WO2022163281A1 - 活性エネルギー線硬化性粘着シート、離型フィルム付き粘着シート、積層体、積層体の製造方法、積層シート、画像表示装置用積層体、フレキシブル画像表示装置,フレキシブルディスプレイ用粘着シートおよび画像表示装置用積層体の製造方法 - Google Patents
活性エネルギー線硬化性粘着シート、離型フィルム付き粘着シート、積層体、積層体の製造方法、積層シート、画像表示装置用積層体、フレキシブル画像表示装置,フレキシブルディスプレイ用粘着シートおよび画像表示装置用積層体の製造方法 Download PDFInfo
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- WO2022163281A1 WO2022163281A1 PCT/JP2021/048543 JP2021048543W WO2022163281A1 WO 2022163281 A1 WO2022163281 A1 WO 2022163281A1 JP 2021048543 W JP2021048543 W JP 2021048543W WO 2022163281 A1 WO2022163281 A1 WO 2022163281A1
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- WIPO (PCT)
- Prior art keywords
- adhesive sheet
- pressure
- sensitive adhesive
- meth
- active energy
- Prior art date
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 239000003230 hygroscopic agent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical compound OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical class CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
-
- 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
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
Definitions
- the present invention relates to an adhesive sheet that can be suitably used for an image display device having a curved surface, a bendable flexible image display device, and the like.
- a pressure-sensitive adhesive sheet that can be suitably used for bonding members for constituting an image display device having a stepped portion on the bonding surface, a pressure-sensitive adhesive sheet with a release film using the pressure-sensitive adhesive sheet, a laminate, and a laminate Laminate sheet, laminate for image display device, flexible image display device, adhesive sheet for flexible display, and method for producing laminate for image display device.
- Such a display device has a laminated structure in which multiple sheet members such as a cover lens, a circularly polarizing plate, a touch film sensor, and a light-emitting element are bonded together with a transparent adhesive sheet. When applied, it can be regarded as a laminate in which the member and the adhesive sheet are laminated.
- Patent Document 1 by setting the product value of the creep compliance fluctuation value and the relaxation elastic modulus fluctuation value to a suitable range, it is applied to a repeatedly bending device, and the bending state can be maintained for a long period of time.
- the pressure-sensitive adhesive for repeatedly bending devices and the pressure-sensitive adhesive that exhibits high resilience such as suppressing deformation of the pressure-sensitive adhesive layer after being released from the bending state in the case of being placed in a curved state and mitigating the effects of being placed in the bending state Sheets and flex laminate members and repeat flex devices are disclosed.
- the surface of a member constituting the image display device (also referred to as “image display device constituent member”) is made uneven by wiring, printing, pattern development, surface treatment, or the like.
- the pressure-sensitive adhesive sheet for bonding image display device constituent members having such a stepped portion follows the step while being thin, under the limitation that it cannot be thickened due to the demand for thinning of the image display device. If it is not possible to fill all the corners of the adhesive layer, air bubbles may be generated inside the adhesive layer, so the adhesive sheet is required to have high fluidity. However, it has been difficult to stably exhibit resilience and durability in a wide temperature range with a pressure-sensitive adhesive sheet having high fluidity at the time of lamination.
- the present invention enables even an image display device component having a stepped portion on the surface to be filled to every corner so as to follow the stepped portion so as not to generate air bubbles, and to display an image.
- a laminate having a configuration in which a device component and an adhesive sheet are laminated can exhibit excellent resilience and durability even when bending is performed in a high temperature environment, and when bending is performed in a low temperature environment.
- the present invention proposes an active energy ray-curable pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing a meth)acrylic polymer (A) and satisfying the following requirements (1) to (3).
- (1) It has a thickness of 0.8 mm to 1.5 mm and a strain (creep strain) of 50% or more when a pressure of 1000 Pa is applied at a temperature of 25° C. for 3600 seconds.
- (2) After irradiating an active energy ray with a wavelength of 365 nm with an integrated light amount of 2000 to 4000 mJ / cm 2 with a thickness of 0.8 mm to 1.5 mm, a pressure of 1000 Pa at a temperature of 80 ° C. is applied for 180 seconds. creep strain) becomes 10% or more.
- the present invention also proposes a release film-attached pressure-sensitive adhesive sheet having a structure in which the active energy ray-curable pressure-sensitive adhesive sheet proposed by the present invention and a release film are laminated.
- the present invention also provides a method in which a release film and a member for constituting an image display device having a step with a height difference of 2 ⁇ m or more on the surface to be laminated are laminated via the active energy ray-curable adhesive sheet proposed by the present invention.
- a laminate having a structure of
- a release film and an image display device constituting member having a step with a height difference of 2 ⁇ m or more on the surface to be laminated are laminated via the active energy ray-curable adhesive sheet proposed by the present invention,
- a method for producing a laminate is proposed in which the pressure-sensitive adhesive sheet is irradiated with an active energy ray through the release film from the release film side.
- the present invention also proposes a laminated sheet having a structure in which the active energy ray-curable pressure-sensitive adhesive sheet proposed by the present invention and another pressure-sensitive adhesive sheet are laminated.
- the present invention also includes a structure in which two image display device constituent members are laminated via the active energy ray-curable pressure-sensitive adhesive sheet proposed by the present invention, and at least one of the image display device constituent members is proposes a layered product for an image display device having a step having a height difference of 2 ⁇ m or more on the contact surface with the pressure-sensitive adhesive sheet.
- the present invention also provides a flexible display pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer containing a (meth)acrylic polymer (A),
- the thickness is 15 ⁇ m or more and 50 ⁇ m or less,
- a member for constituting an image display device having active energy ray curability and having steps with a height difference of 2 to 10 ⁇ m at intervals of 10 mm or less is laminated under the following bonding conditions, there is no foaming around the steps.
- a pressure-sensitive adhesive sheet for a flexible display characterized by: (Lamination conditions) a) A pressure-sensitive adhesive sheet having a thickness of 15 to 50 ⁇ m is irradiated with ultraviolet rays so that the integrated amount of light at 365 nm is 2000 to 4000 mJ/cm 2 . b) The pressure-sensitive adhesive sheet is vacuum-bonded to the surface of a substrate having steps with height differences of 2 to 10 ⁇ m at intervals of 10 mm or less under conditions of a press pressure of 0.2 MPa and 30 seconds. c) Perform autoclave treatment under conditions of 70° C., atmospheric pressure of 0.45 MPa, and 20 minutes.
- the present invention also provides a method for producing a laminate for image display device comprising two image display device constituent members 1 and 2 laminated via an active energy ray-curable adhesive sheet, comprising:
- a method for producing a laminate for an image display device is proposed, which has the following steps 1 to 3, and is characterized by performing steps 1 and 2 and then performing step 3.
- Step 1 One surface of the active energy ray-curable pressure-sensitive adhesive sheet proposed by the present invention is attached to the member 1 for constituting an image display device.
- Step 2 The active energy ray-curable pressure-sensitive adhesive sheet proposed by the present invention is cured by irradiating it with an active energy ray.
- Step 3 The image display device constituting member 2 is adhered to the other surface of the pressure-sensitive adhesive sheet to form a laminate.
- the pressure-sensitive adhesive sheet proposed by the present invention fills every corner of the adherend so as to follow the step so as not to generate air bubbles even if there is a step on the sticking surface of the image display device constituent member that is the adherend. can do. Furthermore, the pressure-sensitive adhesive sheet proposed by the present invention exhibits excellent resilience and durability even when a laminate having a configuration in which the pressure-sensitive adhesive sheet and image display device constituent members are laminated is operated to bend in a high-temperature environment. Excellent durability can be exhibited even when a bending operation is performed in a low-temperature environment. Therefore, for example, even when the laminate is folded, curved, or wound up in a high-temperature or low-temperature environment, excellent durability or resilience can be exhibited. From the above points, the pressure-sensitive adhesive sheet proposed by the present invention can be suitably used, for example, as a pressure-sensitive adhesive sheet for flexible displays.
- a pressure-sensitive adhesive sheet (referred to as "the present pressure-sensitive adhesive sheet") according to an example of the embodiment of the present invention includes a (meth)acrylic polymer (A), particularly a pressure-sensitive adhesive layer (“the present pressure-sensitive adhesive layer ”) is an active energy ray-curable pressure-sensitive adhesive sheet.
- the present pressure-sensitive adhesive layer in the present pressure-sensitive adhesive sheet contains, for example, a (meth)acrylic polymer (A), particularly the (meth)acrylic polymer (A) as a main component resin, preferably a cross-linking agent (B) and/or a polymerization initiator (C) and, if necessary, a pressure-sensitive adhesive composition (referred to as "the present pressure-sensitive adhesive composition”) containing other components.
- the "active energy ray-curable adhesive sheet” is a pressure-sensitive adhesive sheet having properties that can be cured by an active energy ray, in other words, an active energy ray-curable adhesive sheet that leaves room for curing by an active energy ray. is the meaning of This pressure-sensitive adhesive sheet may have been cured (also referred to as “temporary curing”) in a state in which there is room for curing by the active energy ray, or may have not been cured at all (referred to as “uncured”). ) and can be cured by active energy rays. If the adhesive sheet is temporarily cured or uncured, the adhesive sheet is cured with active energy rays before or after bonding the adhesive sheet to the adherend ("main curing ), which can result in increased cohesion and improved adhesion.
- the "main component resin” means the resin having the highest mass ratio among the resins constituting the pressure-sensitive adhesive layer or the pressure-sensitive adhesive composition.
- the content of the main component resin is 70% by mass or more, especially 80% by mass or more, and 90% by mass or more (including 100% by mass) of the resins constituting the present pressure-sensitive adhesive layer or the present pressure-sensitive adhesive composition. may occupy.
- the pressure-sensitive adhesive sheet preferably has a thickness of 0.8 mm to 1.5 mm and a strain (creep strain) of 50% or more when a pressure of 1000 Pa is applied at a temperature of 25° C. for 3600 seconds.
- the fact that the pressure-sensitive adhesive sheet has a creep strain of 50% or more when a pressure of 1000 Pa is applied at a temperature of 25° C. for 3600 seconds before curing indicates that it is easily deformable in this state. Even if the surface of the member constituting the image display device, which is the adherend, has unevenness, it can be made to follow every corner of the stepped portion, which is preferable.
- the pressure-sensitive adhesive sheet preferably has a creep strain of 50% or more, more preferably 100% or more, more preferably 105% or more, particularly 110% or more.
- the creep strain is preferably 10000% or less because the shape can be maintained at room temperature or lower.
- the creep strain of the present pressure-sensitive adhesive sheet is more preferably 5000% or less, more preferably 2500% or less, further preferably 1000% or less, more preferably 500% or less, particularly 250% or less. % or less is more preferable.
- the creep strain in the present pressure-sensitive adhesive sheet is a numerical value when the thickness is 0.8 mm to 1.5 mm. It is necessary to avoid fluctuations in measurement results due to the influence of measurement jigs due to insufficient thickness. To this end, it is necessary to measure the present pressure-sensitive adhesive sheet after adjusting it within a certain range of thickness. By adjusting the thickness of the pressure-sensitive adhesive sheet in advance within the above range and then measuring the creep strain, the creep strain of the pressure-sensitive adhesive sheet can be accurately determined without being affected by the measuring jig.
- the above-mentioned "thickness of 0.8 mm to 1.5 mm” means that if the thickness of the adhesive sheet as a measurement sample is less than this range, the thickness of the measurement sample may be adjusted by stacking several sheets. It means to adjust the depth to this range. The same is true when the thickness of the measurement sample is specified in other tests.
- the composition and molecular weight of the (meth)acrylic polymer (A) are adjusted, and the type and amount of the cross-linking agent (B) are adjusted. is preferred. However, it is not limited to this means.
- the pressure-sensitive adhesive sheet had a thickness of 0.8 mm to 1.5 mm, and was irradiated with an active energy ray having a wavelength of 365 nm in an integrated light amount of 2000 to 4000 mJ/cm 2 , and then a pressure of 1000 Pa was applied at a temperature of 80 ° C. for 180 seconds. It is preferable that the time strain (creep strain) is 10% or more.
- This PSA sheet has a strain (creep strain) of 10% or more when a pressure of 1000 Pa is applied at a temperature of 80° C. for 180 seconds after curing.
- the creep strain after curing with active energy rays is more preferably 10% or more, more preferably 20% or more, more preferably 30% or more, more preferably 40% or more.
- the upper limit of the strain (creep strain) after curing is too high, the pressure-sensitive adhesive sheet may protrude from the end face of the laminate in a high-temperature environment and the end face may become sticky, cohesive peeling may occur during folding, It is preferably 500% or less, more preferably 300% or less, even more preferably 100% or less, and 80% or less because there is a risk of impairing the resilience when opened from the state. is particularly preferred, and 60% or less is most preferred.
- the creep strain of the present pressure-sensitive adhesive sheet after curing with active energy rays is also measured after adjusting the thickness of the present pressure-sensitive adhesive sheet to 0.8 mm to 1.5 mm in the same manner as described above. As described above, is based on consideration of the influence of the measuring jig, and is not intended to require the thickness of the pressure-sensitive adhesive sheet to be within the above range.
- the composition and molecular weight of the (meth)acrylic polymer (A), which is the base polymer described later, may be adjusted, or the cross-linking agent ( It is preferable to adjust the type and addition amount of B) or to adjust the irradiation dose of the active energy ray.
- the type and addition amount of B may be adjusted, or the cross-linking agent ( It is preferable to adjust the type and addition amount of B) or to adjust the irradiation dose of the active energy ray.
- This pressure-sensitive adhesive sheet preferably has a recovery rate of 60% or more after 200% deformation at 25° C., which is represented by the following formula when irradiated with an active energy ray having a wavelength of 365 nm with an accumulated amount of light of 2000 to 4000 mJ/cm 2 .
- the recovery rate is represented by the following formula.
- Restoration rate (%) ⁇ (xy)/x ⁇ x 100 (x is the initial strain applied in the shear direction to the adhesive sheet with a thickness of 0.8 mm to 1.5 mm, and y is the residual strain after 600 seconds after the initial strain was applied for 600 seconds and released. A more specific measurement method is described in Examples.)
- the recovery rate of this adhesive sheet after curing is 60% or more, permanent deformation can be suppressed, and the recovery property when unfolded from the folded state is also good. From this point of view, the recovery rate is preferably 70% or more, more preferably 75% or more, and more preferably 80% or more.
- the recovery rate of the present pressure-sensitive adhesive sheet is also measured after adjusting the thickness of the pressure-sensitive adhesive sheet to 0.8 mm to 1.5 mm in the same manner as described above. It is intended to take into consideration the influence of the measuring jig, and is not intended to require the thickness of the pressure-sensitive adhesive sheet to be within the above range.
- the adhesive sheet Before being cured by active energy rays, the adhesive sheet is preferably in an uncrosslinked state or a slightly crosslinked state, that is, in a state where the gel fraction is 0% or more and 20% or less. From the viewpoint of conformability to irregularities on the adherend surface, the gel fraction is more preferably 10% or less, even more preferably 8% or less, and even more preferably 5% or less.
- the gel fraction after curing with active energy rays is 10% or more, the shape stability of the pressure-sensitive adhesive sheet, and the resilience and durability when folded when formed into a laminate can be imparted.
- the gel fraction after curing with active energy rays is preferably 10% or more, more preferably 30% or more, and more preferably 40% or more.
- the gel fraction after active energy ray curing is preferably 85% or less.
- the gel fraction after curing with active energy rays is more preferably 70% or less, more preferably 60% or less, and even more preferably 55% or less.
- this pressure-sensitive adhesive sheet is cured by irradiating an active energy ray with a wavelength of 365 nm at an accumulated light amount of 1000 mJ/cm 2 , the gel fraction does not change or increases by less than 0.5% compared to before curing. There may be.
- the present pressure-sensitive adhesive sheet may have such a low photosensitivity.
- the composition and molecular weight of the (meth)acrylic polymer (A), which is the base polymer, may be adjusted, or the type of the cross-linking agent (B) may be adjusted. It is preferable to adjust the addition amount of the active energy ray, and to adjust the intensity of the active energy ray to be irradiated and the integrated amount of light. However, it is not limited to this means.
- the pressure-sensitive adhesive sheet preferably has the following properties (4). (4) Adhesive strength to the surface of soda lime glass at 23° C. 50% RH, peel angle 180°, peel speed 300 mm / min is 1 N / cm or more.
- the adhesive strength is 1 N/cm or more, it is preferable because it facilitates positioning and temporary fixation when bonding the image display device constituent members to be described later. From this point of view, the adhesive strength is preferably 1 N/cm or more, more preferably 2 N/cm or more, still more preferably 4 N/cm or more, and particularly preferably 5 N/cm or more. , 10 N/cm or more. Incidentally, the normal upper limit is 40 N/cm.
- the pressure-sensitive adhesive sheet also preferably has the following properties (5).
- the adhesive strength is 1 N/cm or more, it is preferable because when a laminated body is formed by laminating together with the image display device constituent members described later, delamination or the like does not occur at the time of bending, and durability is improved.
- the adhesive strength when irradiated with active energy rays after lamination to soda lime glass is preferably 1 N/cm or more, more preferably 2 N/cm or more, and 3 N/cm or more. It is more preferable that it is 5 N/cm or more. Incidentally, the normal upper limit is 40 N/cm.
- the pressure-sensitive adhesive sheet further preferably has the following properties (6).
- (6) After irradiating an active energy ray with a wavelength of 365 nm at an integrated light amount of 2000 to 4000 mJ/cm 2 , when the adhesive sheet is laminated to soda lime glass, peeling at 23 ° C. 50% RH and peeling from the surface of the soda lime glass.
- Adhesive strength is 1 N/cm or more at an angle of 180° and a peeling speed of 300 mm/min
- the adhesive strength is 1 N/cm or more, it is preferable because delamination or the like does not occur at the time of bending when a laminate is formed by laminating together with the image display device constituent members described later, and durability is improved.
- the pressure-sensitive adhesive sheet has an adhesive force of 1 N/cm or more, more preferably 2 N/cm or more, more preferably 3 N/cm or more when the adhesive sheet is laminated to soda lime glass after being cured with an active energy ray. /cm or more, and more preferably 5 N/cm or more.
- the normal upper limit is 40 N/cm.
- the pressure-sensitive adhesive sheet preferably has a thickness of 0.8 mm to 1.5 mm, and a loss tangent obtained by dynamic viscoelasticity measurement in a shear mode at a frequency of 1 Hz is 0.8 or more at -30°C. It is more preferably 1 or more, especially 1.2 or more, still more preferably 1.5 or more, and more preferably 2.0 or less, still more preferably 1.8 or less.
- the loss tangent (tan ⁇ ) of the present adhesive sheet is within the above range, even if the adherend has irregularities on the adherend surface, the adhesive resin can flow and fill the stepped portions by heating, which is preferable.
- the pressure-sensitive adhesive sheet after curing the active energy ray, that is, after irradiating the active energy ray with a wavelength of 365 nm in an integrated light amount of 2000 to 4000 mJ/cm 2 , the pressure-sensitive adhesive sheet has a thickness of 0.8 mm to 1.5 mm and a shear at a wave number of 1 Hz.
- the loss tangent obtained by dynamic viscoelasticity measurement in mode is preferably 0.5 or more and 2.3 or less in the range of -30°C or more and -10°C or less.
- the loss tangent (tan ⁇ ) after curing is within the above range, even if the laminate using the present pressure-sensitive adhesive sheet is folded in a low-temperature environment, peeling or buckling at the interface of image display device constituent members, and image display device constituent members do not occur. It is preferable because it does not cause cracks or the like.
- the loss tangent (tan ⁇ ) in the range of ⁇ 30° C. or higher and ⁇ 10° C. or lower is preferably 0.5 or higher and 2.3 or lower, especially 0.8 or higher or 2.0 or lower. is more preferable, and among them, 1.1 or more or 1.9 or less is more preferable.
- the pressure-sensitive adhesive sheet has a thickness of 0.8 mm to 1.5 mm, and the maximum loss tangent obtained when dynamic viscoelasticity is measured in a shear mode at a frequency of 1 Hz is ⁇ 20° C. or less. is preferred. It is preferable that the maximum point of the loss tangent is ⁇ 20° C. or less, because the laminate can have durability when folded. From this point of view, the maximum point of the loss tangent is more preferably ⁇ 25° C. or less, more preferably ⁇ 30° C. or less, even more preferably ⁇ 33° C. or less, and particularly preferably ⁇ 35° C. or less. Also, the lower limit is usually -60° C. or higher.
- the loss tangent before or after curing of the pressure-sensitive adhesive sheet is also measured after adjusting the thickness of the pressure-sensitive adhesive sheet to 0.8 mm to 1.5 mm in the same manner as described above. As described above, is based on consideration of the influence of the measuring jig, and is not intended to require the thickness of the pressure-sensitive adhesive sheet to be within the above range.
- the composition and molecular weight of the (meth)acrylic polymer (A), which is the base polymer described later, may be adjusted, or the cross-linking agent (B ) is preferably adjusted and the amount of active energy ray irradiation is adjusted.
- the cross-linking agent (B ) is preferably adjusted and the amount of active energy ray irradiation is adjusted.
- the adhesive sheet has a thickness of 0.8 mm to 1.5 mm and a storage modulus (G′) of 0.01 to 0.2 MPa obtained by dynamic viscoelasticity measurement in a shear mode at a temperature of 25° C. and a frequency of 1 Hz. It is preferable to have When the storage elastic modulus (G′) of the present pressure-sensitive adhesive sheet is within such a range, even if the adherend surface of the adherend has unevenness, it can be attached so as to follow the unevenness and absorb the unevenness.
- the storage elastic modulus (G') of the present pressure-sensitive adhesive sheet is preferably 0.01 MPa or more and 0.2 MPa or less at a temperature of 25° C. and a frequency of 1 Hz, especially 0.02 MPa or more or 0.1 MPa or less. and more preferably 0.03 MPa or more or 0.09 MPa or less.
- the pressure-sensitive adhesive sheet after curing the active energy ray, that is, after irradiating the active energy ray with a wavelength of 365 nm in an integrated light amount of 2000 to 4000 mJ/cm 2 , the pressure-sensitive adhesive sheet has a thickness of 0.8 mm to 1.5 mm and a temperature of 25°C.
- the storage elastic modulus (G') obtained by dynamic viscoelasticity measurement in shear mode at a frequency of 1 Hz is preferably 0.02 MPa or more and 0.24 MPa or less.
- the storage elastic modulus (G′) after curing of the pressure-sensitive adhesive sheet is within such a range, when a layered product is formed by laminating it with an image display device item painter member described later, delamination or the like does not occur when bending, and the adhesive sheet is durable. good properties.
- the storage elastic modulus (G′) after curing of the pressure-sensitive adhesive sheet is preferably 0.02 MPa or more and 0.24 MPa or less at a temperature of 25° C. and a frequency of 1 Hz. It is preferably 0.20 MPa or less, more preferably 0.04 MPa or more or 0.10 MPa or less.
- the storage elastic modulus (G') of the pressure-sensitive adhesive sheet before or after curing is also measured after adjusting the thickness of the pressure-sensitive adhesive sheet to 0.8 mm to 1.5 mm in the same manner as described above.
- the reason for this is that the influence of the measuring jig is considered, and the thickness of the pressure-sensitive adhesive sheet is not necessarily within the above range.
- the composition and molecular weight of the (meth)acrylic polymer (A), which is the base polymer described later, may be adjusted, or the cross-linking agent may be adjusted. It is preferable to adjust the type and amount of addition of (B), and to adjust the dose of active energy rays. However, it is not limited to this means.
- the pressure-sensitive adhesive composition is a composition containing a (meth)acrylic polymer (A), preferably a cross-linking agent (B) and/or a polymerization initiator (C), and optionally other components. .
- the pressure-sensitive adhesive composition contains a (meth)acrylic polymer (A), especially as a main component resin. That is, the (meth)acrylic polymer (A) is a resin having the highest mass ratio among the resins constituting the pressure-sensitive adhesive composition. At this time, among the resins constituting the present pressure-sensitive adhesive composition, the mass ratio of the (meth)acrylic polymer (A) is 50% by mass or more, especially 70% by mass or more, especially 80% by mass or more, especially 90% by mass. % or more (including 100% by mass).
- the (meth)acrylic polymer (A) As the (meth)acrylic polymer (A), the following formula 1 (wherein R 1 represents a hydrogen atom or a methyl group and R 2 represents a linear or branched alkyl having 4 to 18 carbon atoms group or an alicyclic hydrocarbon), and is preferably obtained by polymerizing a polymer component containing 50% by mass or more of the monomer component.
- the (meth)acrylic polymer (A) is more preferably polymerized to contain 55% by mass or more of the monomer component as a polymerization component, and particularly preferably polymerized to contain 60% by mass or more.
- (meth)acrylic means acrylic and methacrylic
- (meth)acryloyl means acryloyl and methacryloyl
- (meth)acrylate means acrylate and methacrylate, respectively.
- (co)polymer is meant to include polymers and copolymers.
- Examples of the monomer represented by Formula 1 include n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl ( meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, unde
- butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate and lauryl (meth)acrylate is particularly preferable.
- the (meth)acrylic polymer (A) is preferably a copolymer having "another copolymerizable monomer" other than the monomer component as a copolymerization component.
- the above-mentioned "other copolymerizable monomer” is preferably contained in the (meth)acrylic polymer (A) in an amount of 1 to 30% by mass, and is contained in a proportion of 2% by mass or more or 25% by mass or less. is more preferred.
- Examples of the “other copolymerizable monomer” include (a) a carboxyl group-containing monomer (hereinafter also referred to as “copolymerizable monomer a1”), (b) a hydroxyl group-containing monomer (hereinafter also referred to as “copolymerizable monomer a2").
- Examples of the copolymerizable monomer a1 include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypropyl (meth)acrylate, carboxybutyl (meth)acrylate, ⁇ -carboxypolycaprolactone mono(meth)acrylate, 2- (Meth) acryloyloxyethyl hexahydrophthalate, 2-(meth) acryloyloxypropyl hexahydrophthalate, 2-(meth) acryloyloxyethyl phthalate, 2-(meth) acryloyloxypropyl phthalate, 2-(meth) ) ) acryloyloxyethyl maleate, 2-(meth)acryloyloxypropyl maleate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxypropyl succinate, crotonic acid, fumaric acid, maleic acid, itacon Men
- Examples of the copolymerizable monomer a2 include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy Butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol Hydroxyalkyl (meth)acrylates such as polybutylene glycol mono(meth)acrylate, polypropylene glycol polybutylene glycol mono(meth)acrylate and hydroxyphenyl(meth)acrylate can be mentioned. These may be used alone or in combination of two or more.
- Examples of the copolymerizable monomer a3 include aminoalkyl (meth)acrylates such as aminomethyl (meth)acrylate, aminoethyl (meth)acrylate, aminopropyl (meth)acrylate, aminoisopropyl (meth)acrylate, N-alkylamino Examples include N,N-dialkylaminoalkyl (meth)acrylates such as alkyl (meth)acrylates, N,N-dimethylaminoethyl (meth)acrylate, and N,N-dimethylaminopropyl (meth)acrylate. These may be used alone or in combination of two or more.
- Examples of the copolymerizable monomer a4 include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether. . These may be used alone or in combination of two or more.
- Examples of the copolymerizable monomer a5 include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, Mention may be made of N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, diacetone(meth)acrylamide, maleic acid amide and maleimide. These may be used alone or in combination of two or more.
- Examples of the copolymerizable monomer a6 include compounds having a vinyl group in the molecule.
- Examples of such compounds include functional monomers having functional groups such as alkoxylalkyl groups such as ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate, methoxydipropylene glycol acrylate, and methoxypolypropylene glycol acrylate.
- polyalkylene glycol di(meth)acrylates and vinyl ester monomers such as vinyl acetate, N-vinyl-2-pyrrolidone, vinyl propionate and vinyl laurate, and styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene and Other aromatic vinyl monomers such as substituted styrene can be exemplified. These may be used alone or in combination of two or more.
- Examples of the copolymerizable monomer a7 include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, and the like. These may be used alone or in combination of two or more.
- the macromonomer as the copolymerizable monomer a8 is a macromonomer having a terminal functional group and a high-molecular-weight skeleton component.
- the "other copolymerizable monomer” is the copolymerizable monomer a8
- the (meth)acrylic polymer (A) is a copolymer containing a macromonomer-derived structural unit.
- the skeleton component of the macromonomer is preferably composed of an acrylic acid ester polymer or a vinyl polymer.
- the (meth)acrylate having a linear or branched alkyl group having 4 to 18 carbon atoms, the copolymerizable monomer a1, the copolymerizable monomer a2, the copolymerizable monomer a6, the copolymerizable Those exemplified by the monomer a7 and the like can be mentioned, and these can be used alone or in combination of two or more.
- the number average molecular weight of the macromonomer is preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more. The upper limit of the number average molecular weight is usually 20,000.
- the macromonomer is a macromonomer obtained by copolymerizing a (meth)acrylate having a linear or branched alkyl group having 1 to 3 carbon atoms. It is good because it can improve the properties.
- the number average molecular weight of such a macromonomer is preferably 1,000 to 10,000, particularly preferably 1,500 or more or 5,000 or less, and still more preferably 2,000 or more or 4,000 or less.
- the macromonomer is a macromonomer obtained by copolymerizing a (meth)acrylate having a linear or branched alkyl group having 8 to 18 carbon atoms, the adhesion surface of the adherend becomes more uneven.
- the number average molecular weight of such a macromonomer is preferably 2,000 to 20,000, particularly preferably 3,000 or more or 15,000 or less, and still more preferably 4,000 or more or 10,000 or less.
- a macromonomer can be introduced as a branch component of the graft copolymer, and the (meth)acrylic acid ester copolymer can be made into a graft copolymer.
- a (meth)acrylic polymer (A) comprising a copolymer containing a macromonomer-derived structural unit as a branch component can be used. Therefore, the properties of the main chain and the side chains of the graft copolymer can be changed by selecting the copolymerizable monomer a8 and the other monomers and blending ratio.
- the copolymerization ratio of the macromonomer in the (meth)acrylic polymer (A) is preferably 30% by mass or less in terms of imparting fluidity during hot-melt, more preferably 2 % by mass or more and 15% by mass or less, more preferably 3% by mass or more and 10% by mass or less, particularly preferably 4% by mass or more and 7% by mass or less.
- Examples of the copolymerizable monomer a9 include benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, nonylphenol EO-modified (meth)acrylate, and the like. These may be used alone or in combination of two or more.
- Examples of the copolymerizable monomer a10 include (meth)acryl-modified silicone, 2-acryloyloxyethyl acid phosphate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-- Tetrafluoropropyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H,2H,2H-tridecafluoro- Examples include fluorine-containing monomers such as n-octyl (meth)acrylate. These may be used alone or in combination of two or more.
- the glass transition temperature of at least one of the (meth)acrylic acid ester-derived repeating units of the acrylic polymer (A) is preferably -70 to 0°C.
- the glass transition temperature of the copolymer component means a value calculated by the Fox formula from the glass transition temperature of the polymer obtained from the homopolymer of each component of the copolymer and the composition ratio.
- the glass transition temperature of at least one of the (meth)acrylic acid ester-derived repeating units of the acrylic polymer (A) is -70. ⁇ 0°C is preferred.
- (Meth)acrylic acid esters constituting such repeating units include, for example, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate, 2-ethylhexyl acrylate, 2 -ethylhexyl methacrylate, 2-methylhexyl acrylate, isooctyl acrylate, isononyl acrylate, isodecyl acrylate, isodecyl methacrylate, isostearyl acrylate, isostearyl (meth)acrylate, multi-branched stearyl acrylate, multi-branched stearyl (meth)acrylate, etc. can be mentioned, but are not limited to these.
- the glass transition temperature of at least one repeating unit derived from the (meth)acrylic acid ester of the acrylic polymer (A) is 20 to 120° C.
- excellent workability and storage are obtained. It is preferable because stability can be maintained.
- the glass transition temperature (Tg) is preferably 30° C. to 120° C., especially 40° C. or higher or 110° C. or lower, especially 50° C. or higher, because it affects the hot-melt temperature of the pressure-sensitive adhesive sheet. Alternatively, it is more preferably 100° C. or less. If there is a repeating unit having such a glass transition temperature (Tg), it is possible to maintain excellent workability and storage stability by adjusting the molecular weight, and to adjust it so that it hot melts at 50 ° C. or higher. can.
- (Meth)acrylic acid esters constituting such repeating units include, for example, methyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl acrylates, isobutyl acrylate, isobutyl methacrylate, isobornyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, tetrahydrofurfuryl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, etc. can be mentioned.
- the (meth)acrylic polymer (A) is preferably a block copolymer and/or a graft copolymer from the viewpoint of imparting hot-melt properties to the pressure-sensitive adhesive.
- a block copolymer or a graft copolymer as the (meth)acrylic polymer (A), a pressure-sensitive adhesive sheet having excellent shape stability and hot-melt properties can be obtained.
- the block copolymer refers to a copolymer having a plurality of polymer chains containing repeating units derived from (meth)acrylic acid ester, and having a plurality of polymer chains with different chemical structures bonded in a straight chain.
- some blocks of the block copolymer contain repeating units derived from the macromonomer.
- graft copolymers are copolymers containing repeating units derived from (meth)acrylic acid ester as a trunk component, and depending on the method of introducing the branch component, they can be comb-shaped polymers, brush-shaped polymers, star polymers, palm-shaped polymers, and so on.
- a copolymer containing repeating units derived from a macromonomer as a branch component of the graft copolymer is preferred.
- a graft copolymer containing repeating units derived from a macromonomer is used as the base polymer.
- block copolymers containing repeating units derived from macromonomers it is common to graft copolymers that the repeating units derived from macromonomers aggregate and phase-separate to exert an effect. It can be expected that a block copolymer containing a can also obtain the same effect as a graft copolymer containing a macromonomer.
- the (meth)acrylic polymer (A) is a copolymer containing a structural unit derived from a macromonomer as described above, if the copolymerization ratio of the macromonomer is 2% by mass or more, the hot-melt property On the other hand, if it is 30% by mass or less, when it is laminated with the image display device constituent members described later to form a laminate, delamination or the like does not occur during bending, and durability is improved.
- the copolymerization ratio of the macromonomer in the (meth)acrylic polymer (A) is preferably 2% by mass or more, more preferably 3% by mass or more, and more preferably 4% by mass or more. On the other hand, it is preferably 30% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 7% by mass or less.
- a (meth)acrylic polymer (A) using a macromonomer obtained by copolymerizing a (meth)acrylate having a linear or branched alkyl group having 1 to 3 carbon atoms is used as the macromonomer.
- the glass transition temperature of the repeating unit derived from the macromonomer is preferably 20 to 150°C, more preferably 40°C or higher or 130°C or lower, and more preferably 60°C or higher or 120°C or lower.
- the content of the copolymer component having a glass transition temperature within the above range is preferably 3% by mass or more, more preferably 4% by mass or more, relative to the (meth)acrylic polymer (A).
- it is preferably 10% by mass or less, more preferably 9% by mass or less, more preferably 8% by mass or less, even more preferably 7% by mass or less.
- the repeating unit derived from the macromonomer that is, the copolymer component having a glass transition temperature of 20 to 150 ° C.
- the cross-linking agent (B) is a compound or composition that forms a cross-linked structure in the pressure-sensitive adhesive composition, and is a compound having two or more cross-linkable functional groups.
- the present pressure-sensitive adhesive composition contains the cross-linking agent (B)
- the present pressure-sensitive adhesive composition forms a cross-linked structure and can impart durability and restorability to the present pressure-sensitive adhesive sheet.
- crosslinkable functional groups examples include isocyanate groups, epoxy groups, (meth)acryloyl groups, thioisocyanate groups, primary or secondary amino groups, and thiol groups. These may be protected with a suitable protecting group.
- crosslinkable functional groups contained in the crosslinker include only epoxy groups, only isocyanate groups, only (meth)acryloyl groups, only thioisocyanate groups, only thiol groups, only primary or secondary amino groups, epoxy and (meth)acryloyl groups, and combinations of isocyanate groups and (meth)acryloyl groups.
- a polyfunctional (meth)acrylate (b) having two or more (meth)acryloyl groups is used as the cross-linking agent (B). is preferred.
- the content of the polyfunctional (meth)acrylate (b) is preferably 0.5 parts by mass or more, preferably 1 part by mass or more, with respect to 100 parts by mass of the (meth)acrylic polymer (A). Among them, 1.5 parts by mass or more is more preferable. Regarding the upper limit, it is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, from the viewpoint of maintaining appropriate flexibility and ensuring followability to the adherend when bent. It is more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, particularly preferably 2 parts by mass or less.
- the amount is preferably 5 parts by mass or less, especially from the viewpoint of imparting flexibility to the extent that it can follow the step. 3 parts by mass or less, more preferably 2 parts by mass or less.
- Polyfunctional (meth)acrylates (b) include, for example, 1,4-butanediol di(meth)acrylate, glycerin di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerin glycidyl ether di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethacrylate, tricyclodecanedimethanol di(meth)acrylate, bisphenol A polyethoxydi(meth)acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, ⁇ -
- the adhesive composition may further contain a monofunctional (meth)acrylate component (D) having one (meth)acryloyl group.
- a monofunctional (meth)acrylate component By including a monofunctional (meth)acrylate component, the molecular weight between cross-linking points of the cured product can be increased, so that the degree of freedom of movement of the molecular chains is increased, and the components constituting the image display device are bonded via the pressure-sensitive adhesive sheet.
- the pressure-sensitive adhesive sheet made of the pressure-sensitive adhesive composition can be deformed accordingly.
- Examples of the monofunctional (meth)acrylate component (D) include ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, Acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate Acrylate, dodecyl (meth)acrylate, isododecyl (meth)acrylate, tetradecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate
- the content ratio by mass of the polyfunctional (meth)acrylate (b) and the monofunctional (meth)acrylate component (D) is the polyfunctional (meth)acrylate (b):
- Monofunctional (meth)acrylate (D) is preferably 1:0.1 to 1:9, more preferably 1:1 to 1:9, and preferably 1:2 to 1:9. More preferred. Within this range, the amount of the monofunctional (meth)acrylate component is not too large, and there is no concern that the sensitivity to light will decrease and the productivity will decrease.
- the polymerization initiator (C) imparts active energy ray curability to the present pressure-sensitive adhesive sheet, and may be any compound that generates radicals by means of active energy rays.
- the polymerization initiator (C) is roughly classified into two groups according to the mechanism of radical generation: a cleavage-type photoinitiator capable of cleaving and decomposing a single bond of the polymerization initiator itself to generate radicals, and an excited initiator. and a hydrogen abstraction type photoinitiator capable of forming an exciplex with a hydrogen donor in the system and transferring hydrogen of the hydrogen donor.
- the polymerization initiator (C) may be either a cleavage photoinitiator or a hydrogen abstraction photoinitiator, each of which may be used alone or a mixture of both may be used. may be used alone or in combination of two or more.
- a hydrogen abstraction type photoinitiator is used as the photoinitiator, a hydrogen abstraction reaction also occurs from the acrylic (co)polymer, and not only the active energy ray-curable compound but also the acrylic (co)polymer has a crosslinked structure. It is preferable in terms of being able to form a crosslinked structure with many crosslinked points.
- cleavage type photoinitiator when used as the polymerization initiator (C), once radicals are generated, it decomposes and deactivates, which is preferable in that there is no risk of unexpected reaction or deterioration after curing.
- cleavage-type photoinitiators examples include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one. , 1-(4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4- ⁇ 4-(2-hydroxy-2- Methyl-propionyl)benzyl ⁇ phenyl]-2-methyl-propan-1-one, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone), phenylglyoxylic acid methyl, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one , 2-(dimethylamino)-2-[(4-methylpheny
- Hydrogen abstraction photoinitiators include, for example, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(meth)acryloyl Oxybenzophenone, methyl 2-benzoylbenzoate, methyl benzoylformate, bis(2-phenyl-2-oxoacetic acid)oxybisethylene, 4-(1,3-acryloyl-1,4,7,10,13-pentaoxo tridecyl)benzophenone, thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2,4-dimethylthioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone and derivatives thereof, etc. can be mentioned.
- the content of the polymerization initiator (C) is not particularly limited.
- “Other components" other than the above contained in the present pressure-sensitive adhesive composition include, for example, silane coupling agents, tackifying resins, plasticizers, antioxidants, light stabilizers, metal deactivators, if necessary.
- Various additives such as a curing agent, anti-aging agent, hygroscopic agent, polymerization inhibitor, ultraviolet absorber, anticorrosive agent, inorganic particles, sensitizer and pigment can be incorporated as appropriate.
- the amounts of these additives are typically preferably selected so as not to adversely affect the curing of the adhesive sheet or adversely affect the physical properties of the adhesive sheet.
- a reaction catalyst such as a tertiary amine compound, a quaternary ammonium compound, a tin laurate compound, or the like may be appropriately contained.
- silane coupling agent examples include compounds having a hydrolyzable functional group such as an alkoxy group together with an unsaturated group such as a vinyl group, an acryloxy group and a methacryloxy group, an amino group, an epoxy group, and the like. .
- silane coupling agents include N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropyl Examples include triethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, and the like. Among them, ⁇ -glycidoxypropyltrimethoxysilane or ⁇ -methacryloxypropyltrimethoxysilane can be preferably used from the viewpoint of good adhesiveness and little discoloration such as yellowing.
- the silane coupling agents may be used singly or in combination of two or more.
- silane coupling agent When the silane coupling agent is contained, it is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the (meth)acrylic polymer, and is preferably 0.2 parts by mass or more or 3 parts by mass or less. More preferred. Coupling agents such as organic titanate compounds can also be effectively used in the same manner as silane coupling agents.
- the present pressure-sensitive adhesive composition can contain a hydrocarbon tackifier in order to impart stickiness and hot-melt properties to the present pressure-sensitive adhesive sheet.
- Hydrocarbon tackifiers include terpene resins such as polyterpenes (e.g., ⁇ -pinene-based resins, ⁇ -pinene-based resins, and limonene-based resins) and aromatic-modified polyterpene resins (e.g., phenol-modified polyterpene resins), and coumaran-indene.
- Resins C5-based hydrocarbon resins, C9-based hydrocarbon resins, C5/C9-based hydrocarbon resins, petroleum-based resins such as dicyclopentadiene-based resins, modified rosins, hydrogenated rosins, polymerized rosins, rosins such as rosin esters can be mentioned.
- the hydrocarbon tackifier is preferably compatible with the present pressure sensitive adhesive composition.
- the content of the hydrocarbon tackifier is not particularly limited. It is preferably 0.1 to 20 parts by mass, more preferably 0.5 parts by mass or more or 15 parts by mass or less, based on 100 parts by mass of the (meth)acrylic polymer.
- silane coupling agents and tackifiers By including these silane coupling agents and tackifiers, it is possible to suitably prepare a pressure-sensitive adhesive composition having excellent adhesive properties.
- this adhesive sheet in addition to the (meth)acrylic polymer (A), if necessary, a crosslinking agent (B) and / or a polymerization initiator (C), and optionally other components are mixed in predetermined amounts to prepare the present pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition is formed into a sheet, and if necessary, the curable compound is crosslinked or polymerized to be cured, and the present pressure-sensitive adhesive sheet should be made.
- a crosslinking agent (B) and / or a polymerization initiator (C) e.g., it is not limited to this method.
- the raw materials are kneaded using a temperature-controllable kneader (e.g., single-screw extruder, twin-screw extruder, planetary mixer, twin-screw mixer, pressure kneader, etc.). Just do it.
- a temperature-controllable kneader e.g., single-screw extruder, twin-screw extruder, planetary mixer, twin-screw mixer, pressure kneader, etc.
- various additives such as silane coupling agents and antioxidants may be blended in advance with the resin and then supplied to the kneader, or all the materials may be melted and mixed in advance.
- a masterbatch in which only the additive is concentrated in the resin in advance may be prepared and supplied.
- Methods for forming the present pressure-sensitive adhesive composition into a sheet include known methods such as wet lamination, dry lamination, extrusion casting using a T-die, extrusion lamination, calendering, inflation, injection molding, and injection molding.
- a liquid curing method or the like can be employed.
- the wet lamination method, the extrusion casting method, and the extrusion lamination method are suitable for producing a sheet.
- the present pressure-sensitive adhesive composition contains a radical initiator
- a cured product can be produced by curing by irradiating heat and/or active energy rays.
- the present pressure-sensitive adhesive sheet can be produced by irradiating heat and/or active energy rays to a molded article, for example, a sheet formed from the present pressure-sensitive adhesive composition.
- the active energy rays to be irradiated include ⁇ rays, ⁇ rays, ⁇ rays, ionizing radiation such as neutron rays and electron beams, ultraviolet rays, visible rays, and the like. Ultraviolet rays are preferable from the viewpoint of suppression and reaction control.
- the irradiation energy, irradiation time, irradiation method, and the like of the active energy ray are not particularly limited as long as the initiator can be activated to polymerize the (meth)acrylate component.
- the present pressure-sensitive adhesive composition can be dissolved in an appropriate solvent and various coating techniques can be used.
- the pressure-sensitive adhesive sheet can also be obtained by thermal curing in addition to the active energy ray irradiation curing described above.
- the thickness of the adhesive sheet can be adjusted by the coating thickness and the solid content concentration of the coating liquid.
- the present pressure-sensitive adhesive sheet may have a single-layer structure composed of the present pressure-sensitive adhesive layer, or may have a multi-layer structure of two or more layers provided with the present pressure-sensitive adhesive layer.
- the composition of the layers other than the layer composed of the pressure-sensitive adhesive composition is arbitrary.
- the pressure-sensitive adhesive composition forming a layer other than the present pressure-sensitive adhesive layer also It is preferably formed from a pressure-sensitive adhesive composition containing a (meth)acrylic polymer, and more preferably contains the same (meth)acrylic polymer (A) as that of the present pressure-sensitive adhesive layer. Furthermore, it is more preferable that layers other than the pressure-sensitive adhesive layer also contain a cross-linking agent (B) and/or a polymerization initiator (C).
- B cross-linking agent
- C polymerization initiator
- the pressure-sensitive adhesive sheet has a multi-layer structure of two or more layers, it is preferable that at least the outermost layer, the backmost layer, or both layers correspond to the pressure-sensitive adhesive layer. All the layers may be layers corresponding to the pressure-sensitive adhesive layer.
- the thickness of the layer corresponding to the pressure-sensitive adhesive layer preferably accounts for 10% or more and 100% or less of the total thickness of the pressure-sensitive adhesive sheet. % or more or 70% or less, more preferably 20% or more or 50% or less.
- the thickness of the pressure-sensitive adhesive sheet Since the bending stress at the time of bending or bending is proportional to the thickness, if the thickness of the pressure-sensitive adhesive sheet is 50 ⁇ m or less, the stress at the time of bending or bending can be alleviated, and the thickness of the laminate can be reduced. In addition, it can contribute to thinning of the flexible image display device. On the other hand, when the thickness is 15 ⁇ m or more, the handling property is good, and even if there is an uneven portion having a height difference of 2 ⁇ m or more and 10 ⁇ m or less in the constituent member of the image display device, it is possible to follow the step.
- the thickness of the pressure-sensitive adhesive sheet is preferably 50 ⁇ m or less, more preferably 45 ⁇ m or less, more preferably 40 ⁇ m or less, particularly 35 ⁇ m or less.
- the lower limit is preferably 15 ⁇ m or more, more preferably 17 ⁇ m or more, and more preferably 20 ⁇ m or more.
- the pressure-sensitive adhesive sheet is thin as described above, it can be deformed to follow the unevenness on the surface of the member for an image display device and penetrate into the unevenness. Therefore, the surface of the pressure-sensitive adhesive sheet, that is, the surface opposite to the adhesive surface can be made smooth by absorbing the unevenness. At this time, if the height difference of the unevenness is 12% or less of the thickness of the present pressure-sensitive adhesive sheet, it can be absorbed.
- An example of the present pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet for a flexible display, which has a pressure-sensitive adhesive layer containing a (meth)acrylic polymer (A), has a thickness of 15 ⁇ m or more and 50 ⁇ m or less, and exhibits active energy ray curability. and having a difference in height of 2 ⁇ m or more, for example, steps of 2 to 10 ⁇ m at intervals of 10 mm or less.
- a pressure-sensitive adhesive sheet for a flexible display can be mentioned. (Lamination conditions) a) A pressure-sensitive adhesive sheet having a thickness of 15 to 50 ⁇ m is irradiated with ultraviolet rays so that the integrated amount of light at 365 nm is 2000 to 4000 mJ/cm 2 .
- the pressure-sensitive adhesive sheet is vacuum-bonded to the surface of a base material having a difference in height of 2 ⁇ m or more, for example, 2 to 10 ⁇ m at intervals of 10 mm or less under the conditions of a press pressure of 0.2 MPa and 30 seconds.
- This pressure-sensitive adhesive sheet can also be used as a single pressure-sensitive adhesive sheet.
- the present pressure-sensitive adhesive composition may be directly applied to a member for an image display device to be described later to form a sheet, or the pressure-sensitive adhesive composition may be directly extruded or injected into a mold to obtain the present pressure-sensitive adhesive sheet. can be used.
- the present pressure-sensitive adhesive sheet can also be used by directly filling the present pressure-sensitive adhesive composition between image display device constituent members.
- this pressure-sensitive adhesive sheet can be used by being laminated with other pressure-sensitive adhesive sheets.
- other pressure-sensitive adhesive sheets are more suitable for the flexible image display device if they are more flexible than the present pressure-sensitive adhesive sheet.
- Such other adhesive sheets have a gel fraction of 70% or more, a thickness of 0.8 mm to 1.5 mm, and a maximum loss tangent obtained by dynamic viscoelasticity measurement in a shear mode at a frequency of 1 Hz.
- a pressure-sensitive adhesive sheet having a temperature of -25°C or less can be mentioned.
- the maximum point of the loss tangent is ⁇ 25° C. or less, it is preferable because it can be restored even when it is bent at high and low temperatures.
- the maximum point of the loss tangent of the other PSA sheet is preferably ⁇ 25° C. or lower, more preferably ⁇ 30° C. or lower, and more preferably ⁇ 35° C. or lower.
- the pressure-sensitive adhesive sheet can be used as a pressure-sensitive adhesive sheet with a release film (referred to as a "pressure-sensitive adhesive sheet with a release film") comprising the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition and a release film.
- a pressure-sensitive adhesive sheet with a release film comprising the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition and a release film.
- the present pressure-sensitive adhesive composition can be in the form of a release film-attached pressure-sensitive adhesive sheet formed by molding a single-layer or multilayer sheet on a release film.
- polyester film examples include polyester film, polyolefin film, polycarbonate film, polystyrene film, acrylic film, triacetylcellulose film, and fluororesin film.
- polyester films and polyolefin films are particularly preferred.
- the thickness of the release film is not particularly limited. Among them, for example, from the viewpoint of workability and handleability, the thickness is preferably 25 ⁇ m to 500 ⁇ m, more preferably 38 ⁇ m or more or 250 ⁇ m or less, and more preferably 50 ⁇ m or more or 200 ⁇ m or less.
- the release film is preferably a polyester-based film, and from the standpoint of releasability, it is preferable that the release film be easily peeled off even after irradiation with active energy rays. From this point of view, when the active energy ray with a wavelength of 365 nm is irradiated with an accumulated light amount of 2000 to 4000 mJ/cm 2 , the peel force for the present adhesive sheet is 0.1 N/cm or less at a peel angle of 180° and a peel speed of 300 mm/min. It is preferable to be
- a laminate (referred to as "this laminate") according to an example of an embodiment of the present invention includes a release film and a member for constituting an image display device having a step with a height difference of 2 ⁇ m or more on the surface to be laminated, It is a layered product having a configuration in which layers are layered via an adhesive sheet.
- the release film of the laminate is the same as the release film of the pressure-sensitive adhesive sheet with the release film.
- a release film and a member for constituting an image display device having a step with a height difference of 2 ⁇ m or more on the laminated surface are laminated via the present adhesive sheet, and the present adhesive is passed through the release film from the release film side.
- the laminate can be produced by irradiating the sheet with active energy rays.
- the irradiation dose of the active energy rays is preferably 4000 mJ/cm 2 or less, particularly 3500 mJ/cm 2 or less, further preferably 3200 mJ/cm 2 or less, from the viewpoint of step absorption.
- it is preferably 2000 mJ/cm 2 or more, more preferably 2500 mJ/cm 2 or more, and even more preferably 2800 mJ/cm 2 or more.
- a laminate for an image display device according to an example of the embodiment of the present invention (hereinafter sometimes referred to as "this laminate") is provided with an image display device constituent member on at least one side of the above-described present pressure-sensitive adhesive sheet. It is a laminated body.
- the laminate includes a first image display device constituent member (hereinafter sometimes referred to as “first member”), the present pressure-sensitive adhesive sheet, and a second image display device constituent member (hereinafter sometimes referred to as “second member”). (sometimes referred to as “members”) are preferably laminated in this order. Further, the first member, the second member and the third image display device constituting member (hereinafter sometimes referred to as “third member”) are laminated in this order with the adhesive sheet interposed therebetween. It may also be a laminated body having a different configuration. Two or more members to be laminated may be the same or different.
- the thickness of the laminate is not particularly limited.
- the laminate when used in an image display device, the laminate is in the form of a sheet, and if the thickness is 0.02 mm or more, the handleability is good, and the thickness is 1.0 mm or less. If it is, it can contribute to thickness reduction of a laminated body. Therefore, the thickness of the laminate is preferably 0.02 mm or more, more preferably 0.03 mm or more, particularly 0.05 mm or more.
- the upper limit is preferably 1.0 mm or less, more preferably 0.7 mm or less, particularly 0.5 mm or less.
- the present laminate can be produced by attaching the present adhesive sheet to the first member, the second member and/or the third member. However, it is not limited to such a manufacturing method.
- the first member, the second member, and the third member include, for example, A cover lens, a polarizing plate, a retardation film, a barrier film, a touch sensor film, a light emitting element, a PSA and the like can be mentioned.
- the first member preferably has a touch input function.
- the second member to the third member may have a touch input function.
- at least one of the members may have various irregularities formed by wiring, printing, pattern development, surface treatment, embossing, etc. on the contact surface with the pressure-sensitive adhesive sheet.
- the height difference of the unevenness is preferably 2 ⁇ m or more, for example, 2 ⁇ m or more and 10 ⁇ m or less, more preferably 8 ⁇ m or less, and more preferably 3 ⁇ m or more or 7 ⁇ m or less. is more preferable, and among them, 4 ⁇ m or more or 6 ⁇ m or less is more preferable.
- At least one of the members for forming an image display device (including the first member, the second member, and the third member) to be laminated is made of urethane resin, cycloolefin resin, triacetylcellulose resin, (meta) It may be a resin sheet or a thin film glass mainly composed of one or more resins selected from the group consisting of acrylate resins, epoxy resins and polyimide resins.
- the term "main component” refers to a component that accounts for the largest mass ratio among the components constituting the image display device constituent member, and specifically, the image display device constituent member or the member forming the member. It accounts for 50% by mass or more of the pressure-sensitive adhesive composition, more preferably 55% by mass or more, and more preferably 60% by mass or more.
- This adhesive sheet can be hot-melted after being cured by active energy rays. With such a hot melt, even if the adherend surface of the adherend has unevenness, it can be laminated so as to follow the unevenness and absorb the unevenness, and the surface can be smoothed. . Therefore, when two image display device constituent members are bonded via the present pressure-sensitive adhesive sheet, even if one or both of the image display device constituent members are members that do not transmit light, the unevenness can be absorbed. Two members for forming an image display device can be pasted together.
- This image display device> Forming a flexible image display device (also referred to as "present image display device") comprising this laminate by incorporating this laminate, for example, by laminating this laminate on another image display device constituent member. can be done.
- a flexible image display device leaves no trace of bending even after repeated bending, bending, or winding operations, and can be bent, bent, or wound up when the bending, bending, or winding state is released. It is an image display device that can quickly recover to the state before the display and can display an image without distortion.
- the laminate conforms to and absorbs unevenness having a height difference of 2 ⁇ m or more on the contact surface of the constituent member of the image display device with the adhesive sheet so as not to generate air bubbles.
- a display device can be manufactured.
- the present pressure-sensitive adhesive sheet can be placed on the viewing side of an image display panel such as a liquid crystal panel, or can be placed on the side opposite to the viewing side of the image display panel, that is, on the light source side. can.
- the present laminate can be produced by a method for producing a laminate for an image display device including the following steps 1 to 3 and, if necessary, step 4.
- Step 1 One surface of the pressure-sensitive adhesive sheet is attached to the member 1 for constituting an image display device.
- Step 2 The pressure-sensitive adhesive sheet is cured by irradiation with active energy rays.
- Step 3 The image display device constituting member 2 is adhered to the other surface of the pressure-sensitive adhesive sheet to form a laminate.
- Step 4 The laminate is heat-treated to hot-melt the pressure-sensitive adhesive sheet.
- Step 2 may be carried out after Step 1, or Step 1 may be carried out after Step 2. After performing steps 1 and 2, step 3 is performed.
- Step 1 is a step of bonding one surface of the pressure-sensitive adhesive sheet to the member 1 for constituting an image display device.
- a lamination method known methods such as roll lamination, press lamination using a parallel plate, and diaphragm lamination can be used.
- the lamination environment there are an air lamination method in which lamination is performed under normal pressure and a vacuum lamination method in which lamination is performed under reduced pressure. From the viewpoint of preventing air bubbles during lamination, a method of laminating with a parallel plate under a reduced pressure environment is preferable. Moreover, you may adjust bonding temperature suitably.
- Step 2 is a step of curing the adhesive sheet by irradiating it with active energy rays.
- active energy rays ultraviolet rays and visible rays are suitable.
- the light source when irradiating the active energy ray it is possible to use properly according to the wavelength and irradiation amount of the light to be irradiated from, for example, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a halogen lamp, an LED lamp, a fluorescent lamp, etc. can.
- irradiation time and irradiation means are not particularly limited, for example, in the case of ultraviolet irradiation, it is preferable to irradiate so that the integrated light amount at a wavelength of 365 nm is 2000 mJ/cm 2 or more, particularly 3000 mJ/cm 2 or more.
- the present pressure-sensitive adhesive sheet is hot-melted. can absorb the step by following the step, and preferably the surface of the laminate can be smoothed.
- Step 3 is a step of laminating the member 2 for constituting an image display device to the other surface of the pressure-sensitive adhesive sheet that has undergone steps 1 and 2 to form a laminate.
- the image display device-constituting member 1 and/or the image display device-constituting member 2 may be heated and the image display device-constituting member 2 may be bonded together as needed.
- the heating at this time is performed, for example, by applying a press plate heated to a predetermined temperature to a laminate for an image display device composed of image display device constituent member 1/adhesive sheet/image display device constituent member 2 from both sides.
- a method of applying pressure can be mentioned.
- the heating temperature at this time is preferably 50° C. or higher and 80° C. or lower. That is, the image display device constituent member 1 and/or the image display device constituent member 2 are heated to 50° C. or more and 80° C. or less to hot-melt the adhesive sheet, and the image display device constituent member 2 is bonded. is preferred.
- the press pressure when pressing with the press plate is preferably 0.01 MPa or more or 0.4 MPa or less, more preferably 0.02 MPa or more or 0.35 MPa or less.
- Step 4 is a step of heat-treating the laminated body obtained in Step 3 to hot-melt the pressure-sensitive adhesive sheet. This step 4 may be performed as required.
- the surface of the first member or the second member for example, the surface to be laminated, has a height difference of 2 ⁇ m or more, for example, 2 ⁇ m or more and 10 ⁇ m or less. Even if the adhesive sheet has unevenness having a level difference, the pressure-sensitive adhesive sheet can follow the level difference and absorb the level difference, thereby smoothing the surface.
- the heating temperature for the heat treatment of the laminate is preferably 40° C. or higher and 90° C. or lower. Above all, the temperature is preferably 50° C. or higher or 80° C. or lower, more preferably 60° C. or higher or 70° C. or lower.
- an air pressure of 0.2 MPa or more and 0.8 MPa or less may be applied to the laminate for 5 minutes or more. At this time, the atmospheric pressure is preferably 0.2 MPa or more and 0.8 MPa or less, more preferably 0.4 MPa or more or 0.6 MPa or less.
- the treatment time is preferably 5 minutes or more or 60 minutes or less, more preferably 10 minutes or more or 30 minutes or less.
- a press pressure of 0.01 MPa or more and 0.4 MPa or less may be applied to the laminate in combination with the heat treatment.
- the pressing pressure is preferably 0.01 MPa or more or 0.4 MPa or less, more preferably 0.02 MPa or more or 0.35 MPa or less.
- the treatment time is preferably 5 seconds or more or 10 minutes or less, more preferably 10 seconds or more or 5 minutes or less.
- the hot-melt treatment is preferably performed within 30 minutes after irradiating the adhesive sheet with active energy rays. The reason for this is that if the hot-melt treatment is performed before the adhesive is completely cured, it becomes easier to follow the unevenness having a level difference of 2 ⁇ m or more. From this point of view, the time from the irradiation of the active energy ray to the hot-melt treatment is preferably within 30 minutes, more preferably within 20 minutes, and even more preferably within 10 minutes.
- the term “film” includes the “sheet”
- the term “sheet” includes the “film”.
- the expression “panel” such as an image display panel, a protective panel, etc. includes a plate, a sheet and a film.
- (Meth)acrylic polymer (A-1) 6 parts by mass of polymethyl methacrylate macromonomer (Tg 105°C) having a number average molecular weight of 2800, 90 parts by mass of butyl acrylate (Tg -55°C), and acrylic acid ( Tg 106° C.) 4 parts by mass of acrylic graft copolymer (mass average molecular weight: 220,000, Tg ⁇ 45° C.) -
- the glass transition temperature of each copolymer component in the (meth)acrylic polymer is the literature value of the glass transition temperature obtained from the homopolymer of the component.
- the macromonomer the literature value of the glass transition temperature obtained from the homopolymer of the component forming the high-molecular-weight skeleton in the macromonomer was used.
- the glass transition temperature of the acrylic copolymer the theoretical Tg calculated by the Fox calculation formula is described from the glass transition temperature and the composition ratio of each component of the copolymer.
- ⁇ Crosslinking agent (B)> ⁇ Crosslinking agent (B-1): propoxylated pentaerythritol triacrylate
- the sheet-shaped pressure-sensitive adhesive composition a release film having a thickness of 75 ⁇ m (PET film manufactured by Mitsubishi Chemical Corporation) that has been subjected to silicone release treatment is laminated to form a laminate, and the release film/ A pressure-sensitive adhesive sheet 1 with a release film composed of pressure-sensitive adhesive sheet 1/release film was obtained.
- the adhesive sheet 1 was an active energy ray-curable adhesive sheet having an active energy ray-curable adhesive sheet that is cured by irradiation with an active energy ray.
- Adhesive sheet 2 and adhesive sheet 2 with a release film composed of release film/adhesive sheet 2/release film were produced in the same manner as in Example 1, except that the thickness was changed as shown in Table 1.
- the adhesive sheet 2 was an active energy ray-curing adhesive sheet that was cured by irradiation with light.
- Example 3 Each component was prepared as shown in Table 1 and used as a raw material for the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive composition was applied to a release film of 100 ⁇ m (PET film manufactured by Mitsubishi Chemical Corporation, thickness 100 ⁇ m) and a release film of 75 ⁇ m (Mitsubishi Chemical Corporation).
- PET film that is, sandwiched between two release films, hot-melt molded into a sheet with a thickness of 50 ⁇ m, and release film/adhesive sheet 3/release film-attached adhesive sheet 3 consisting of release film got
- the adhesive sheet 3 was an active energy ray-curing adhesive sheet that was cured by irradiation with light.
- Example 4 Each component was prepared as shown in Table 1 and used as a raw material for the pressure-sensitive adhesive layer.
- Adhesive sheet 4 and adhesive sheet 4 with a release film composed of release film/adhesive sheet 4/release film were prepared in the same manner as in Example 3.
- the adhesive sheet 4 was an active energy ray-curing adhesive sheet that was cured by irradiation with light.
- Example 5 Each component was prepared as shown in Table 1 and used as a raw material for the pressure-sensitive adhesive layer.
- Adhesive sheet 5 and adhesive sheet 5 with a release film composed of release film/adhesive sheet 5/release film were prepared in the same manner as in Example 1.
- the adhesive sheet 5 was an active energy ray-curing adhesive sheet that was cured by irradiation with light.
- Example 6 Each component was prepared as shown in Table 1 and used as a raw material for the pressure-sensitive adhesive layer.
- Adhesive sheet 6 and adhesive sheet 6 with a release film composed of release film/adhesive sheet 6/release film were prepared in the same manner as in Example 3.
- the adhesive sheet 6 was an active energy ray-curing adhesive sheet that was cured by irradiation with light.
- Example 7 Each component was prepared as shown in Table 1 and used as a raw material for the pressure-sensitive adhesive layer.
- Adhesive sheet 7 and adhesive sheet 7 with a release film composed of release film/adhesive sheet 7/release film were prepared in the same manner as in Example 3.
- the adhesive sheet 7 was an active energy ray-curing adhesive sheet that was cured by irradiation with light.
- a release film having a thickness of 75 ⁇ m (PET film manufactured by Mitsubishi Chemical Corporation) subjected to silicone release treatment is laminated to form a laminate, and a metal halide lamp irradiation device is formed.
- a metal halide lamp irradiation device (Ushio Denki, UVC-0516S1, lamp UVL-8001M3-N) was applied to the pressure-sensitive adhesive composition through the release film so that the cumulative irradiation dose at a wavelength of 365 nm was 3000 mJ/cm 2 . Irradiation was performed to obtain a pressure-sensitive adhesive sheet laminate in which release films were laminated on both front and back sides of a 25 ⁇ m pressure-sensitive adhesive sheet (adhesive sheet 8).
- the adhesive sheet 8 is an adhesive sheet in which the reaction due to light irradiation has progressed sufficiently and there is almost no room for active energy ray curing.
- the pressure-sensitive adhesive composition was applied to a release film of 100 ⁇ m (PET film manufactured by Mitsubishi Chemical Corporation, thickness 100 ⁇ m) and a release film of 75 ⁇ m (Mitsubishi Chemical Corporation).
- PET film that is, sandwiched between two release films, hot-melt molded into a sheet with a thickness of 25 ⁇ m, and release film/adhesive sheet 9/release film-attached adhesive sheet 9 consisting of release film got
- the adhesive sheet 9 was an active energy ray-curing adhesive sheet that was cured by irradiation with light.
- ⁇ Creep test> The release film was removed from the release film-attached pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples, and the stacking was repeated with a hand roller so that the thickness was about 0.9 mm.
- a pressure-sensitive adhesive sheet with a release film was produced by punching into a shape, and this was used as a sample.
- the release film was removed when installed in a rheometer ("DHR-2" manufactured by TA Instruments), and the measurement jig was a parallel plate with a diameter of 8 mm, temperature: 25 ° C., pressure: 1000 Pa. , the strain (creep strain) (%) after 3600 seconds was measured.
- the pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were examined with an integrated amount of light at 365 nm of 3000 mJ/cm 2 for the pressure-sensitive adhesive sheets 1 to 4 and 6-7, and 4000 mJ/cm 2 for the pressure-sensitive adhesive sheets 5 and 9.
- the adhesive sheet was irradiated with ultraviolet rays through the release film to cure the adhesive sheet.
- the adhesive sheet 8 produced in Comparative Example 1 is an adhesive sheet in which the reaction due to light irradiation has progressed sufficiently and there is almost no room for active energy ray curing. did.
- the adhesive sheets after curing were laminated to a thickness of about 0.9 mm, and a circle with a diameter of 8 mm was punched out and used as a sample.
- a rheometer (DHR-2" manufactured by TA Instruments) measuring jig: diameter 8 mm parallel plate, temperature: 80 ° C., pressure: 1000 Pa, strain after 180 seconds (creep strain ) (%) was measured.
- the integrated light quantity at 365 nm was 3000 mJ/cm 2 for adhesive sheets 1 to 4 and 6 to 7, and for adhesive sheets 5 and 9.
- the adhesive sheet was irradiated with ultraviolet rays through the release film so as to be 4000 mJ/cm 2 to cure the adhesive sheet.
- the adhesive sheet 8 produced in Comparative Example 1 is an adhesive sheet in which the reaction due to light irradiation has progressed sufficiently and there is almost no room for active energy ray curing. did.
- the adhesive sheets after curing were laminated so as to have a thickness of about 0.9 mm, and a circle with a diameter of 8 mm was punched out and used as a sample.
- a rheometer (“DHR-2" manufactured by TA Instruments Co., Ltd., measuring jig: 8 mm diameter parallel plate) was used at a temperature of 25 ° C., and the shear strain as the initial strain (x) was 200%.
- a shear stress was applied to the sample for 600 seconds. After that, the stress was released and the residual strain (y) was measured after 600 seconds had passed, and the recovery rate was obtained from the following formula.
- the integrated light quantity at 365 nm was 3000 mJ/cm 2 for adhesive sheets 1 to 4 and 6 to 7, and for adhesive sheets 5 and 9.
- the adhesive sheet was irradiated with ultraviolet rays through the release film so as to be 4000 mJ/cm 2 to cure the adhesive sheet.
- the gel fraction after curing with active energy rays was obtained in the same manner as the gel fraction evaluation procedure described above.
- the adhesive sheet 8 produced in Comparative Example 1 is an adhesive sheet in which the reaction due to light irradiation has progressed sufficiently and there is almost no room for active energy ray curing, so this is measured as the gel fraction after curing. provided.
- ⁇ Adhesive strength> One of the release films was removed from the pressure-sensitive adhesive sheets with release films prepared in Examples and Comparative Examples, and a polyethylene terephthalate film ("Cosmo Shine A4300" manufactured by Toyobo Co., Ltd., thickness 100 ⁇ m) was applied as a backing film to a hand roller. and roll crimped. This was cut into strips of 10 mm width ⁇ 150 mm length, the remaining release film was peeled off, and the exposed adhesive surface was roll-bonded to soda lime glass using a hand roller. ° C., gauge pressure of 0.2 MPa, 20 minutes), and finished adhesion was performed to prepare an adhesive force measurement sample. At 23 ° C.
- the backing film was peeled from the soda lime glass, the tensile strength was measured with a load cell, and the adhesive strength to the soda lime glass. (N/cm) was measured.
- One of the release films was removed from the pressure-sensitive adhesive sheets with release films prepared in Examples and Comparative Examples, and a polyethylene terephthalate film ("Cosmo Shine A4300" manufactured by Toyobo Co., Ltd., thickness 100 ⁇ m) was applied as a backing film to a hand roller. and roll crimped. This was cut into strips of 10 mm width ⁇ 150 mm length, the remaining release film was peeled off, and the exposed adhesive surface was roll-bonded to soda lime glass using a hand roller. ° C., gauge pressure of 0.2 MPa, 20 minutes) to finish pasting.
- the pressure-sensitive adhesive sheets were placed through a backing film so that the integrated amount of light at 365 nm was 3000 mJ/cm 2 for pressure-sensitive adhesive sheets 1 to 4 and 6-7, and 4000 mJ/cm 2 for pressure-sensitive adhesive sheets 5 and 9. was irradiated with ultraviolet rays to cure the adhesive sheet, and an adhesive force measurement sample was produced.
- the backing film was peeled off from the soda lime glass while being pulled at an angle of 180° at a peeling speed of 300 mm/min, and the tensile strength was measured with a load cell.
- the 180° peel strength (N/cm) of the sheet against soda lime glass was measured and taken as adhesive strength (curing after lamination).
- the pressure-sensitive adhesive sheet 8 produced in Comparative Example 1 was not subject to this measurement because the reaction due to light irradiation had sufficiently progressed and there was almost no room for active energy ray curing.
- the adhesive sheet cured as described above was cut into strips with a width of 10 mm and a length of 150 mm, and the remaining release film was peeled off.
- This laminate was subjected to an autoclave treatment (60° C., gauge pressure 0.2 MPa, 20 minutes) and then finished and adhered to prepare an adhesive force measurement sample.
- the backing film was peeled off from the soda lime glass while being pulled at an angle of 180° at a peeling speed of 300 mm/min, and the tensile strength was measured with a load cell.
- the 180° peel strength (N/cm) of the sheet against soda lime glass was measured and taken as the adhesive strength (curing before lamination).
- the pressure-sensitive adhesive sheet with a release film prepared in Examples and Comparative Examples was cut into a size of 5 cm ⁇ 5 cm, and the pressure-sensitive adhesive surface exposed by peeling one release film and the step of the evaluation substrate were provided.
- the side surfaces are opposed to each other, vacuum lamination is performed under the conditions of a press pressure of 0.2 MPa for 30 seconds, and an autoclave treatment is performed under the conditions of 70 ° C. and an air pressure of 0.45 MPa for 20 minutes to prepare a laminate for step absorption evaluation. did.
- the produced laminate was visually observed and evaluated according to the following evaluation criteria.
- ⁇ The pressure-sensitive adhesive sheet followed in the vicinity of all steps, and there were no air bubbles.
- Good Two or less bubbles were generated near the step.
- x The pressure-sensitive adhesive sheet did not follow the surface at three or more locations near the step, and air bubbles were generated.
- the pressure-sensitive adhesive surface exposed by peeling off one release film of the pressure-sensitive adhesive sheet cured as described above is opposed to the surface of the side having a step of the evaluation substrate, and the press pressure is 0.2 MPa for 30 seconds.
- Vacuum lamination was performed under the conditions of 70° C., atmospheric pressure of 0.45 MPa, and autoclave treatment for 20 minutes. The above procedure was performed within 10 minutes after the ultraviolet irradiation treatment to prepare a laminate for evaluation of step absorbability after curing. The produced laminate was visually observed and evaluated according to the same evaluation criteria as the step absorbability evaluation described above.
- the integrated light quantity at 365 nm was 3000 mJ/cm for the adhesive sheets 1 to 4, 6 to 7 and the laminated sheet of Reference Example 1 for the adhesive sheets with release films prepared in Examples and Comparative Examples. 2.
- the adhesive sheets 5 and 9 were cured by irradiating the adhesive sheets with ultraviolet rays through the release film so as to obtain 4000 mJ/cm 2 .
- the adhesive sheet 8 produced in Comparative Example 1 is an adhesive sheet in which the reaction due to light irradiation has progressed sufficiently and there is almost no room for active energy ray curing.
- each adhesive sheet was removed, and a transparent polyimide film (manufactured by Kolon Co., Ltd., thickness 50 ⁇ m) was rolled on both sides of the adhesive sheet with a hand roll. After that, autoclave treatment was performed under the conditions of 60° C., atmospheric pressure of 0.2 MPa, and 20 minutes to obtain a laminate sample for flexibility evaluation.
- a transparent polyimide film manufactured by Kolon Co., Ltd., thickness 50 ⁇ m
- the laminate sheet of Reference Example 1 was evaluated with the side of the adhesive sheet 5 as another adhesive sheet set inside. After being bent 200,000 times in a test environment of ⁇ 20° C. or 60° C. and 90% RH, evaluation was made according to the following evaluation criteria.
- ⁇ None of delamination, breakage, buckling, and flow occurred at the bent portion.
- x Any of delamination, breakage, buckling, or flow occurred at the bent portion.
- the laminate sample was bent at a radius of curvature R of 3 mm, stored at 60° C. and 90% RH for 24 hours, and then evaluated according to the following evaluation criteria.
- the laminated sheet of Reference Example 1 was tested in a state in which the pressure-sensitive adhesive sheet 5 as another pressure-sensitive adhesive sheet was positioned inside and bent at a radius of curvature R of 3 mm.
- ⁇ None of delamination, breakage, buckling, and flow occurred at the bent portion.
- x Any of delamination, rupture, buckling, or flow was observed at the bent portion.
- Table 1 shows the results obtained by measuring and evaluating the adhesive sheet and laminate.
- the pressure-sensitive adhesive sheets of Examples 1-7 exhibited good bonding properties in the step absorption test, excellent restorability, and exhibited excellent durability in the bending test when formed into a laminate. Furthermore, the pressure-sensitive adhesive sheets of Examples 1-4 exhibited good lamination properties in the level difference absorption test even when laminated after being cured. The pressure-sensitive adhesive sheet of Reference Example 1 also exhibited excellent step absorbability and excellent bending durability. On the other hand, the pressure-sensitive adhesive sheet produced in Comparative Example 1 used a material that did not have high fluidity, so the strain after 3,600 seconds at 25°C was 50% or less, and the step absorbability was poor. .
- the pressure-sensitive adhesive sheet prepared in Comparative Example 2 uses a material with low flexibility after curing, so it has poor restorability after 200% deformation at 25 ° C after curing with active energy, and bending durability when used as a laminate. It was inferior in terms of sex.
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Abstract
Description
このような表示装置では、カバーレンズ、円偏光板、タッチフィルムセンサー、発光素子等の複数のシート部材が、透明な粘着シートで貼り合された積層構造をしており、ある粘着シートに焦点を当てると、部材と粘着シートが積層された積層体とみなすことができる。
また、画面を折り畳んだ状態から開いたときに、速やかに平らな状態に復元する積層体が求められている。
さらに、折り曲げや巻き取り操作を繰り返すうちに、粘着シートの被着体である部材にストレスがかかることで亀裂が生じ、遂には破断する場合があり、特に低温での繰り返しの折り畳み操作で耐久性のある積層体であることも求められている。
粘着シートを含むデバイスは、デバイスの発熱による高温下での使用や、地域や季節等の環境に応じて高温及び低温下での使用が想定されるため、当該粘着シートには幅広い温度範囲で安定して復元性や耐久性を発現する性質が求められる。
しかしながら、貼り合わせ時に高い流動性をもつ粘着シートでは、幅広い温度範囲で安定して復元性や耐久性を発現することが困難であった。
(1)厚さ0.8mm~1.5mmとし、温度25℃にて1000Paの圧力を3600秒印加した時の歪み(クリープ歪)が50%以上である。
(2)厚さ0.8mm~1.5mmとし、波長365nmの活性エネルギー線を積算光量2000~4000mJ/cm2照射した後に、温度80℃にて1000Paの圧力を180秒印加した時の歪み(クリープ歪)が10%以上となる。
(3)波長365nmの活性エネルギー線を積算光量2000~4000mJ/cm2照射した時の、下記式で表される25℃200%変形後の復元率が60%以上となる。
復元率(%)={(x-y)/x}×100
(xは、厚さ0.8mm~1.5mmとした粘着シートにせん断方向に印加する初期歪であり、yは初期歪を600秒間印加した後、解放して600秒経過後の残留歪である。)
厚さが15μm以上50μm以下であり、
活性エネルギー線硬化性を有し、高低差が2~10μmの段差を10mm以下の間隔で有する画像表示装置構成用部材に下記貼合条件で貼り合せたときに、前記段差の周囲に発泡が無いことを特徴とするフレキシブルディスプレイ用粘着シートを提案する。
(貼合条件)
a)厚み15~50μmの粘着シートに、365nmの積算光量が2000~4000mJ/cm2となるよう紫外線を照射する。
b)高低差2~10μmの段差を10mm以下の間隔で有する基材の表面に、前記粘着シートを、プレス圧0.2MPa、30秒の条件で真空貼合する。
c)70℃、気圧0.45MPa、20分の条件でオートクレーブ処理を行う。
以下の工程1~3を有し、工程1および2を行った後、工程3を行うことを特徴とする、画像表示装置用積層体の製造方法を提案する。
工程1:画像表示装置構成用部材1に、本発明が提案する上記活性エネルギー線硬化性粘着シートの一方の表面を貼合する。
工程2:活性エネルギー線を照射して、本発明が提案する上記活性エネルギー線硬化性粘着シートを硬化させる。
工程3:前記粘着シートの他方の表面に画像表示装置構成用部材2を貼合して積層体とする。
さらに本発明が提案する粘着シートは、当該粘着シートと画像表示装置構成部材とが積層してなる構成を備えた積層体を、高温環境下において屈曲操作しても優れた復元性及び耐久性を発現することができ、低温環境下において屈曲操作しても優れた耐久性を発現することができる。
よって、例えば当該積層体を、高温及び低温環境下において、折り曲げたり、湾曲させたり、巻き取ったりした際でも、優れた耐久性乃至復元性を発現することができる。
以上の点から、本発明が提案する粘着シートは、例えばフレキシブルディスプレイ用粘着シートとして好適に利用することができる。
本発明の実施形態の一例に係る粘着シート(「本粘着シート」と称する)は、(メタ)アクリル系重合体(A)を含む、とりわけ主成分樹脂として含む粘着剤層(「本粘着剤層」と称する)を備えた活性エネルギー線硬化性粘着シートである。
本粘着シートにおける本粘着剤層は、例えば、(メタ)アクリル系重合体(A)を含み、とりわけ主成分樹脂として(メタ)アクリル系重合体(A)を含み、好ましくは架橋剤(B)及び/又は重合開始剤(C)、さらに必要に応じてその他成分を含む粘着剤組成物(「本粘着剤組成物」と称する)から形成することができる。
本粘着シートは、活性エネルギー線によって硬化する余地が残された状態に硬化(「仮硬化」とも称する)されたものであってもよいし、未だ何ら硬化されておらず(「未硬化」と称する)、且つ、活性エネルギー線によって硬化し得るものであってもよい。
本粘着シートが、仮硬化された又は未硬化のものであれば、当該本粘着シートを被着体へ貼合する前又は貼合した後、本粘着シートを活性エネルギー線により硬化(「本硬化」とも称する)させることができ、その結果、凝集力を高めて接着性を高めることができる。
本粘着シートは、厚さ0.8mm~1.5mmとし、温度25℃にて1000Paの圧力を3600秒印加した時の歪み(クリープ歪)が50%以上であるのが好ましい。
本粘着シートにおいて、硬化前の状態で、温度25℃にて1000Paの圧力を3600秒印加した時のクリープ歪が50%以上であるということは、この状態で変形し易いことを示しているから、被着体となる画像表示装置構成部材表面に凹凸を有する場合であっても、段差部の隅々まで追従させることができるから好ましい。
かかる観点から、本粘着シートは、前記クリープ歪が50%以上となるのが好ましく、中でも100%以上、その中でも105%以上、特には110%以上となるのがさらに好ましい。
他方、上限については、室温以下において形状を維持できる点から、前記のクリープ歪が10000%以下であることが好ましい。
かかる観点から、本粘着シートは、前記クリープ歪は5000%以下であることがより好ましく、その中でも2500%以下、さらには1000%以下となるのがさらに好ましく、その中でも500%以下、特には250%以下がより好ましい。
本粘着シートの厚さを上記範囲内に予め調整した上でクリープ歪を測定することにより、測定治具の影響を受けることなく、本粘着シートが有するクリープ歪を正確に把握することができる。
本粘着シートは、硬化後において、温度80℃にて、1000Paの圧力を180秒印加した時の歪み(クリープ歪)が10%以上であるということは、硬化後であっても加熱状態では、変形し易いことを示しているから、被着体となる画像表示装置構成部材表面に凹凸を有する場合であっても、硬化後に加熱することで、段差部の隅々までさらに追従させることができ、表面が平滑になるまで段差部を吸収することができる。
かかる観点から、活性エネルギー線硬化後におけるクリープ歪は10%以上となるのがさらに好ましく、中でも20%以上、その中でも30%以上、さらに40%以上となるのが好ましい。
他方、硬化後における前記歪み(クリープ歪)の上限値は、それが高過ぎると、高温環境下で粘着シートが積層体の端面からはみ出して端面がべたついたり、折り曲げ時に凝集剥離を起こしたり、折り曲げ状態から開いた時の復元性を損ねたりするおそれがあることから、500%以下であるのが好ましく、300%以下であるのがより好ましく、100%以下であるのがさらに好ましく、80%以下であるのが特に好ましく、60%以下であるのが最も好ましい。
本粘着シートは、波長365nmの活性エネルギー線を積算光量2000~4000mJ/cm2照射した時の、下記式で表される25℃200%変形後の復元率が60%以上であるのが好ましい。
復元率(%)={(x-y)/x}×100
(xは、厚さ0.8mm~1.5mmとした粘着シートにせん断方向に印加する初期歪みであり、yは初期歪を600秒間印加した後、解放して600秒経過後の残留歪である。より具体的な測定方法は実施例に記載する。)
本粘着シートは、活性エネルギー線によって硬化する前は、未架橋状態または少し架橋された状態、すなわち、ゲル分率が0%以上20%以下の状態であることが好ましい。
被着面における凹凸への追従性の観点からは、ゲル分率が10%以下であるのがより好ましく、8%以下であるのがさらに好ましく、5%以下であるのがより好ましい。
活性エネルギー線硬化後のゲル分率が10%以上であることで、粘着シートの形状安定性や、積層体とした時の折り曲げ時の復元性や耐久性を付与することができる。
かかる観点から活性エネルギー線硬化後のゲル分率は10%以上であるのが好ましく、中でも30%以上、その中でも40%以上であるのがより好ましい。
他方、活性エネルギー線硬化後におけるゲル分率が85%以下であることが好ましい。
本粘着シートは、このように光感度が鈍いものであってもよい。
本粘着シートは、下記(4)の特性を有することが好ましい。
(4)ソーダライムガラス表面に対する、23℃50%RH、剥離角180°、剥離速度300mm/分における粘着力が1N/cm以上
かかる観点から、当該粘着力は1N/cm以上であるのが好ましく、2N/cm以上であるのがより好ましく、4N/cm以上であるのがさらに好ましく、5N/cm以上であるのが特に好ましく、10N/cm以上であるのがより好ましい。なお、通常上限は40N/cmである。
(5)粘着シートをソーダライムガラスに貼合した後、波長365nmの活性エネルギー線を積算光量2000~4000mJ/cm2照射した時の、23℃50%RH、剥離角180°、剥離速度300mm/分における前記ソーダライムガラス表面に対する粘着力が1N/cm以上
かかる観点から、ソーダライムガラスに貼り合わせた後、活性エネルギー線照射した時の粘着力は、1N/cm以上であるのが好ましく、2N/cm以上であるのがより好ましく、3N/cm以上であるのがさらに好ましく、5N/cm以上であるのがより好ましい。なお、通常上限は40N/cmである。
(6)波長365nmの活性エネルギー線を積算光量2000~4000mJ/cm2照射した後、該粘着シートをソーダライムガラスに貼合した時の、前記ソーダライムガラス表面に対する、23℃50%RH、剥離角180°、剥離速度300mm/分における粘着力が1N/cm以上
かかる観点から、本粘着シートに活性エネルギー線硬化した後、ソーダライムガラスに貼り合わせた時の粘着力は、1N/cm以上であるのが好ましく、2N/cm以上であるのがより好ましく、3N/cm以上であるのがさらに好ましく、5N/cm以上であるのがより好ましい。なお、通常上限は40N/cmである。
本粘着シートは、厚さ0.8mm~1.5mmとし、周波数1Hzの剪断モードで動的粘弾性測定により得られる損失正接が、-30℃において、0.8以上であるのが好ましい。より好ましくは1以上、中でも1.2以上、さらに好ましくは1.5以上であり、また、より好ましくは2.0以下、更に好ましくは1.8以下である。
本粘着シートの損失正接(tanδ)が上記範囲にあることで、被着体が被着面に凹凸を有する場合であっても、加熱により段差部に粘着樹脂が流動充填できる点で好ましい。
硬化後の損失正接(tanδ)が上記範囲にあることで、本粘着シートを用いた積層体を低温環境下で折り曲げても、画像表示装置構成部材界面の剥離や座屈、画像表示装置構成部材の割れ等を起こすことがないため、好ましい。かかる観点から、-30℃以上-10℃以下の範囲における当該損失正接(tanδ)は、0.5以上2.3以下であるのが好ましく、中でも0.8以上或いは2.0以下であるのがさらに好ましく、その中でも1.1以上或いは1.9以下であるのがより好ましい。
損失正接の極大点が-20℃以下であることで、積層体とした時の折り曲げ時の耐久性を付与できる点から好ましい。かかる観点から、当該損失正接の極大点は-25℃以下がより好ましく、-30℃以下がより好ましく、-33℃以下がさらに好ましく、-35℃以下が特に好ましい。また通常、下限は-60℃以上である。
本粘着シートは、厚さ0.8mm~1.5mmとし、温度25℃、周波数1Hzの剪断モードで動的粘弾性測定により得られる貯蔵弾性率(G’)が0.01~0.2MPaであるのが好ましい。
本粘着シートの前記貯蔵弾性率(G’)がかかる範囲であることで、被着体の被着面に凹凸を有する場合であっても、該凹凸に追随しかつ凹凸を吸収するように貼合することができるなどの効果を得ることができる。
かかる観点から、本粘着シートの前記貯蔵弾性率(G’)は、温度25℃、周波数1Hzにおいて、0.01MPa以上0.2MPa以下であるのが好ましく、中でも0.02MPa以上或いは0.1MPa以下であるのが好ましく、その中でも0.03MPa以上或いは0.09MPa以下であることがさらに好ましい。
本粘着シートの硬化後の前記貯蔵弾性率(G’)がかかる範囲であることで、後述する画像表示装置項絵師部材と貼り合わせて積層体とした際、折り曲げ時にデラミ等を起こさず、耐久性が良好となる。
かかる観点から、本粘着シートの硬化後の前記貯蔵弾性率(G’)は、温度25℃、周波数1Hzにおいて、0.02MPa以上0.24MPa以下であるのが好ましく、中でも0.03MPa以上或いは0.20MPa以下であるのが好ましく、その中でも0.04MPa以上或いは0.10MPa以下であるのがさらに好ましい。
本粘着剤組成物は、(メタ)アクリル系重合体(A)、好ましくは架橋剤(B)及び/又は重合開始剤(C)、その他さらに必要に応じてその他の成分を含む組成物である。
本粘着剤組成物において、(メタ)アクリル系重合体(A)を含有し、とりわけ主成分樹脂として含有するものである。
すなわち、(メタ)アクリル系重合体(A)は、本粘着剤組成物を構成する樹脂の中で最も質量割合が高い樹脂である。この際、本粘着剤組成物を構成する樹脂のうち、(メタ)アクリル系重合体(A)の質量割合は50質量%以上、中でも70質量%以上、その中でも80質量%以上、その中でも90質量%以上(100質量%を含む)であってもよい。
前記「他の共重合性モノマー」が共重合性モノマーa8である場合、前記(メタ)アクリル系重合体(A)は、マクロモノマー由来の構造単位を含む共重合体である。
マクロモノマーの数平均分子量は、好ましくは1000以上であり、より好ましくは1500以上であり、さらに好ましくは2000以上である。なお、数平均分子量の上限は通常20000である。
かかるマクロモノマーの数平均分子量としては、好ましくは1000~10000、特に好ましくは1500以上或いは5000以下、更に好ましくは2000以上或いは4000以下である。
また、前記マクロモノマーが、炭素数8~18の直鎖もしくは分岐状のアルキル基を持つ(メタ)アクリレートが共重合されたマクロモノマーであることで、より被着体の被着面に凹凸がある場合でも、凹凸追従性を良好にすることができるから良好である。
かかるマクロモノマーの数平均分子量としては、好ましくは2000~20000、特に好ましくは3000以上或いは15000以下、更に好ましくは4000以上或いは10000以下である。
したがって、共重合性モノマーa8と、それ以外のモノマーの選択や配合比率によって、グラフト共重合体の主鎖と側鎖の特性を変化させることができる。
特に本樹脂組成物においては、(メタ)アクリル系重合体(A)におけるマクロモノマーの共重合割合が30質量%以下であることがホットメルト時の流動性付与の点で好ましく、より好ましくは2質量%以上或いは15質量%以下、さらに好ましくは3質量%以上或いは10質量%以下、とくに好ましくは4質量%以上或いは7質量%以下である。
Foxの計算式とは、以下の式により求められる計算値であり、ポリマーハンドブック〔PolymerHandBook,J.Brandrup,Interscience,1989〕に記載されている値を用いて求めることができる。
1/(273+Tg)=Σ(Wi/(273+Tgi))
[式中、Wiはモノマーiの重量分率、TgiはモノマーiのホモポリマーのTg(℃)を示す。]
このようなガラス転移温度(Tg)を有する繰り返し単位があれば、分子量を調整することにより、優れた加工性や保管安定性を保持できると共に、50℃以上でホットメルトするように調整することができる。
(メタ)アクリル系重合体(A)が、ブロック共重合体又はグラフト共重合体であることによって、形状安定性、及び、ホットメルト性に優れた粘着シートとすることができる。
当該ブロック共重合体の一部のブロックが、マクロモノマー由来の繰り返し単位を含有するものであるのが好ましい。
他方、グラフト共重合体は、幹成分として(メタ)アクリル酸エステル由来の繰り返し単位を含有する共重合体であり、枝成分の導入方法により、櫛型ポリマー、ブラシ状ポリマー、スターポリマー、ヤシ状ポリマー、ダンベルポリマー等の構造をもつものをいう。
当該グラフト共重合体の枝成分としてマクロモノマー由来の繰り返し単位を含有する共重合体であるのが好ましい。
なお、後述する実施例では、ベースポリマーとして、マクロモノマー由来の繰り返し単位を含有するグラフト共重合体を使用している。マクロモノマー由来の繰り返し単位を含有するブロック共重合体であっても、マクロモノマー由来の繰り返し単位が凝集して相分離して効果を発揮することは、グラフト共重合体と共通するため、マクロモノマーを含有するブロック共重合体も、マクロモノマーを含有するグラフト共重合体と同様の効果を得ることができると予想できる。
かかる観点から、(メタ)アクリル系重合体(A)におけるマクロモノマーの共重合割合は2質量%以上であるのが好ましく、中でも3質量%以上、中でも4質量%以上であるのがさらに好ましい。他方、30質量%以下であるのが好ましく、中でも15質量%以下であるのが好ましく、中でも10質量%以下、その中でも8質量%以下、さらにその中でも7質量%以下であるのがさらに好ましい。
そして、前記(メタ)アクリル系重合体(A)が、ブロック共重合体、及び/又は、グラフト共重合体である場合において、ガラス転移温度が上記範囲にある共重合成分の含有量は、上記と同様の理由から、前記(メタ)アクリル系重合体(A)に対して3質量%以上であるのが好ましく、中でも4質量%以上であるのがさらに好ましい。他方、10質量%以下であるのが好ましく、中でも9質量%以下、その中でも8質量%以下、さらにその中でも7質量%以下であるのがさらに好ましい。
なお、後述する実施例で確認しているように、マクロモノマー由来の繰り返し単位、すなわち、ガラス転移温度が20~150℃である共重合体成分は、(メタ)アクリル系重合体(A)に対して3質量%以上であれば、ホットメルト性を付与することができ、4質量%以上であれば、形状を安定させることができることから、この範囲であれば、実施例と同様の効果を得ることができる。
架橋剤(B)は、本粘着剤組成物に架橋構造を形成する化合物乃至組成物であり、2以上の架橋性官能基を有する化合物である。
本粘着剤組成物が、架橋剤(B)を含むことにより、本粘着剤組成物が架橋構造を形成し、本粘着シートに耐久性や復元性を付与することができる。
中でも、本粘着シートが活性エネルギー線を照射されることにより硬化する性質を担保する観点から、架橋剤(B)として、(メタ)アクリロイル基を2つ以上有する多官能(メタ)アクリレート(b)であるのが好ましい。
上限値に関しては、適度な柔軟性を維持して折り曲げ時の被着体への追従性を担保する観点から、10質量部以下であるのが好ましく、7質量部以下であるのがより好ましく、5質量部以下であるのがさらに好ましく、さらにその中でも3質量部以下、その中でも2質量部以下である方が特に好ましい。
特に、硬化後に、段差を有する画像表示装置構成部材等へ貼合する場合において、段差に追従することができる程度な柔軟性を付与する観点からは、5質量部以下であるのが好ましく、中でも3質量部以下、その中でも2質量部以下である方がより好ましい。
重合開始剤(C)は、本粘着シートに活性エネルギー線硬化性を付与するものであり、活性エネルギー線によってラジカルを発生する化合物であればよい。
重合開始剤(C)は、ラジカル発生機構によって大きく2つに分類され、重合開始剤自身の単結合を開裂分解してラジカルを発生させることができる開裂型光開始剤と、励起した開始剤と系中の水素供与体とが励起錯体を形成し、水素供与体の水素を転移させることができる水素引抜型光開始剤と、に大別される。
光開始剤として水素引抜型光開始剤を用いた場合、アクリル系(共)重合体からも水素引抜反応を起こして、活性エネルギー線硬化性化合物のみならずアクリル系(共)重合体も架橋構造に取り込まれ、架橋点が多い架橋構造を形成することができる点で好ましい。
また、重合開始剤(C)として開裂型光開始剤を用いた場合、一度ラジカル発生させると分解して失活することから、硬化後に予期せぬ反応や劣化をおこす恐れがない点で好ましい。
本粘着剤組成物に含まれる前記以外の「その他の成分」として、例えば、必要に応じて、シランカップリング剤や、粘着付与樹脂、可塑剤、酸化防止剤、光安定化剤、金属不活性化剤、老化防止剤、吸湿剤、重合禁止剤、紫外線吸収剤、防錆剤、無機粒子、増感剤、顔料などの各種の添加剤を適宜含有させることが可能である。これら添加剤の量は、典型的には、粘着シートの硬化に悪影響を与えないように、又は、粘着シートの物理的特性に悪影響を与えないように選択するのが好ましい。
また、必要に応じて、三級アミン系化合物、四級アンモニウム系化合物、ラウリル酸スズ化合物などの反応触媒を適宜含有してもよい。
シランカップリング剤の具体例としては、例えば、N-(β-アミノエチル)-γ-アミノプロピルトリメトキシシラン、N-(β-アミノエチル)-γ-アミノプロピルメチルジメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-メタクリロキシプロピルトリメトキシシラン等を例示することができる。
中でも、接着性が良好であり、黄変等の変色が少ないこと等の観点から、γ-グリシドキシプロピルトリメトキシシラン又はγ-メタクリロキシプロピルトリメトキシシランを好ましく用いることができる。
前記シランカップリング剤は、1種のみを単独で又は2種以上を組み合わせて用いることができる。
なお、シランカップリング剤と同様に、有機チタネート化合物等のカップリング剤も有効に活用できる。
炭化水素粘着付与剤としては、ポリテルペン(例えば、αピネン系樹脂、βピネン系樹脂、及びリモネン系樹脂)、及び芳香族変性ポリテルペン樹脂(例えば、フェノール変性ポリテルペン樹脂)等のテルペン樹脂、クマラン-インデン樹脂、並びにC5系炭化水素樹脂、C9系炭化水素樹脂、C5/C9系炭化水素樹脂、及びジシクロペンタジエン系樹脂等の石油系樹脂、変性ロジンや水素化ロジン、重合ロジン、ロジンエステル等ロジン類を挙げることができる。
炭化水素粘着付与剤は本粘着剤組成物に相溶することが好ましい。
次に、本粘着シートの製造方法について説明する。ただし、以下の説明は、本粘着シートを製造する方法の一例であり、本粘着シートはかかる製造方法により製造されるものに限定されるものではない。
なお、種々の原料を混合する際、シランカップリング剤、酸化防止剤等の各種添加剤は、予め樹脂とともにブレンドしてから混練機に供給してもよいし、予め全ての材料を溶融混合してから供給してもよいし、添加剤のみを予め樹脂に濃縮したマスターバッチを作製し供給してもよい。
ここで、照射する活性エネルギー線としては、α線、β線、γ線、中性子線、電子線などの電離性放射線、紫外線、可視光線などを挙げることができ、中でも光学装置構成部材へのダメージ抑制や反応制御の観点から紫外線が好適である。
また、活性エネルギー線の照射エネルギー、照射時間、照射方法などに関しては特に限定されず、開始剤を活性化させて(メタ)アクリレート成分を重合できればよい。
コーティング手法を用いた場合、上記の活性エネルギー線照射硬化の他、熱硬化させることにより本粘着シートを得ることもできる。
本粘着シートは、本粘着剤層からなる単層構成であっても、本粘着剤層を備えた2層以上の複数層構成であってもよい。
本粘着シートが2層以上の複数層構成である場合、本粘着剤組成物からなる層以外の層の組成は任意である。ただし、例えば中間層や最表層或いは最裏層を本粘着剤層以外の層で形成する場合、層間接着性をより高める観点から、本粘着剤層以外の層を形成する粘着剤組成物も、(メタ)アクリル系重合体を含む粘着剤組成物から形成するのが好ましく、中でも、本粘着剤層と同じ(メタ)アクリル系重合体(A)を含むのがより好ましい。さらには、本粘着剤層以外の層も、架橋剤(B)および/又は重合開始剤(C)を含むのがより好ましい。
折り曲げ時や湾曲時の曲げ応力は厚みに比例することから、本粘着シートは、厚みが50μm以下であれば、折り曲げ時や湾曲時の応力を緩和することができ、また、積層体の薄型化、ひいてはフレキシブル画像表示装置の薄膜化に寄与することができる。一方、15μm以上であれば、ハンドリング性が良好であり、画像表示装置構成部材に高低差2μm以上10μm以下の段差を有する凹凸部がある場合でも段差に追従することができる。
よって、本粘着シートの厚みは、50μm以下であるのが好ましく、中でも45μm以下、さらにその中でも40μm以下、特に35μm以下であるのがさらに好ましい。一方、下限に関しては、15μm以上であるのが好ましく、中でも17μm以上、その中でも20μm以上であるのがより好ましい。
この際、凹凸の段差高低差が、本粘着シートの厚さの12%以下であれば吸収することができる。
(貼合条件)
a)厚み15~50μmの粘着シートに、365nmの積算光量が2000~4000mJ/cm2となるよう紫外線を照射する。
b)高低差2μm以上、例えば2~10μmの段差を10mm以下の間隔で有する基材の表面に、前記粘着シートを、プレス圧0.2MPa、30秒の条件で真空貼合する。
c)70℃、気圧0.45MPa、20分の条件でオートクレーブ処理を行う。
本粘着シートは、粘着シート単体として用いることも可能である。例えば、後述する画像表示装置用部材に本粘着剤組成物を直接塗布してシート状に形成したり、本粘着剤組成物を直接押出成形したり、型に注入したりして、本粘着シートを使用することができる。更には、画像表示装置構成部材間に本粘着剤組成物を直接充填することによって、本粘着シートを使用することもできる。
例えば、他の粘着シートが、本粘着シートよりも屈曲性に優れたものであれば、フレキシブル画像表示装置により好適である。
そのような他の粘着シートとして、ゲル分率が70%以上であり、厚さ0.8mm~1.5mmとし、周波数1Hzの剪断モードで動的粘弾性測定により得られる損失正接の極大点が-25℃以下である粘着シートを挙げることができる。
この際、当該損失正接の極大点が-25℃以下であれば、高温及び低温下での折り曲げにおいても復元することができるため好ましい。
かかる観点から、他の粘着シートの当該損失正接の極大点は-25℃以下であるのが好ましく、中でも-30℃以下、その中でも-35℃以下であるのがさらに好ましい。
本粘着シートは、本粘着剤組成物から形成される本粘着剤層と、離型フィルムとを備えた離型フィルム付き粘着シート(「本離型フィルム付き粘着シート」と称する)として使用することも可能である。例えば、本粘着剤組成物を、離型フィルム上に単層又は多層のシート状に成型した離型フィルム付き粘着シートの形態とすることもできる。
本発明の実施形態の一例に係る積層体(「本積層体」と称する)は、離型フィルムと、高低差2μm以上の段差を被積層面に有する画像表示装置構成用部材とが、前記本粘着シートを介して積層してなる構成を備えた積層体である。
この際、活性エネルギー線の照射量は、段差吸収性の点から、4000mJ/cm2以下であることが好ましく、特に3500mJ/cm2以下、更に3200mJ/cm2以下であるのがさらに好ましい。また、十分に硬化させて復元性を向上させる点から、2000mJ/cm2以上が好ましく、2500mJ/cm2以上がより好ましく、2800mJ/cm2以上がさらに好ましい。
本発明の実施形態の一例に係る画像表示装置用積層体(以下、「本積層体」と称することがある。)は、上述した本粘着シートの少なくとも片面に、画像表示装置構成用部材を備えた積層体である。
さらに、第1の部材、第2の部材及び第3の画像表示装置構成用部材(以下「第3の部材」と称することがある)とが、それぞれ本粘着シートを介してこの順で積層されてなる構成を備えた積層体であってもよい。積層する2以上の部材は同じでもよいし、異なるものでもよい。
よって、本積層体の厚みは、0.02mm以上であるのが好ましく、中でも0.03mm以上、特に0.05mm以上であるのがより好ましい。一方、上限に関しては、1.0mm以下であるのが好ましく、中でも0.7mm以下、特に0.5mm以下であるのがさらに好ましい。
フレキシブル画像表示装置の構成や本粘着シートの位置にも依るが、第1の部材、第2の部材及び第3の部材(これらをまとめて「本部材」と称する場合がある)としては、例えばカバーレンズ、偏光板、位相差フィルム、バリアフィルム、タッチセンサーフィルム、発光素子、PSA等を挙げることができる。
また、本部材のうちの少なくとも一つは、本粘着シートとの接触面に、配線、印刷、パターン現像や表面処理、エンボス加工等により種々の凹凸が賦形されていてもよい。部材の表面が凹凸を有する場合、凹凸の段差の高低差は2μm以上、例えば2μm以上10μm以下であるのが好ましく、中でも8μm以下であるのがより好ましく、その中でも3μm以上或いは7μm以下であるのがより好ましく、その中でも4μm以上或いは6μm以下であるのがさらに好ましい。
ここで「主成分」とは、画像表示装置構成用部材を構成する成分のうち最も多い質量比率を占める成分であることをいい、具体的には画像表示装置構成用部材又は該部材を形成する粘着剤組成物の50質量%以上を占めるものであり、55質量%以上、中でも60質量%以上を占めるのがさらに好ましい。
本積層体を組み込むことで、例えば本積層体を他の画像表示装置構成部材に積層することで、本積層体を備えたフレキシブル画像表示装置(「本画像表示装置」とも称する)を形成することができる。
フレキシブル画像表示装置とは、繰り返し折り曲げや湾曲操作、巻き取り操作をしても曲げ跡を残さず、折り曲げ状態や湾曲状態、巻き取り状態を解放した際には折り曲げや湾曲操作、巻き取り操作をする前の状態まで素早く回復することができ、歪みなく画像を表示できる画像表示装置をいう。特に本積層体は、画像表示装置構成部材の本粘着シートとの接触面に、高低差2μm以上の段差を有する凹凸があっても、気泡を発生させないように、段差に追従して段差を吸収することができるばかりか、低温或いは高温における環境下で折り曲げや湾曲、巻き取り操作をしても、積層体のデラミや割れを防止でき、復元性も良好であるので、フレキシブル性にすぐれた画像表示装置を製造できることが特徴の一つである。
次に、本積層体の製造方法の一例について説明する。ただし、本積層体の製造方法が、次に説明する方法に限定されるものではない。
工程1:画像表示装置構成用部材1に、本粘着シートの一方の表面を貼合する。
工程2:活性エネルギー線を照射して本粘着シートを硬化させる。
工程3:前記粘着シートの他方の表面に画像表示装置構成用部材2を貼合して積層体とする。
工程4:前記積層体に加熱処理を施して前記粘着シートをホットメルトさせる。
工程1は、画像表示装置構成用部材1に、本粘着シートの一方の表面を貼合する工程である。
貼合方法としては、ロール貼合、平行平板によるプレス貼合、ダイヤフラム貼合等の既知の方式を用いることができる。
貼合環境としては、常圧で貼り合わせる大気貼合方式と、減圧下で貼り合わせる真空貼合方式がある。貼合時の気泡を防止する観点からは、減圧環境下で平行平板にて貼合する方法が好ましい。また、貼合温度を適宜調整してもよい。
工程2は、活性エネルギー線を照射して本粘着シートを硬化させる工程である。
活性エネルギー線としては、紫外線及び可視光線が好適である。
活性エネルギー線を照射する際の光源については、例えば高圧水銀ランプ、メタルハライドランプ、キセノンランプ、ハロゲンランプ、LEDランプ、蛍光ランプなどの中から、照射する光の波長や照射量に応じて使い分けることができる。
照射時間や照射手段に関しては特に限定されないが、例えば紫外線照射であれば、波長365nmにおける積算光量が2000mJ/cm2以上、特に3000mJ/cm2以上となるように照射するのが好ましい。
工程3は、工程1及び工程2を経た本粘着シートの他方の表面に画像表示装置構成用部材2を貼合して積層体とする工程である。
工程3では、必要に応じて、画像表示装置構成用部材1及び/又は画像表示装置構成用部材2を加熱すると共に、画像表示装置構成用部材2を貼合するようにしてもよい。
この際の加熱は、例えば、画像表示装置構成用部材1/本粘着シート/画像表示装置構成用部材2からなる画像表示装置用積層体を、両側から、所定温度に加熱されたプレス板で加圧する方法などを挙げることができる。
また、この際の加熱温度は、温度50℃以上80℃以下であるのが好ましい。すなわち、50℃以上80℃以下に画像表示装置構成用部材1及び/又は画像表示装置構成用部材2を加熱して前記粘着シートをホットメルトさせながら、画像表示装置構成用部材2を貼合するのが好ましい。
また、プレス板で加圧する際のプレス圧は、0.01MPa以上或いは0.4MPa以下、その中でも0.02MPa以上或いは0.35MPa以下であるのがさらに好ましい。
工程4は、工程3で得られた、貼合後の前記積層体に加熱処理を施して前記粘着シートをホットメルトさせる工程である。この工程4は、必要に応じて実施すればよい。
貼合後の前記積層体に加熱処理を施して前記粘着シートをホットメルトさせることにより、第1の部材又は第2の部材の表面、例えば被積層面に高低差2μm以上、例えば2μm以上10μm以下の段差を有する凹凸を有する場合であっても、前記粘着シートは当該段差に追従して段差を吸収してその表面を平滑にすることができる。
また、加熱処理と併せて、0.2MPa以上0.8MPa以下の気圧を5分間以上、本積層体に掛けるようにしてもよい。この際の気圧は、0.2MPa以上0.8MPa以下であるのが好ましく、その中でも0.4MPa以上或いは0.6MPa以下であるのがさらに好ましい。
上記処理時間は、5分以上或いは60分以下、その中でも10分以上或いは30分以下であるのがさらに好ましい。
上記プレス圧は、0.01MPa以上或いは0.4MPa以下、その中でも0.02MPa以上或いは0.35MPa以下であるのがさらに好ましい。
上記処理時間は、5秒以上或いは10分以下、その中でも10秒以上或いは5分以下であるのがさらに好ましい。
本製造方法は、第1及び第2の部材が活性エネルギー線を透過しない場合に有効である。
硬化後の本粘着シートをホットメルトさせる場合、本粘着シートに活性エネルギー線を照射した後30分以内にホットメルト処理するのが好ましい。その理由は完全に硬化する前にホットメルト処理をすることで、2μm以上の段差を有する凹凸により一層追従させ易くなるからである。かかる観点から、活性エネルギー線を照射してからホットメルト処理するまでの時間は30分以内が好ましく、20分以内がより好ましく、10分以内がさらに好ましい。
本発明においては、「フィルム」と称する場合でも「シート」を含むものとし、「シート」と称する場合でも「フィルム」を含むものとする。
また、画像表示パネル、保護パネル等のように「パネル」と表現する場合、板体、シートおよびフィルムを包含するものである。
また、「X以上」(Xは任意の数字)と記載した場合、特にことわらない限り「好ましくはXより大きい」の意を包含し、「Y以下」(Yは任意の数字)と記載した場合、特にことわらない限り「好ましくはYより小さい」の意も包含するものである。
・(メタ)アクリル系重合体(A-1):数平均分子量2800のポリメタクリル酸メチルマクロモノマー(Tg105℃)6質量部と、ブチルアクリレート(Tg-55度)90質量部と、アクリル酸(Tg106℃)4質量部とが共重合してなるアクリル系グラフト共重合体(質量平均分子量:22万、Tg-45℃)
・(メタ)アクリル系重合体(A-2):数平均分子量2800のポリメタクリル酸メチルマクロモノマー(Tg105℃)15質量部と、ブチルアクリレート(Tg-55℃)81質量部と、アクリル酸4(106℃)質量部とが共重合してなるアクリル系グラフト共重合体(質量平均分子量:16万、Tg-36℃)
・(メタ)アクリル系重合体(A-3):2-エチルヘキシルアクリレート(Tg-70℃)、メチルアクリレート(Tg8℃)、エチルアクリレート(Tg-20℃)、2-ヒドロキシエチルアクリレート(Tg-15℃)及び4-ヒドロキシブチルアクリレート(Tg-40℃)が共重合してなるアクリル共重合体(質量平均分子量:約70万、Tg-54℃)
・(メタ)アクリル系重合体(A-4):数平均分子量5500のSLMA(ラウリルメタクリレート)マクロモノマー(Tg-65℃)15質量部と、ブチルアクリレート(Tg-55℃)85質量部とがランダム共重合してなるアクリル系グラフト共重合体(質量平均分子量:41万、Tg-38℃)
・(メタ)アクリル系重合体(A-5):数平均分子量2800のポリメタクリル酸メチルマクロモノマー(Tg105℃)9質量部と、ブチルアクリレート(Tg-55℃)87質量部と、アクリル酸4(106℃)質量部とが共重合してなるアクリル系グラフト共重合体(質量平均分子量:16万、Tg-36℃)
・(メタ)アクリル系重合体(A-6):2-エチルヘキシルアクリレート(Tg-70℃)、メチルアクリレート(Tg8℃)、2-ヒドロキシエチルアクリレート(Tg-15℃)が共重合してなるアクリル共重合体(質量平均分子量:約40万、Tg-50℃)
アクリル系共重合体のガラス転移温度は、上記共重合各成分のガラス転移温度と構成比率から、Foxの計算式によって算出される理論Tgを記載した。
・架橋剤(B-1):プロポキシ化ペンタエリスリトールトリアクリレート
・架橋剤(B-2):ポリテトラメチレングリコールジ(メタ)アクリレート
・開始剤(C-1):2,4,6-トリメチルベンゾフェノン及び4-メチルベンゾフェノンの混合物(IGM社製「Esacure TZT」)
・単官能(メタ)アクリレート(D-1):4-ヒドロキシブチルアクリレート
・単官能(メタ)アクリレート(D-2):プロピレングリコール骨格含有単官能ウレタンアクリレート(AGC社製「PEM-X264」、質量平均分子量:1万)
・シランカップリング剤(E-1):KBM403(信越シリコーン社製)
・防錆剤(E-2):1,2,3-ベンゾトリアゾール
(メタ)アクリル系重合体(A-1)100質量部、架橋剤(B-1)1.5質量部、開始剤(C-1)1.5質量部、防錆剤(E-2)0.5質量部を均一混合し、粘着剤組成物を作製した。
シリコーン離型処理された厚さ100μmの離型フィルム(三菱ケミカル社製PETフィルム)上に、前記粘着剤組成物の厚みが25μmとなるようにシート状に展開した。
なお、粘着シート1は、活性エネルギー線を照射することにより硬化する活性エネルギー線硬化性を備えた活性エネルギー線硬化性粘着シートであった。
表1に示したように厚みを変更した以外、実施例1と同様に粘着シート2及び離型フィルム/粘着シート2/離型フィルムからなる離型フィルム付き粘着シート2を作製した。
なお、粘着シート2は、光を照射することにより硬化する活性エネルギー線硬化性を備えた粘着シートであった。
表1に示したように各成分を準備し、粘着剤層の原料とした。
なお、粘着シート3は、光を照射することにより硬化する活性エネルギー線硬化性を備えた粘着シートであった。
表1に示したように各成分を準備し、粘着剤層の原料とした。
なお、粘着シート4は、光を照射することにより硬化する活性エネルギー線硬化性を備えた粘着シートであった。
表1に示したように各成分を準備し、粘着剤層の原料とした。
実施例1と同様に粘着シート5および離型フィルム/粘着シート5/離型フィルムからなる離型フィルム付き粘着シート5を作製した。
なお、粘着シート5は、光を照射することにより硬化する活性エネルギー線硬化性を備えた粘着シートであった。
表1に示したように各成分を準備し、粘着剤層の原料とした。
実施例3と同様に粘着シート6および離型フィルム/粘着シート6/離型フィルムからなる離型フィルム付き粘着シート6を作製した。
なお、粘着シート6は、光を照射することにより硬化する活性エネルギー線硬化性を備えた粘着シートであった。
表1に示したように各成分を準備し、粘着剤層の原料とした。
実施例3と同様に粘着シート7および離型フィルム/粘着シート7/離型フィルムからなる離型フィルム付き粘着シート7を作製した。
なお、粘着シート7は、光を照射することにより硬化する活性エネルギー線硬化性を備えた粘着シートであった。
(メタ)アクリル系重合体(A-3)100質量部、単官能(メタ)アクリレート(D-1)25量部、開始剤(C-1)3質量部、シランカップリング剤0.3質量部、防錆剤0.3質量部を配合して粘着剤組成物を作製し、シリコーン処理された厚さ100μmの離型フィルム(三菱ケミカル社製PETフィルム)上に、前記粘着剤組成物の厚みが25μmとなるようにシート状に展開した。
粘着シート8は光照射による反応が十分進行しており、活性エネルギー線硬化の余地がほとんどない粘着シートである。
(メタ)アクリル系重合体(A-2)100質量部、架橋剤(B-1)2.5質量部、単官能(メタ)アクリレート(D-1)7.5量部、開始剤(C-1)1.5質量部、防錆剤0.3質量部を準備し、粘着剤層の原料とした。
なお、粘着シート9は、光を照射することにより硬化する活性エネルギー線硬化性を備えた粘着シートであった。
実施例1で作製した粘着シート1と、他の粘着シートとしての比較例1で作製した粘着シート8をハンドローラーにて積層し、総厚み50μmの積層シートを作製した。
なお、他の粘着シートとしての粘着シート5のゲル分率は70%であり、周波数1Hzの剪断モードで動的粘弾性測定により得られる損失正接の極大点が-37℃であった。
実施例で得た粘着シートの測定・評価を次のように行った。
実施例及び比較例で作製した離型フィルム付き粘着シートから離型フィルムを取り除き、ハンドローラーにて積層することを繰り返して、厚さが約0.9mmになるように積層し、直径8mmの円状に打ち抜いた離型フィルム付き粘着シートを作製し、これをサンプルとした。
上記サンプルについて、レオメータ(TAインスツルメント社製「DHR-2」)への設置時に離型フィルムを取り除いて使用し、測定治具:直径8mmパラレルプレート、温度:25℃、圧力:1000Paにて、3600秒後の歪み(クリープ歪)(%)を測定した。
なお、比較例1で作製した粘着シート8は、光照射による反応が十分進行しており、活性エネルギー線硬化の余地がほとんどない粘着シートであるため、上記の紫外線照射は行わず、測定に供した。
上記サンプルについて、レオメータ(TAインスツルメント社製「DHR-2」)を用いて、測定治具:直径8mmパラレルプレート、温度:80℃、圧力:1000Paにて、180秒後の歪み(クリープ歪)(%)を測定した。
実施例及び比較例で作製した離型フィルム付き粘着シートに対して、高圧水銀ランプを用いて、365nmの積算光量が粘着シート1~4、6~7では3000mJ/cm2、粘着シート5、9では4000mJ/cm2となるよう、離型フィルムを介して粘着シートに紫外線を照射し、粘着シートを硬化させた。
なお、比較例1で作製した粘着シート8は、光照射による反応が十分進行しており、活性エネルギー線硬化の余地がほとんどない粘着シートであるため、上記の紫外線照射は行わず、測定に供した。
上記サンプルについて、レオメータ(TAインスツルメント社製「DHR-2」、測定治具:直径8mmパラレルプレート)を用いて、温度25℃にて、初期歪(x)としてのせん断歪が200%となるように、600秒間サンプルにせん断方向に応力を印加した。その後、応力を解放して600秒経過後の残留歪(y)を測定し、復元率を下記式より求めた。
復元率(%)={(x-y)/x}×100
上記式において、xは、厚さ約0.9mmになるように積層した粘着シートに、せん断方向に印加する初期歪みであり、yは初期歪を600秒間印加した後、解放して600秒経過後の残留歪である。
実施例及び比較例で作製した粘着シートを、厚さが約0.9mmになるように積層し、直径8mmの円状に打ち抜いたものを作製した。
上記サンプルについて、粘弾性測定装置(T.A.Instruments社製,製品名「DHR-2」)を用いて、測定治具:直径8mmパラレルプレート、周波数:1Hz、測定温度:-50~150℃、昇温速度:5℃/分にて動的粘弾性測定を行い、得られたデータから、-30℃における損失正接(tanδ)の値を読みとった。
実施例及び比較例で作製した各離型フィルム付き粘着シートから離型フィルムを取り除き、約0.1gの粘着シート片を採取した。
採取した粘着シート片は、あらかじめ袋状にした質量(X)のSUSメッシュ(#150)に包み、袋の口を閉じてサンプルを作製して、当該サンプルの質量(Y)を測定した。前記サンプルを酢酸エチルに浸漬させた状態で23℃、24時間暗所保管したのち、前記サンプルを取り出して70℃で4.5時間加熱することで酢酸エチルを蒸発させ、乾燥させたサンプルの質量(Z)を測定した。測定したそれぞれの質量を下記式によって、硬化前のゲル分率を算出した。
ゲル分率(%)=[(Z-X)/(Y-X)]×100
なお、比較例1で作製した粘着シート8は、光照射による反応が十分進行しており、活性エネルギー線硬化の余地がほとんどない粘着シートであるため、これを硬化後のゲル分率として測定に供した。
実施例及び比較例で作製した各離型フィルム付き粘着シートから、一方の離型フィルムを取り除き、裏打ちフィルムとしてポリエチレンテレフタレートフィルム(東洋紡績社製「コスモシャインA4300」、厚さ100μm)をハンドローラーにてロール圧着した。これを、10mm幅×150mm長の短冊状に裁断し、残る離型フィルムを剥がして露出した粘着面を、ソーダライムガラスにハンドローラーを用いてロール貼着し、この積層体にオートクレーブ処理(60℃、ゲージ圧0.2MPa、20分)を施して仕上げ貼着し、粘着力測定サンプルを作製した。
23℃、40%RHにて、180°をなす角度に剥離速度300mm/分にて引っ張りながら、ソーダライムガラスから裏打ちフィルムを剥離し、ロードセルで引張強度を測定して、ソーダライムガラスに対する粘着力(N/cm)を測定した。
実施例及び比較例で作製した各離型フィルム付き粘着シートから、一方の離型フィルムを取り除き、裏打ちフィルムとしてポリエチレンテレフタレートフィルム(東洋紡績社製「コスモシャインA4300」、厚さ100μm)をハンドローラーにてロール圧着した。これを、10mm幅×150mm長の短冊状に裁断し、残る離型フィルムを剥がして露出した粘着面を、ソーダライムガラスにハンドローラーを用いてロール貼着し、この積層体にオートクレーブ処理(60℃、ゲージ圧0.2MPa、20分)を施して仕上げ貼着した。その後、高圧水銀ランプを用いて、365nmの積算光量が粘着シート1~4、6~7では3000mJ/cm2、粘着シート5、9では4000mJ/cm2となるよう、裏打ちフィルムを介して粘着シートに紫外線を照射して粘着シートを硬化させ、粘着力測定サンプルを作製した。
23℃40%RHにて、180°をなす角度に剥離速度300mm/分にて引っ張りながら、ソーダライムガラスから裏打ちフィルムを剥離し、ロードセルで引張強度を測定して、活性エネルギー線硬化後における粘着シートのソーダライムガラスに対する180°剥離強度(N/cm)を測定し、粘着力(貼合後硬化)とした。
なお、比較例1で作製した粘着シート8は、光照射による反応が十分進行しており、活性エネルギー線硬化の余地がほとんどない粘着シートであるため、本測定は行わなかった。
実施例及び比較例で作製した各離型フィルム付き粘着シートから、一方の離型フィルムを取り除き、裏打ちフィルムとしてポリエチレンテレフタレートフィルム(東洋紡績社製「コスモシャインA4300」、厚さ100μm)をハンドローラーにてロール圧着した。高圧水銀ランプを用いて、365nmの積算光量が粘着シート1~4、6~7では3000mJ/cm2、粘着シート5、9では4000mJ/cm2となるよう、裏打ちフィルムを介して粘着シートに紫外線を照射し、粘着シートを硬化させた。
なお、比較例1で作製した粘着シート8は、光照射による反応が十分進行しており、活性エネルギー線硬化の余地がほとんどない粘着シートであるため、これを貼合前硬化したシートとして測定に供した。
23℃40%RHにて、180°をなす角度に剥離速度300mm/分にて引っ張りながら、ソーダライムガラスから裏打ちフィルムを剥離し、ロードセルで引張強度を測定して、活性エネルギー線硬化後における粘着シートのソーダライムガラスに対する180°剥離強度(N/cm)を測定し、粘着力(貼合前硬化)とした。
54mm×82mm×厚さ0.55mmのソーダライムガラス上に、6mm×100mm×厚さ5.4μmのPETフィルムを10mm間隔で2枚配置し、高低差5.4μmの段差を有する凸状部を表面に形成してなる評価用基材とした。
◎:全ての段差近傍で粘着シートが追従し気泡がなかった。
○:段差近傍で発生する気泡が2ヵ所以下であった。
×:段差近傍で3ヵ所以上粘着シートが追従せず気泡が発生した。
実施例1~4で作製した離型フィルム付き粘着シートに対して、高圧水銀ランプを用いて、365nmの積算光量が3000mJ/cm2となるよう、離型フィルムを介して粘着シートに紫外線を照射し、粘着シートを硬化させた。
実施例及び比較例で作製した離型フィルム付き粘着シートに対して、高圧水銀ランプを用いて、365nmの積算光量が粘着シート1~4、6~7および参考例1の積層シートでは3000mJ/cm2、粘着シート5,9では4000mJ/cm2となるよう、離型フィルムを介して粘着シートに紫外線を照射し、粘着シートを硬化させた。
なお、比較例1で作製した粘着シート8は、光照射による反応が十分進行しており、活性エネルギー線硬化の余地がほとんどない粘着シートであるため、上記の紫外線照射は行わず、屈曲性評価用の積層体サンプルとした。
前記積層体サンプルを、恒温恒湿器内耐久システムと面状体無負荷U字伸縮試験機(ユアサシステム機器(株)製)を用いて、曲率半径R=3mm、60rpm(1Hz)の設定にて、U字曲げのサイクル評価を行った。
なお、参考例1の積層シートについては、他の粘着シートとしての粘着シート5側を内側として評価を行った。
試験環境-20℃又は60℃、90%RHにおいて20万回折り曲げ後、下記の評価基準で評価した。
×:屈曲部のデラミ、破断、座屈、流動の何れかが発生した。
前記積層体サンプルを、曲率半径R=3mmにて屈曲し、60℃、90%RHの条件で24時間保管後、下記の評価基準で評価した。
なお、参考例1の積層シートについては、他の粘着シートとしての粘着シート5を内側として曲率半径R=3mmにて屈曲した状態で試験を行った。
○:屈曲部のデラミ、破断、座屈、流動のいずれも発生しなかった。
×:屈曲部でデラミ・破断・座屈・流動の何れかが見られた。
参考例1の粘着シートも、優れた段差吸収性及び優れた屈曲耐久性を示した。
一方、比較例1で作製した粘着シートは、高い流動性をもたない材料を使用しているため、25℃3600秒後のひずみが50%以下であり、段差吸収性に劣るものであった。
比較例2で作製した粘着シートは、硬化後の柔軟性が低い材料を使用しているため、活性エネルギー硬化後において25℃200%変形後の復元性に劣り、積層体とした時の屈曲耐久性にも劣るものであった。
Claims (32)
- (メタ)アクリル系重合体(A)を含む粘着剤層を備え、下記(1)~(3)の要件を満たす活性エネルギー線硬化性粘着シート。
(1)厚さ0.8mm~1.5mmとし、温度25℃にて1000Paの圧力を3600秒印加した時の歪み(クリープ歪)が50%以上である。
(2)厚さ0.8mm~1.5mmとし、波長365nmの活性エネルギー線を積算光量2000~4000mJ/cm2照射した後に、温度80℃にて1000Paの圧力を180秒印加した時の歪み(クリープ歪)が10%以上となる。
(3)波長365nmの活性エネルギー線を積算光量2000~4000mJ/cm2照射した時の、下記式で表される25℃200%変形後の復元率が60%以上となる。
復元率(%)={(x-y)/x}×100
(xは、厚さ0.8mm~1.5mmとした粘着シートにせん断方向に印加する初期歪であり、yは初期歪を600秒間印加した後、解放して600秒経過後の残留歪である。) - 前記(メタ)アクリル系重合体(A)は、ブロック共重合体、及び/又はグラフト共重合体である、請求項1に記載の活性エネルギー線硬化性粘着シート。
- 前記粘着シートを厚さ0.8mm~1.5mmとし、周波数1Hzの剪断モードで動的粘弾性測定した際に得られる損失正接の極大点が-20℃以下である、請求項1又は2に記載の活性エネルギー線硬化性粘着シート。
- 前記(メタ)アクリル系重合体(A)は、マクロモノマー由来の構造単位を含む共重合体である、請求項1~3の何れか一項に記載の活性エネルギー線硬化性粘着シート。
- 前記マクロモノマーは、炭素数1~3の直鎖もしくは分岐状のアルキル基を持つ(メタ)アクリレートが共重合されたマクロモノマーである、請求項1~4の何れか一項に記載のエネルギー線硬化性粘着シート。
- 前記マクロモノマーは、炭素数8~18の直鎖もしくは分岐状のアルキル基を持つ(メタ)アクリレートが共重合されたマクロモノマーである、請求項1~4の何れか一項に記載のエネルギー線硬化性粘着シート。
- (メタ)アクリル系重合体(A)は、マクロモノマーの共重合割合が2質量%以上30質量%以下である請求項4~6の何れか一項に記載の活性エネルギー線硬化性粘着シート。
- 前記粘着剤層は、(メタ)アクリル系重合体(A)、架橋剤(B)及び/又は重合開始剤(C)を含む粘着剤組成物から形成された層である、請求項1~7の何れか一項に記載の活性エネルギー線硬化性粘着シート。
- 前記架橋剤(B)は、多官能(メタ)アクリレート(b)である、請求項8に記載の活性エネルギー線硬化性粘着シート。
- 前記多官能(メタ)アクリレート(b)の含有質量は、前記(メタ)アクリル系重合体(A)100質量部に対して0.5質量部以上10質量部以下である、請求項9に記載の活性エネルギー線硬化性粘着シート。
- ゲル分率が0%以上20%以下である、請求項1~10の何れか一項に記載の活性エネルギー線硬化性粘着シート。
- 波長365nmの活性エネルギー線を積算光量2000~4000mJ/cm2照射した時、照射前に比べてゲル分率が上昇し、該ゲル分率が10%以上85%以下となる、請求項1~11の何れか一項に記載の活性エネルギー線硬化性粘着シート。
- 厚さ0.8mm~1.5mmとし、周波数1Hzの剪断モードで動的粘弾性測定により得られる損失正接が、-30℃において、0.8以上である、請求項1~12の何れか一項に記載のエネルギー線硬化性粘着シート。
- 下記の(4)及び(5)の特性をさらに有することを特徴とする、請求項1~13の何れか一項に記載の活性エネルギー線硬化性粘着シート。
(4)ソーダライムガラス表面に対する、23℃50%RH、剥離角180°、剥離速度300mm/分における粘着力が1N/cm以上。
(5)粘着シートをソーダライムガラスに貼合した後、波長365nmの活性エネルギー線を積算光量2000~4000mJ/cm2照射した時の、23℃50%RH、剥離角180°、剥離速度300mm/分における前記ソーダライムガラス表面に対する粘着力が1N/cm以上。 - さらに、(6)の特性を有することを特徴とする、請求項14に記載の活性エネルギー線硬化性粘着シート。
(6)波長365nmの活性エネルギー線を積算光量2000~4000mJ/cm2照射した後、該粘着シートをソーダライムガラスに貼合した時の、前記ソーダライムガラス表面に対する、23℃40%RH、剥離角180°、剥離速度300mm/分における粘着力が1N/cm以上。 - 厚みが15μm以上50μm以下である、請求項1~15の何れか一項に記載の活性エネルギー線硬化性粘着シート。
- 請求項1~16の何れか一項に記載の活性エネルギー線硬化性粘着シートと、離型フィルムとが積層してなる構成を備えた離型フィルム付き粘着シート。
- 前記離型フィルムが、ポリエステル系フィルムであり、波長365nmの活性エネルギー線を積算光量2000~4000mJ/cm2照射した後の前記活性エネルギー線硬化性粘着シートに対する剥離力が、剥離角180°、剥離速度300mm/分において0.1N/cm以下となる、請求項17記載の離型フィルム付き粘着シート。
- 離型フィルムと、高低差2μm以上の段差を被積層面に有する画像表示装置構成用部材とが、請求項1~16の何れか一項に記載の活性エネルギー線硬化性粘着シートを介して積層してなる構成を備えた、積層体。
- 離型フィルムと、高低差2μm以上の段差を被積層面に有する画像表示装置構成用部材とを、請求項1~16の何れか一項に記載の活性エネルギー線硬化性粘着シートを介して積層し、前記離型フィルム側から該離型フィルムを通して前記粘着シートに活性エネルギー線照射を行う、積層体の製造方法。
- 請求項1~16の何れか一項に記載の活性エネルギー線硬化性粘着シートと、他の粘着シートとが積層してなる構成を備えた、積層シート。
- 前記他の粘着シートが、ゲル分率が70%以上であり、厚さ0.8mm~1.5mmとし、周波数1Hzの剪断モードで動的粘弾性測定により得られる損失正接の極大点が-25℃以下である、請求項21に記載の積層シート。
- 2つの画像表示装置構成用部材が、請求項1~16の何れか一項に記載の活性エネルギー線硬化性粘着シートを介して積層してなる構成を備え、
前記画像表示装置構成用部材の少なくとも一方が、前記粘着シートとの接触面に、高低差2μm以上の段差を有する画像表示装置用積層体。 - 前記画像表示装置構成用部材の少なくとも一方が、ウレタン樹脂、シクロオレフィン樹脂、トリアセチルセルロース樹脂、(メタ)アクリレート樹脂、エポキシ樹脂及びポリイミド樹脂からなる群から選択される一種若しくは二種以上の樹脂を主成分とする樹脂シート又は薄膜ガラスである、請求項23に記載の画像表示装置用積層体。
- 請求項23又は24に記載の積層体を備えたフレキシブル画像表示装置。
- (メタ)アクリル系重合体(A)を含む粘着剤層を備えたフレキシブルディスプレイ用粘着シートであって、
厚さが15μm以上50μm以下であり、
活性エネルギー線硬化性を有し、高低差が2~10μmの段差を10mm以下の間隔で有する画像表示装置構成用部材に下記貼合条件で貼り合せたときに、前記段差の周囲に発泡が無いことを特徴とするフレキシブルディスプレイ用粘着シート。
(貼合条件)
a)厚み15~50μmの粘着シートに、365nmの積算光量が2000~4000mJ/cm2となるよう紫外線を照射する。
b)高低差2~10μmの段差を10mm以下の間隔で有する基材の表面に、前記粘着シートを、プレス圧0.2MPa、30秒の条件で真空貼合する。
c)70℃、気圧0.45MPa、20分の条件でオートクレーブ処理を行う。 - 2つの画像表示装置構成用部材1、2が、活性エネルギー線硬化性粘着シートを介して積層されてなる構成を備えた画像表示装置構成用積層体の製造方法であって、
以下の工程1~3を有し、工程1および2を行った後、工程3を行うことを特徴とする、画像表示装置用積層体の製造方法。
工程1:画像表示装置構成用部材1に、請求項1~16の何れか一項に記載の活性エネルギー線硬化性粘着シートの一方の表面を貼合する。
工程2:活性エネルギー線を照射して、請求項1~16の何れか一項に記載の活性エネルギー線硬化性粘着シートを硬化させる。
工程3:前記粘着シートの他方の表面に画像表示装置構成用部材2を貼合して積層体とする。 - 前記工程3において、50℃以上80℃以下に前記粘着シートを加熱してホットメルトさせながら画像表示装置構成用部材2を貼合して積層体とする、請求項27に記載の画像表示装置用積層体の製造方法。
- 前記工程3の後、さらに、前記積層体に加熱処理を施して前記粘着シートをホットメルトさせる工程4を有する、請求項27又は28に記載の画像表示装置用積層体の製造方法。
- 前記工程4において、前記加熱処理では、前記積層体を温度40℃以上90℃以下に加熱すると共に、0.2MPa以上0.8MPa以下の気圧を5分間以上加えることを特徴とする、請求項29に記載の画像表示装置用積層体の製造方法。
- 前記工程1~4は、工程1,2,3,4の順に実施する、請求項29又は30に記載の画像表示装置用積層体の製造方法。
- 画像表示装置構成用部材1又は画像表示装置構成用部材2の少なくとも一方が、前記粘着シートとの接触面に、高低差2μm以上の段差を有することを特徴とする請求項27~31の何れか一項に記載の画像表示装置用積層体の製造方法。
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JP2022578190A JPWO2022163281A1 (ja) | 2021-01-27 | 2021-12-27 | |
CN202180091745.1A CN116806245A (zh) | 2021-01-27 | 2021-12-27 | 活性能量射线固化性粘合片、带脱模薄膜的粘合片、层叠体、层叠体的制造方法、层叠片、图像显示装置用层叠体、柔性图像显示装置、柔性显示器用粘合片和图像显示装置用层叠体的制造方法 |
KR1020237019425A KR20230136732A (ko) | 2021-01-27 | 2021-12-27 | 활성 에너지선 경화성 점착 시트, 이형 필름을 구비하는 점착 시트, 적층체, 적층체의 제조 방법, 적층 시트, 화상 표시 장치용 적층체, 플렉시블 화상 표시 장치, 플렉시블 디스플레이용 점착 시트 및 화상 표시 장치용 적층체의 제조 방법 |
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WO2023054218A1 (ja) * | 2021-09-28 | 2023-04-06 | 三菱ケミカル株式会社 | 活性エネルギー線硬化性粘着シート、離型フィルム付き粘着シート積層体、画像表示装置構成用積層体、画像表示装置及び画像表示装置構成用積層体の製造方法 |
WO2024111438A1 (ja) * | 2022-11-22 | 2024-05-30 | 三菱ケミカル株式会社 | 透明粘着シート、離型フィルム付き透明粘着シート、フレキシブル画像表示装置構成部材用透明粘着シート、画像表示装置用積層体及びフレキシブル画像表示装置 |
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TW202239915A (zh) | 2022-10-16 |
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