of cross-linking the PVA molecules of the PVA layer to which iodine was adsorbed was performed by immersing the colored laminate in a boric acid crosslinking aqueous solution at 30 ° C. for 60 seconds.
  • the boric acid content is 3 parts by weight with respect to 100 parts by weight of water
  • the potassium iodide content is 3 parts by weight with respect to 100 parts by weight of water.
  • the obtained colored laminate is stretched in an aqueous solution of boric acid at a stretching temperature of 70 ° C. and stretched 3.05 times in the same direction as the stretching in the previous air (stretching in boric acid water), An optical film laminate having a draw ratio of 5.50 was obtained.
  • the optical film laminate was removed from the aqueous boric acid solution, and the boric acid attached to the surface of the PVA layer was washed with an aqueous solution in which the potassium iodide content was 4 parts by weight with respect to 100 parts by weight of water.
  • the washed optical film laminate was dried by a hot air drying process at 60 ° C.
  • the thickness of the polarizing film contained in the obtained optical film laminate was 5 ⁇ m.
  • Protective film As a protective film, after extruding the methacrylic resin pellet which has a glutar imide ring unit, shape
  • This protective film had a thickness of 20 ⁇ m and was an acrylic film having a moisture permeability of 160 g / m 2 .
  • the polarizing film and the protective film were bonded to each other using an adhesive shown below to obtain a polarizing film.
  • each component is mixed according to the recipe described in Table 1 and stirred at 50 ° C. for 1 hour, an adhesive (active energy ray curable adhesive A) was prepared.
  • the numerical values in the table indicate weight% when the total amount of the composition is 100% by weight.
  • Each component used is as follows.
  • HEAA hydroxyethyl acrylamide M-220: ARONIX M-220, tripropylene glycol diacrylate), manufactured by Toagosei Co., Ltd.
  • ACMO acryloyl morpholine
  • AAEM 2-acetoacetoxyethyl methacrylate, manufactured by Japan Synthetic Chemical Industry UP-1190: ARUFON UP- 1190
  • Toagosei IRG 907 IRGACURE 907, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one
  • BASF DETX-S KAYACURE DETX-S, diethylthioxanthone, Nipponized Pharmaceutical company
  • the adhesive after laminating the protective film and the polarizing film through the adhesive, the adhesive is cured by irradiating ultraviolet rays, and the adhesive layer Formed.
  • a gallium-filled metal halide lamp Fusion UV Systems, Inc., trade name “Light HAMMER 10”, bulb: V bulb, peak illuminance: 1600 mW / cm 2 , integrated dose 1000 / mJ / cm 2 (wavelength 380-440 nm) was used.
  • the retardation film (1 ⁇ 4 wavelength retardation plate) of the present embodiment is composed of two layers, a retardation layer for quarter wave plate and a retardation layer for half wave plate, in which a liquid crystal material is oriented and fixed. It was a retardation film. Specifically, it was manufactured as follows.
  • Liquid crystal material As a material for forming a retardation layer for a half wave plate and a retardation layer for a quarter wave plate, a polymerizable liquid crystal material (manufactured by BASF, trade name: Paliocolor LC242) exhibiting a nematic liquid crystal phase was used.
  • a photopolymerization initiator (manufactured by BASF: trade name Irgacure 907) for the polymerizable liquid crystal material was dissolved in toluene. Furthermore, in order to improve the coating property, about 0.1 to 0.5% was added according to the liquid crystal thickness to a DIC megafac series to prepare a liquid crystal coating liquid.
  • the liquid crystal coating liquid was applied onto the alignment substrate by a bar coater, and then dried by heating at 90 ° C. for 2 minutes, and then the alignment was fixed by ultraviolet curing under a nitrogen atmosphere.
  • a substrate for example, one that can transfer the liquid crystal coating layer later, such as PET, was used.
  • a fluorine-based polymer a DIC megafac series
  • MIBK methyl isobutyl ketone
  • cyclohexanone or MIBK
  • the coating liquid was coated on a substrate by a wire bar, and a drying process for 3 minutes was obtained at a setting of 65 ° C., and the orientation was fixed by ultraviolet curing under a nitrogen atmosphere.
  • a substrate for example, one that can transfer the liquid crystal coating layer later, such as PET, was used.
  • the manufacturing process of this embodiment will be described with reference to FIG.
  • the numbers in FIG. 7 are different from the numbers in the other drawings.
  • the substrate 14 was provided by a roll, and the substrate 14 was supplied from the supply reel 21.
  • the coating liquid of the ultraviolet curable resin 10 was applied to the base 14 by the die 22.
  • the roll plate 30 was a cylindrical shaping mold in which the concavo-convex shape related to the alignment film for the 1 ⁇ 4 wavelength plate of the 1 ⁇ 4 wavelength retardation plate was formed on the circumferential side.
  • the substrate 14 coated with the ultraviolet curable resin is pressed against the circumferential side surface of the roll plate 30 by the pressure roller 24, and the ultraviolet curable resin is irradiated by the ultraviolet irradiation by the ultraviolet irradiation device 25 consisting of a high pressure mercury crucible. It was allowed to cure. Thereby, the manufacturing process 20 transferred the uneven
  • the liquid crystal material was cured by irradiation of ultraviolet rays by the ultraviolet irradiation device 27, and thereby, a configuration relating to the retardation layer for a 1 ⁇ 4 wavelength plate was created.
  • the substrate 14 is conveyed to the die 32 by the conveyance roller 31, and the coating liquid of the ultraviolet curable resin 12 is applied onto the retardation layer for quarter wave plate of the substrate 14 by the die 32.
  • the roll plate 40 was a cylindrical shaping mold in which the concavo-convex shape of the alignment film for a half wave plate of the quarter wave retardation plate was formed on the peripheral side.
  • the substrate 14 coated with the ultraviolet curable resin is pressed against the circumferential side surface of the roll plate 40 by the pressure roller 34, and the ultraviolet curable resin is irradiated by the ultraviolet irradiation by the ultraviolet irradiation device 35 made of high pressure mercury. It was allowed to cure. Thereby, the manufacturing process 20 transferred the uneven
  • the liquid crystal material is cured by the irradiation of ultraviolet light by the ultraviolet light irradiation device 37, and thereby, the configuration according to the retardation layer for a half wave plate is created, the retardation layer for a quarter wave plate, half wave A retardation film with a thickness of 7 ⁇ m composed of two layers of the retardation layer for plate was obtained.
  • optical film optical laminate
  • the retardation film obtained as described above and the polarizing film obtained as described above are continuously bonded using a roll-to-roll method using the above-mentioned adhesive, and the axis of the slow axis and the absorption axis
  • a laminated film optical laminated body was produced so that the angle was 45 °.
  • acrylic-type polymer A1 solution Part benzoyl peroxide (trade name: Niper BMT, manufactured by Nippon Oil and Fats Co., Ltd.) and 0.3 part by weight of a peroxide cross-linking agent, and acetoacetyl group-containing silane coupling agent (trade name: A-100, Koken) 0.3 part by weight of Chemical Co., Ltd.) was blended to prepare an acrylic pressure-sensitive adhesive composition (P1).
  • benzoyl peroxide trade name: Niper BMT, manufactured by Nippon Oil and Fats Co., Ltd.
  • acetoacetyl group-containing silane coupling agent trade name: A-100, Koken
  • the acrylic pressure-sensitive adhesive composition (P1) is uniformly coated with a fountain coater on the surface of a 75 ⁇ m-thick polyethylene terephthalate film (separator) treated with a silicone release agent, and an air circulating constant temperature of 155 ° C. It dried in oven for 2 minutes, and formed the 70-micrometer-thick 2nd adhesive layer on the surface of a base material. Subsequently, the separator on which the second pressure-sensitive adhesive layer was formed was transferred to the protective film side (corona treated) of the obtained optical laminate, to produce an optical laminate with a pressure-sensitive adhesive layer.
  • the first pressure-sensitive adhesive layer is formed into a first pressure-sensitive adhesive layer having a thickness of 50 ⁇ m based on the contents of the formulations in Tables 2 and 3, and a polyimide film having a thickness of 75 ⁇ m
  • a separator with a first pressure-sensitive adhesive layer was transferred to the surface (corona-treated) of (PI film, Toray DuPont Co., Ltd., Kapton 300V, base material) to form a pressure-sensitive adhesive layer-attached PI film .
  • the third pressure-sensitive adhesive layer is formed into a 50 ⁇ m-thick third pressure-sensitive adhesive layer based on the formulation contents in Tables 2 and 3, and a 125 ⁇ m-thick PET film A separator with a third adhesive layer was transferred to the surface (corona treated) of a transparent substrate (Mitsubishi resin Co., Ltd., trade name: diamond foil) to form a PET film with an adhesive layer. .
  • the first to third pressure-sensitive adhesive layers (with each transparent base material) obtained as described above are used as PET films to be a 25 ⁇ m thick transparent base material 8-1.
  • Pressure-sensitive adhesive layer 12-1 is attached, the third pressure-sensitive adhesive layer 12-3 is attached to the retardation film 3, and the first pressure-sensitive adhesive layer 12-1 is attached to the transparent base 8-1.
  • the second pressure-sensitive adhesive layer 12-2 was attached to the surface of the (PET film) on which the transparent conductive layer 6 was formed, to prepare a laminate 11 for a flexible image display used in the example.
  • oligomer B1 an acrylic oligomer
  • the weight average molecular weight of the oligomer B1 was 4500.
  • a predetermined amount of the obtained oligomer B1 was added when mixing a crosslinking agent and the like to prepare an acrylic pressure-sensitive adhesive composition (P2).
  • Example 2 and Comparative Examples 1 and 2 In preparing the polymer ((meth) acrylic polymer), the acrylic oligomer, the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive layer to be used, it was changed as shown in Tables 2 to 4 except for those specified. A laminate for a flexible image display was produced in the same manner as in Example 1 except for the above.
  • Examples 3 to 6 100 parts by weight of the monomer mixture shown in Table 2, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “IRGACURE 651”, manufactured by BASF Japan Ltd.) which is a photopolymerization initiator, and 0.05 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name “IRGACURE 184”, manufactured by BASF Japan Ltd.) is placed in a four-necked flask, and the viscosity (BH viscosity system No.
  • a partially polymerized monomer syrup (partially polymerized product of monomer components) A2 to A5 was obtained by irradiating with ultraviolet light and photopolymerizing until it had a rotor of 10 rpm and a temperature of 30 ° C.) of about 15 Pa ⁇ s.
  • 1,6-hexanediol diacrylate (trade name “A-HD-N”, manufactured by Shin-Nakamura Chemical Co., Ltd., HDDA, multifunctional) as shown in Table 3 in 100 parts by weight of each partially polymerized monomer syrup obtained.
  • Monomer 0.3 parts by weight, and 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “IRGACURE 651”, manufactured by BASF Japan Ltd., a photopolymerization initiator (additional initiator)) 0 .6 parts by weight and 0.3 parts by weight of silane coupling agent (trade name "KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly mixed to prepare acrylic pressure-sensitive adhesive compositions (P3) to (P6).
  • silane coupling agent trade name "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.
  • Irgacure 184 Photopolymerization initiator, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF)
  • Irgacure 651 Photopolymerization initiator, 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF)
  • AIBN azo polymerization initiator, 2,2'-azobisisobutyro nitrile (manufactured by Kishda Chemical Co., Ltd.)
  • ⁇ Measurement of thickness> The thicknesses of the polarizing film, the retardation film, the protective film, the optical laminate, the pressure-sensitive adhesive layer and the like were measured using a dial gauge (manufactured by Mitutoyo).
  • FIGS. 5A and 5B show schematic views of a bending test based on a U-shaped stretch tester (Yuasa System Instruments Co., Ltd.).
  • the testing machine has a mechanism that repeats U-shaped 180 ° bending without load on a planar work in a thermostatic chamber, and adjusts the bending radius by adjusting the distance between the U-shaped surfaces. It can be changed.
  • the 2.5 cm ⁇ 10 cm laminate for a flexible image display obtained in each Example and Comparative Example is set in a tester so that it can be bent in the long side direction, 25 ° C.
  • the evaluation was performed under the conditions of 180 °, bending radius 3 mm, and bending speed 1 second / times.
  • the configuration shown in FIG. 6 is adopted, and the transparent substrate 8-2 (PET film) is concave side (inner side), and the substrate 9 (PI film) is convex side (outside) And evaluated by bending in the direction of the long side near the center.
  • the bending resistance was evaluated by the number of times until cracking or peeling of an interlayer occurs at a bent portion of the laminate for a flexible image display device.
  • the test was discontinued.
  • first adhesive layer 50 ⁇ m
  • second adhesive layer 70 ⁇ m
  • third adhesive layer 50 ⁇ m

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Electroluminescent Light Sources (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne : un corps stratifié destiné à un dispositif d'affichage d'image souple, comprenant une couche adhésive et un film optique comprenant au moins une membrane polarisante. L'angle de pliage restant lorsque le corps en couches est plié à 180° et remis ensuite dans un état plat est compris dans une plage spécifique. Le corps stratifié destiné à un dispositif d'affichage d'image souple présente une excellente résistance à la flexion ou une excellente adhésion, ne se décolle pas et ne se rompt pas, même après des flexions répétées. L'invention concerne un dispositif d'affichage d'image souple dans lequel le corps stratifié pour dispositif d'affichage d'image souple est installé. Le corps stratifié pour dispositif d'affichage d'image souple comprend une couche adhésive et un film optique comprenant au moins une membrane polarisante, ledit corps stratifié pour dispositif d'affichage d'image souple étant caractérisé par l'angle de pliage restant lorsque le corps stratifié est plié à 180° et remis ensuite dans un état plat, compris entre 0° et 60°.
PCT/JP2018/028091 2017-07-31 2018-07-26 Corps stratifié pour dispositif d'affichage d'image souple, et dispositif d'affichage d'image souple WO2019026760A1 (fr)

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WO2021171807A1 (fr) * 2020-02-28 2021-09-02 住友化学株式会社 Corps optique en couches et dispositif d'affichage d'image souple
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JP2021081700A (ja) * 2019-11-20 2021-05-27 住友化学株式会社 光学積層体及び表示装置
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JP2021081699A (ja) * 2019-11-20 2021-05-27 住友化学株式会社 光学積層体及び表示装置
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CN115135737A (zh) * 2020-03-17 2022-09-30 日东电工株式会社 用于挠性图像显示装置内的层叠体的粘合片、用于挠性图像显示装置的层叠体、以及挠性图像显示装置
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