WO2022250041A1 - フレキシブルディスプレイ用粘着剤、粘着シート、積層体、およびフレキシブルディスプレイ - Google Patents
フレキシブルディスプレイ用粘着剤、粘着シート、積層体、およびフレキシブルディスプレイ Download PDFInfo
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- WO2022250041A1 WO2022250041A1 PCT/JP2022/021206 JP2022021206W WO2022250041A1 WO 2022250041 A1 WO2022250041 A1 WO 2022250041A1 JP 2022021206 W JP2022021206 W JP 2022021206W WO 2022250041 A1 WO2022250041 A1 WO 2022250041A1
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- monomer
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- sensitive adhesive
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- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000002960 margaryl 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])C([H])([H])[H] 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 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
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001196 nonadecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 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
- 125000002958 pentadecyl 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])[H] 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 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
- 238000010992 reflux Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- WAAWAIHPWOJHJJ-UHFFFAOYSA-N tributoxy(propyl)silane Chemical compound CCCCO[Si](CCC)(OCCCC)OCCCC WAAWAIHPWOJHJJ-UHFFFAOYSA-N 0.000 description 1
- FQYWWLSIKWDAEC-UHFFFAOYSA-N tributoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)CCCOCC1CO1 FQYWWLSIKWDAEC-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- JRSJRHKJPOJTMS-MDZDMXLPSA-N trimethoxy-[(e)-2-phenylethenyl]silane Chemical compound CO[Si](OC)(OC)\C=C\C1=CC=CC=C1 JRSJRHKJPOJTMS-MDZDMXLPSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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]
-
- 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]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/206—Organic displays, e.g. OLED
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
Definitions
- One embodiment of the present invention has a pressure-sensitive adhesive sheet for forming a laminate comprising a light-transmitting flexible substrate, a pressure-sensitive adhesive layer, and a polarizing plate, and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive sheet. It relates to a laminate.
- the laminate is used for flexible displays.
- an image display device such as a liquid crystal display (LCD) and an organic electroluminescence (organic EL) display (OLED) and a touch panel
- LCD liquid crystal display
- organic EL organic electroluminescence
- a transparent conductive film used for a touch panel is laminated on a member such as support glass via an adhesive layer.
- a polarizing plate film used in an image device is attached to a liquid crystal module and an organic EL module via an adhesive layer.
- the adhesive layer has traditionally required properties that do not cause foaming or peeling in high-temperature and high-humidity environments, but in recent years, flexibility has become even more necessary. Flexibility, for example, in the case of a foldable display, is the suitability (bendability) to accommodate bending of the display so that it can be used in a foldable display. In general, flexibility is required to have properties (dynamic flexibility) that do not cause foaming, floating, or peeling when repeatedly bent.
- Patent Document 1 contains a resin syrup produced by partially polymerizing (meth)acrylate monomers and a photoinitiator, and the storage modulus of the adhesive layer is 25 ° C. and An optically transparent pressure-sensitive adhesive sheet characterized by a pressure of 1.0 ⁇ 10 6 to 1.0 ⁇ 10 7 Pa at 1 Hz is disclosed.
- Patent Document 2 discloses a pressure-sensitive adhesive containing a base polymer, a photocurable compound, and a photoinitiator.
- the rollable display needs to have an aptitude (winding ability) for rolling up the display so that it can be used for the rollable display. In general, windability is required to be such that foaming, lifting and peeling do not occur when the film is kept in a wound state for a long period of time.
- the current situation is that conventional pressure-sensitive adhesive sheets cannot satisfy heat resistance and moist heat resistance at a practically acceptable level, and flexibility such as bendability and windability.
- flexibility requires dynamic bendability, static bendability, and windability depending on the display configuration.
- the current situation is that dynamic flexibility, static flexibility, and windability cannot be satisfied in a high-temperature environment and a high-temperature, high-humidity environment.
- One embodiment of the present invention provides a pressure-sensitive adhesive, a pressure-sensitive adhesive sheet, a laminate, and a flexible display that are excellent in transparency, and are capable of achieving all of heat resistance, moist heat resistance, flexibility, and windability. aim.
- One embodiment of the present invention comprises an acrylic copolymer and a curing agent
- the acrylic copolymer is a copolymer of a monomer mixture containing all of the following monomers (a-1) to (a-4), It is an adhesive for flexible displays that satisfies all of the following (1) to (7).
- alkyl (meth)acrylates having an alkyl group having 1 to 4 carbon atoms ester monomer (1) a storage modulus at ⁇ 20° C. and 1 Hz of 5 ⁇ 10 4 to 3 ⁇ 10 5 Pa; (2) a storage modulus at 25° C.
- the acrylic copolymer contains, in 100% by mass of the monomer mixture, 20 to 60% by mass of the monomer (a-1), 10 to 50% by mass of the monomer (a-2), 0.5 to 2.5% by mass of the monomer (a-3) and 5 to 20% by mass of the monomer (a-4),
- the pressure-sensitive adhesive for a flexible display comprising:
- Another embodiment of the present invention comprises a first acrylic copolymer, a second acrylic copolymer (except when it is the first acrylic copolymer), and a curing agent.
- the first acrylic copolymer is a copolymer of a monomer mixture containing all of the following monomers (a-1) to (a-3)
- the second acrylic copolymer is a copolymer of a monomer mixture containing the following monomer (a-5)
- Monomers having one or more polar groups selected from the group consisting of monomers having a hydroxy group and monomers having a carboxy group (a-5) (meth)acrylic acid alkyl ester monomers having a cycloalkyl group (1) a storage modulus at ⁇ 20° C. and 1 Hz of 5 ⁇ 10 4 to 3 ⁇ 10 5 Pa; (2) a storage modulus at 25° C.
- the first acrylic copolymer contains, in 100% by mass of the monomer mixture, 25 to 80% by mass of the monomer (a-1) 10 to 50% by mass of the monomer (a-2), and 0.5 to 2.5% by mass of the monomer (a-3) including
- the second acrylic copolymer contains, in 100% by mass of the monomer mixture, 40 to 95% by mass of the monomer (a-5)
- the pressure-sensitive adhesive for a flexible display comprising:
- Another embodiment of the present invention is the pressure-sensitive adhesive for a flexible display, comprising 4 to 40 parts by mass of the second acrylic copolymer with respect to 100 parts by mass of the first acrylic copolymer. .
- Another embodiment of the present invention is the pressure-sensitive adhesive for flexible displays, which has a gel fraction of 55 to 90% by mass.
- Another embodiment of the present invention is the adhesive for a flexible display, wherein the monomer (a-2) contains dodecyl (meth)acrylate.
- Another embodiment of the present invention is the adhesive for flexible displays, wherein the curing agent contains an isocyanate compound.
- Another embodiment of the present invention is a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer that is a cured product of the pressure-sensitive adhesive for flexible displays.
- Another embodiment of the present invention is a laminate comprising a light-transmitting flexible substrate, an adhesive layer, and a polarizing plate, wherein the adhesive layer is a cured product of the adhesive for a flexible display. be.
- Another embodiment of the present invention is a flexible display comprising the laminate and an optical element.
- a pressure-sensitive adhesive a pressure-sensitive adhesive sheet, and a laminate using the pressure-sensitive adhesive sheet, which are excellent in transparency and also have good heat resistance, moist heat resistance, flexibility and windability.
- a flexible display having excellent visibility and contrast can be provided.
- FIG. 2 is a schematic cross-sectional view partially showing a laminate, which is an example of using the adhesive sheet. It is a schematic cross-sectional view partially showing a flexible display, which is an example of using the adhesive sheet.
- (Meth)acrylic acid ester includes one or both of acrylic acid ester and methacrylic acid ester.
- a monomer is an ethylenically unsaturated group-containing monomer.
- the adherend refers to the other party to which the pressure-sensitive adhesive sheet is attached. Sheet, film and tape in this embodiment are synonyms.
- (a-1) a (meth)acrylic acid branched alkyl ester monomer having an alkyl group having 6 to 10 carbon atoms
- (a-2) a (meth) having an alkyl group having 12 to 20 carbon atoms
- (a-3) a monomer having one or more polar groups selected from the group consisting of a monomer having a hydroxy group and a monomer having a carboxy group
- a (meth)acrylic acid alkyl ester monomer having an alkyl group and (a-5) a (meth)acrylic acid alkyl ester monomer having a cycloalkyl group are respectively converted into monomer (a-1), monomer (a-2), They are sometimes referred to as monomer (a-3), monomer (a-4), and monomer (a-5).
- the adhesive for flexible displays may be simply called an adhesive.
- the various components described in this specification may be used singly or in combination of
- the flexible display adhesive of the present embodiment contains an acrylic copolymer and a curing agent,
- the acrylic copolymer is a copolymer of a monomer mixture containing all of the following monomers (a-1) to (a-4), All of (1) to (7) below are satisfied.
- the acrylic copolymer and curing agent of the present embodiment are also referred to as copolymer (A) and curing agent (B), respectively.
- a storage modulus at ⁇ 20° C. and 1 Hz of 5 ⁇ 10 4 to 3 ⁇ 10 5 Pa (2) a storage modulus at 25° C. and 1 Hz of 1 ⁇ 10 4 to 5 ⁇ 10 4 Pa; (3) a storage modulus at 80° C. and 1 Hz of 5 ⁇ 10 3 to 3 ⁇ 10 4 Pa; (4) a storage modulus at 200° C. and 1 Hz of 2 ⁇ 10 3 to 3 ⁇ 10 4 Pa; (5) the loss tangent at -50°C and 1Hz is 0.5 to 3.0; (6) the loss tangent at -20°C and 1 Hz is 0.2 to 1.0; (7) Loss tangent at 25° C., 80° C., 200° C. and 1 Hz is 0.01 to 0.5.
- the acrylic copolymer (A) is at least a copolymer of a monomer mixture containing all of the above-described monomers (a-1) to (a-4), and the monomer mixture optionally contains the monomer (a -1) to (a-4) may contain other monomers.
- Monomer (a-1) is a (meth)acrylic acid branched alkyl ester monomer having an alkyl group having 6 to 10 carbon atoms, and specific examples thereof include isohexyl (meth)acrylate and heptyl (meth)acrylate. , isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, and isodecyl (meth)acrylate. From the viewpoint of stress relaxation and adhesion, isooctyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred.
- the stress relaxation property of the pressure-sensitive adhesive is improved, a flexible pressure-sensitive adhesive layer is obtained, and adhesion can be improved.
- the acrylic copolymer (A) has an alkyl group with a branched structure in the side chain.
- the polymers are appropriately entangled with each other, and the stress relaxation property and adhesion to the substrate can be highly improved.
- the monomer (a-1) is preferably contained in an amount of 20 to 60% by mass, more preferably 30 to 60% by mass, based on 100% by mass of the monomer mixture.
- the content is 20% by mass or more, it is easy to obtain sufficient stress relaxation properties.
- the content is 60% by mass or less because cohesive strength and stress relaxation properties are easily compatible.
- Monomer (a-2) is a (meth)acrylic acid alkyl ester monomer having an alkyl group having 12 to 20 carbon atoms, and specific examples thereof include dodecyl (meth)acrylate, tridecyl (meth)acrylate, Tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, icosyl (meth)acrylate, etc. mentioned.
- dodecyl (meth)acrylate, tetradecyl (meth)acrylate, and icosyl (meth)acrylate are preferred from the viewpoint of rubber elasticity, and dodecyl (meth)acrylate is preferred.
- Containing the monomer (a-2) improves the cohesive force of the pressure-sensitive adhesive, provides a tough pressure-sensitive adhesive layer, and improves flexibility.
- the monomer (a-2) is contained in 100% by mass of the monomer mixture, preferably 10 to 50% by mass, more preferably 20 to 50% by mass.
- the content is 10% by mass or more, it is easy to obtain sufficient rubber elasticity.
- the content is 50% by mass or less because it becomes easy to achieve both flexibility and rubber elasticity.
- the monomer (a-3) is a monomer having one or more polar groups selected from the group consisting of monomers having a hydroxy group and monomers having a carboxy group.
- Monomers having a hydroxy group are not limited as long as they are monomers having a hydroxy group in the molecule, and specific examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ( 3-Hydroxypropyl meth)acrylate, 4-hydroxybutyl (meth)acrylate and the like. From the viewpoint of cohesion and adhesion, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred.
- the monomer having a carboxy group is not limited as long as it is a monomer having a carboxy group in the molecule, and specific examples thereof include (meth)acrylic acid, p-carboxybenzyl acrylate, ⁇ -carboxyethyl acrylate, and malein. acids, monoethylmaleic acid, itaconic acid, citraconic acid, fumaric acid, and the like. (Meth)acrylic acid is preferred from the viewpoint of cohesive strength and adhesive strength.
- the cohesive force of the adhesive is improved, a tough adhesive layer is obtained, and the adhesive strength can be improved.
- the monomer (a-3) is contained in 100% by mass of the monomer mixture, preferably 0.5 to 2.5% by mass, more preferably 0.5 to 2.0% by mass.
- the content is 0.5% by mass or more, it becomes easier to obtain sufficient cohesive force.
- the content is 2.5% by mass or less because it becomes easy to achieve both cohesion and stress relaxation.
- Monomer (a-4) is a (meth)acrylic acid alkyl ester monomer having an alkyl group having 1 to 4 carbon atoms in the molecule, specifically, for example, methyl (meth)acrylate, (meth)acrylic ethyl acetate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate and the like. From the viewpoint of cohesive strength and adhesive strength, methyl acrylate, methyl methacrylate, and ethyl acrylate are preferred. Containing the monomer (a-4) improves the cohesive strength of the pressure-sensitive adhesive, provides a tough pressure-sensitive adhesive layer, and improves the adhesive strength.
- the monomer (a-4) is preferably contained in an amount of 5 to 20% by mass, more preferably 5 to 15% by mass, based on 100% of the monomer mixture. Sufficient cohesive force can be easily obtained when the content is 5% by mass or more. In addition, it is preferable that the content is 20% by mass or less because cohesive strength and stress relaxation properties are easily compatible.
- the other monomers are monomers other than the monomers (a-1) to (a-4), and the acrylic copolymer (A) includes the monomers (a-1) to (a-4) and further It may contain a monomer.
- Other monomers include (meth)acrylic acid alkyl ester monomers other than monomer (a-1), monomer (a-2), and monomer (a-4), (meth)acrylic acid monomers having epoxy groups, and amino groups.
- Examples of (meth)acrylic acid alkyl ester monomers other than monomer (a-1), monomer (a-2), and monomer (a-4) include pentyl (meth)acrylate, hexyl (meth)acrylate, ( meth)heptyl acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate and the like.
- Monomers having an epoxy group include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 6-methyl-3,4-(meth)acrylate epoxycyclohexylmethyl and the like.
- Examples of monomers having an amino group include (meth)acrylates such as monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate, and monoethylaminopropyl (meth)acrylate. ) acrylic acid monoalkylamino esters, and the like.
- Examples of monomers having an alkyleneoxy group include monomers represented by the following general formula (1) and monomers represented by general formula (2).
- R 1 in general formula (1) and R 2 in general formula (2) each independently represent a hydrogen atom or a methyl group; n and m are integers representing repeating units; ⁇ m ⁇ 25, preferably 1 ⁇ n ⁇ 13 and 1 ⁇ m ⁇ 5.
- vinyl monomers examples include vinyl acetate, vinyl crotonate, styrene, and acrylonitrile.
- the other monomer preferably contains 100% by mass of the monomer mixture, 20 to 60% by mass.
- the content is 20% by mass or more, the adhesion is further improved.
- the content is 60% by mass or less, it is preferable because it is easy to achieve both cohesion and adhesion.
- the acrylic copolymer (A) can be produced by polymerizing a monomer mixture. Polymerization can be carried out by known polymerization methods such as solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization, but solution polymerization is preferred. Solvents used in solution polymerization are preferably acetone, methyl acetate, ethyl acetate, toluene, xylene, anisole, methyl ethyl ketone, cyclohexanone, and the like. The polymerization temperature is preferably 60-120°C. The polymerization time is preferably about 5 to 12 hours.
- the polymerization initiator used for polymerization is preferably a radical polymerization initiator.
- Radical polymerization initiators are generally peroxides and azo compounds. Peroxides are, for example, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, ⁇ , ⁇ '-bis(t-butylperoxy-m-isopropyl)benzene, 2,5- Dialkyl peroxides such as di(t-butylperoxy)hexyne-3; t-butylperoxybenzoate, t-butylperoxyacetate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane peroxyester; Ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide; 2,2-bis(4,4-di-t-but
- Azo compounds include 2,2'-azobisbutyronitrile such as 2,2'-azobisisobutyronitrile (abbreviation: AIBN) and 2,2'-azobis(2-methylbutyronitrile); 2,2′-azobisvaleronitrile such as 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile); 2,2 2,2'-azobispropionitrile such as '-azobis(2-hydroxymethylpropionitrile); 1,1'-azobis-1-alkanenitrile such as 1,1'-azobis(cyclohexane-1-carbonitrile) and the like.
- AIBN 2,2'-azobisisobutyronitrile
- 2-methylbutyronitrile 2,2′-azobisvaleronitrile
- 2,2′-azobisvaleronitrile such as 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile
- the polymerization initiator is preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, with respect to 100 parts by mass of the monomer mixture.
- the weight average molecular weight of the copolymer (A) is preferably 800,000 to 1,800,000, more preferably 1,000,000 to 1,500,000. When it is in the range of 800,000 to 1,800,000, the cohesive force is further improved, and the wet heat resistance and heat resistance are further improved.
- a weight average molecular weight is a value of polystyrene conversion measured by gel permeation chromatography (GPC) method.
- ⁇ Curing agent (B)> The curing agent (B) reacts with the hydroxy groups and/or carboxy groups of the copolymer (A) to improve the cohesive strength of the pressure-sensitive adhesive layer, thereby improving durability and stain resistance.
- Examples of the curing agent (B) include isocyanate compounds, epoxy compounds, aziridine compounds, carbodiimide compounds, metal chelates, and the like. Among these, it is preferable to use an isocyanate compound as the curing agent (B) because the adhesiveness and durability can be improved.
- An isocyanate compound is an isocyanate having two or more isocyanate groups.
- Isocyanate compounds are preferably isocyanate monomers such as aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates and alicyclic polyisocyanates, and burettes, nurates and adducts thereof.
- Aromatic polyisocyanates are, for example, 1,3-phenylene diisocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4 ''-triphenylmethane triisocyanate and the like.
- Aliphatic polyisocyanates include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.
- trimethylene diisocyanate tetramethylene diisocyanate
- hexamethylene diisocyanate also known as HMDI
- pentamethylene diisocyanate 1,2-propylene diisocyanate
- 2,3-butylene diisocyanate 1,3-butylene diisocyanate
- dodecamethylene diisocyanate 2,4,4-trimethylhexamethylene diisocyanate, and the like.
- Aroaliphatic polyisocyanates are, for example, ⁇ , ⁇ ′-diisocyanate-1,3-dimethylbenzene, ⁇ , ⁇ ′-diisocyanate-1,4-dimethylbenzene, ⁇ , ⁇ ′-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate and the like.
- Alicyclic polyisocyanates include, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI, isophorone diisocyanate), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4 -cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,4-bis(isocyanatomethyl)cyclohexane and the like.
- IPDI isophorone diisocyanate
- 1,3-cyclopentane diisocyanate 1,3-cyclohexane diisocyanate
- 1,4 -cyclohexanediisocyanate 1,4 -cyclohexanediis
- a burette body is a self-condensed product having a burette bond in which isocyanate monomers are self-condensed.
- the burette body includes, for example, a burette body of hexamethylene diisocyanate.
- a nurate body is a trimer of isocyanate monomers. Examples thereof include a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate, a trimer of tolylene diisocyanate, and the like.
- the adduct is a bifunctional or higher isocyanate compound obtained by reacting an isocyanate monomer and a bifunctional or higher low-molecular-weight active hydrogen-containing compound.
- Adducts include, for example, a compound obtained by reacting trimethylolpropane and hexamethylene diisocyanate, a compound obtained by reacting trimethylolpropane and tolylene diisocyanate, a compound obtained by reacting trimethylolpropane and xylylene diisocyanate, trimethylol
- a compound obtained by reacting propane with isophorone diisocyanate, a compound obtained by reacting 1,6-hexanediol with hexamethylene diisocyanate, and the like can be mentioned.
- the isocyanate compound is preferably a trifunctional isocyanate compound.
- the isocyanate compound is more preferably an adduct or a nurate which is a reaction product of an isocyanate monomer and a trifunctional low-molecular-weight active hydrogen-containing compound.
- Isocyanate compounds include trimethylolpropane adduct of hexamethylene diisocyanate, nurate of hexamethylene diisocyanate, trimethylolpropane adduct of tolylene diisocyanate, nurate of tolylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, and isophorone diisocyanate.
- a nurate compound is preferred, and a trimethylolpropane adduct of hexamethylene diisocyanate, a trimethylolpropane adduct of tolylene diisocyanate, and a trimethylolpropane adduct of isophorone diisocyanate are more preferred.
- Epoxy compounds include, for example, glycerol diglycidyl ether, 1,6-hexanediol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N' -diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidylaminophenylmethane and the like.
- Aziridine compounds include, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxite), tris-2,4,6-(1-aziridinyl)-1,3,5-triazine, 4 , 4′-bis(ethyleneiminocarbonylamino)diphenylmethane and the like.
- the carbodiimide compound is preferably a high-molecular-weight polycarbodiimide produced by a decarboxylation condensation reaction of a diisocyanate compound in the presence of a carbodiimidation catalyst.
- Carbodilite series manufactured by Nisshinbo Co., Ltd. is preferable as a commercial product of high-molecular-weight polycarbodiimide.
- Carbodilite V-03, 07 and 09 are preferable because of their excellent compatibility with organic solvents.
- Metal chelates are preferably coordination compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium and acetylacetone or ethyl acetoacetate.
- metal chelates include aluminum ethylacetoacetate/diisopropylate, aluminum trisacetylacetonate, aluminum bisethylacetoacetate/monoacetylacetonate, and aluminum alkylacetoacetate/diisopropylate.
- the curing agent (B) is preferably contained in an amount of 0.02 to 4.0 parts by mass, more preferably 0.04 to 1.0 parts by mass, based on 100 parts by mass of the copolymer (A).
- the content is 0.02 parts by mass or more, the cohesive force is further improved, and when the content is 4 parts by mass or less, cohesive force and flexibility are easily compatible, which is preferable.
- the flexible display adhesive of the present embodiment can further contain an organic silane compound.
- Organosilane compounds include, for example, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropyltripropoxysilane, 3-(meth)acryloxy Alkoxysilane compounds having a (meth)acryloxy group such as propyltributoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane; alkoxysilane compounds having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane
- the organic silane compound is preferably used in an amount of 0.01 to 2 parts by mass, more preferably 0.05 to 1 part by mass, based on 100 parts by mass of the copolymer (A).
- the pressure-sensitive adhesive for flexible displays of the present embodiment contains various resins, oils, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, weather stabilizers, and plasticizers as optional components as long as the problems can be solved. , fillers, anti-aging agents, antistatic agents, and the like.
- the storage modulus and loss tangent of the pressure-sensitive adhesive for flexible displays are determined by viscoelasticity measurement at a frequency of 1 Hz.
- the loss tangent is the ratio of storage modulus to loss modulus, loss modulus/storage modulus.
- the storage elastic modulus corresponds to the portion stored as elastic energy when the material is deformed, and is an index representing the degree of hardness. That is, the higher the storage modulus value, the harder the adhesive, and the lower the storage modulus value, the softer the adhesive.
- the loss modulus corresponds to the loss energy portion dissipated due to internal friction or the like when the material deforms, and represents the degree of viscosity.
- the storage elastic modulus and loss tangent can be controlled by the monomer composition, compounding amount, synthesis conditions, etc. of the copolymer to be used, and the type and compounding amount of the curing agent.
- the pressure-sensitive adhesive for flexible displays has a storage modulus (hereinafter sometimes abbreviated as G'(-20)) at -20°C and 1 Hz of 5 ⁇ 10 4 to 3 ⁇ 10 5 Pa, and 6 ⁇ It is more preferably 10 4 to 2 ⁇ 10 5 Pa.
- G'(-20) is 5 ⁇ 10 4 Pa or more, rigidity in a low temperature environment is improved, and flexibility and windability are improved.
- the adhesive for flexible displays has a storage modulus (hereinafter sometimes abbreviated as G'(25)) at 25° C. and 1 Hz of 1 ⁇ 10 4 to 5 ⁇ 10 4 Pa and 2 ⁇ 10 4 . It is more preferably ⁇ 4 ⁇ 10 4 Pa. Workability improves that G' (25) is 1*10 ⁇ 4> Pa or more. Moreover, when G'(25) is 5 ⁇ 10 4 Pa or less, the adhesive strength is improved.
- G'(25) storage modulus at 25° C. and 1 Hz of 1 ⁇ 10 4 to 5 ⁇ 10 4 Pa and 2 ⁇ 10 4 . It is more preferably ⁇ 4 ⁇ 10 4 Pa. Workability improves that G' (25) is 1*10 ⁇ 4> Pa or more. Moreover, when G'(25) is 5 ⁇ 10 4 Pa or less, the adhesive strength is improved.
- the pressure-sensitive adhesive for flexible displays has a storage modulus (hereinafter sometimes abbreviated as G'(80)) at 80° C. and 1 Hz of 5 ⁇ 10 3 to 3 ⁇ 10 4 Pa and 6 ⁇ 10 3 . It is preferably ⁇ 2 ⁇ 10 4 Pa.
- G'(80) storage modulus
- rigidity in a high-temperature environment is improved, and flexibility and windability are improved.
- G'(80) is 3 ⁇ 10 4 Pa or less, flexibility in a high-temperature environment is improved, and flexibility and windability are improved.
- the adhesive for flexible displays has a storage modulus (hereinafter sometimes abbreviated as G'(200)) at 200° C. and 1 Hz of 2 ⁇ 10 3 to 3 ⁇ 10 4 Pa and 3 ⁇ 10 3 . It is preferably ⁇ 2 ⁇ 10 4 Pa.
- G'(200) storage modulus
- polymer materials soften due to thermal degradation when left in a high-temperature environment for a long period of time.
- G'(200) is correlated with the coating film strength of the pressure-sensitive adhesive under long-term high-temperature environments. That is, when G'(200) is 2 ⁇ 10 3 Pa or more, the rigidity is improved in a long-term high-temperature environment, and flexibility and windability can be maintained.
- G'(200) is 3 ⁇ 10 4 Pa or less, the flexibility can be maintained under a long-term high-temperature environment, and the flexibility and windability are improved.
- the pressure-sensitive adhesive for flexible displays has a loss tangent at -50°C and 1 Hz (hereinafter sometimes abbreviated as tan ⁇ (-50)) of 0.5 to 3.0, and 1.0 to 2.5. is more preferable.
- tan ⁇ (-50) a loss tangent at -50°C and 1 Hz
- polymer materials wear and break when subjected to physical deformation such as bending and winding.
- tan ⁇ (-50) correlates with the coating film strength of the pressure-sensitive adhesive in physical deformation. That is, when tan ⁇ ( ⁇ 50) is 0.5 or more, the stress relaxation properties when subjected to physical deformation are improved, and the bendability and windability are improved.
- tan ⁇ ( ⁇ 50) is 3.0 or less, the rigidity is improved when physical deformation is applied, and the flexibility and windability are improved.
- the pressure-sensitive adhesive for flexible displays has a loss tangent (hereinafter sometimes abbreviated as tan ⁇ (-20)) at ⁇ 20° C. and 1 Hz of 0.2 to 1.0 and 0.4 to 0.8. is more preferable.
- tan ⁇ ( ⁇ 20) is 0.2 or more, the stress relaxation property in a low temperature environment is improved, and the flexibility and windability are improved.
- tan ⁇ ( ⁇ 20) is 1.0 or less, the rigidity in a low temperature environment is improved, and the flexibility and windability are improved.
- the adhesive for flexible displays has a loss tangent at 25°C, 80°C, 200°C and 1 Hz of 0.01 to 0.5, preferably 0.10 to 0.4.
- the loss tangent at 25°C, 80°C, 200°C, and 1 Hz is 0.01 or more, the stress relaxation property is improved, and when it is 0.5 or less, the rigidity is improved, flexibility and winding improve sexuality.
- the loss tangent is within a constant value range of 0.01 to 0.5 over a wide temperature range, it is possible to maintain constant adhesive strength over a wide temperature range.
- the adhesive for flexible displays exhibits the flexibility required for foldable displays and the windability required for rollable displays.
- the adhesive for flexible displays preferably has a gel fraction of 55 to 90% by mass, more preferably 60 to 80% by mass.
- the gel fraction is 55% by mass or more, the cohesive force of the adhesive is improved, a tough adhesive layer is obtained, and the durability is improved, and when it is 90% by mass or less, the stress relaxation property of the adhesive is improved, a flexible pressure-sensitive adhesive layer is obtained, and adhesion is improved.
- the gel fraction can be obtained as an insoluble matter in a solvent such as ethyl acetate. Specifically, as represented by the following formula 1, the mass fraction (unit: mass %).
- the mass fraction (unit: mass %).
- the gel fraction of a polymer is equal to the degree of cross-linking, and the more cross-linked parts in the polymer, the greater the gel fraction.
- the gel fraction (introduction amount of the crosslinked structure) can be adjusted within a desired range by the method of introducing the crosslinked structure, the type and amount of the curing agent, and the like.
- the pressure-sensitive adhesive sheet of the present embodiment is a pressure-sensitive adhesive sheet used for forming the pressure-sensitive adhesive layer in a laminate comprising a light-transmitting flexible substrate and a pressure-sensitive adhesive layer. is used to bond optically transparent flexible substrates.
- FIG. 1 shows an example of a schematic cross-sectional view partially showing an adhesive sheet. In FIG. 1, 1 is the first pressure-sensitive adhesive layer, and 2 is the release film.
- the pressure-sensitive adhesive sheet has a configuration in which release films are formed on both sides of the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer formed between the release films is an acrylic copolymer. It is an adhesive layer formed of a mixture of (A) and a curing agent (B).
- the release film is not particularly limited, but for example, a transparent plastic substrate can be preferably used.
- materials for the transparent plastic substrate include polyesters such as polyethylene terephthalate (PET), acrylic resins such as polymethyl methacrylate (PMMA), and plastic materials such as polycarbonate, triacetyl cellulose, polysulfone, polyarylate, and polycycloolefin. etc.
- PET polyethylene terephthalate
- PMMA polymethyl methacrylate
- plastic materials such as polycarbonate, triacetyl cellulose, polysulfone, polyarylate, and polycycloolefin. etc.
- the plastic materials can be used singly or in combination of two or more.
- the transparent plastic substrate has excellent heat resistance, that is, the deformation is suppressed or prevented under severe conditions such as high temperature, high temperature and high humidity.
- a transparent plastic substrate can be preferably used.
- a PET film or PET sheet is particularly suitable as the transparent plastic substrate.
- the thickness of the transparent plastic substrate is not particularly limited, and is preferably 10 to 200 ⁇ m, more preferably 25 to 150 ⁇ m, for example.
- the release film may have either a single layer or multiple layers.
- the surface of the transparent substrate may be subjected to appropriate surface treatment such as physical treatment such as corona discharge treatment and plasma treatment, and chemical treatment such as undercoating treatment.
- the pressure-sensitive adhesive sheet of the present embodiment can be manufactured according to a normal pressure-sensitive adhesive sheet manufacturing method. For example, a mixture of an acrylic copolymer (A) and a curing agent (B) (hereinafter sometimes simply referred to as "adhesive") is applied to the release-treated surface of the release film so that the thickness after drying is A method of directly coating to a predetermined thickness to form an adhesive layer and attaching a release film, or a method of applying a release film to the release treated surface of two release films, and applying an adhesive to a predetermined thickness after drying. It can be produced by a method of forming two pressure-sensitive adhesive layers respectively by coating so as to have a thickness, and then affixing the respective pressure-sensitive adhesive layers.
- the thickness of the adhesive layer is not particularly limited, and is preferably 10 to 500 ⁇ m, more preferably 50 to 200 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer is 10 to 500 ⁇ m, it is preferable because sufficient cohesive force can be easily obtained and heat resistance, resistance to moist heat, flexibility and windability can be highly compatible.
- a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater can be used.
- the adhesive sheet may be in the form of an adhesive tape wound into a roll by cutting it into a desired width and winding it into a roll.
- the laminate of this embodiment includes a light-transmitting flexible substrate, an adhesive layer, and a polarizing plate, and the adhesive layer is formed using the adhesive sheet of this embodiment.
- the laminate is formed from an adhesive sheet with excellent transparency, heat resistance, heat and humidity resistance, flexibility and windability, so it has excellent transparency, heat resistance, heat and humidity resistance, flexibility and windability.
- FIG. 2 shows an example of a schematic cross-sectional view partially showing a laminate, which is an example of using the adhesive sheet.
- 3 is a light-transmissive flexible substrate (cover panel)
- 1 is a first pressure-sensitive adhesive layer
- 4 is a polarizing plate.
- a light-transmissive flexible base material (cover panel) is attached to the polarizing plate via an adhesive layer made of the adhesive of the present embodiment.
- the pressure-sensitive adhesive sheet of this embodiment can be used in a form in which a transparent pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive is attached to a light-transmitting flexible substrate (cover panel) and a polarizing plate.
- the light-transmissive flexible base material is not particularly limited, but for example, a transparent plastic base material can be suitably used.
- Materials for the transparent plastic substrate include, for example, acrylic resins such as polyethylene terephthalate (PET) and polymethyl methacrylate (PMMA); and plastic materials such as polycarbonate, polycycloolefin, and polyimide.
- PET polyethylene terephthalate
- PMMA polymethyl methacrylate
- plastic materials such as polycarbonate, polycycloolefin, and polyimide.
- the plastic materials can be used singly or in combination of two or more.
- transparent plastic substrates with excellent heat resistance, i.e., under severe conditions such as high temperature, high temperature and high humidity
- a transparent plastic substrate whose deformation is suppressed or prevented can be preferably used.
- PET Polyethylene terephthalate
- polycycloolefin polycycloolefin
- polyimide are particularly suitable as transparent plastic substrates.
- the thickness of the light-transmitting flexible substrate (cover panel) is not particularly limited, and is preferably 100 to 2000 ⁇ m, more preferably 200 to 1000 ⁇ m.
- a flexible display includes the laminate of the present embodiment and an optical element.
- the optical element is not particularly limited, and examples thereof include a liquid crystal element and an organic EL element.
- the flexible display of the present embodiment has a laminate with excellent transparency, heat resistance, resistance to moist heat, flexibility, and rollability, so it is excellent in transparency, heat resistance, resistance to humidity and heat, flexibility, and rollability.
- FIG. 3 shows an example of a schematic cross-sectional view partially showing a flexible display, which is an example of use of the pressure-sensitive adhesive sheet of this embodiment.
- 3 is a light-transmitting flexible substrate (cover panel)
- 1 is a first adhesive layer
- 4 is a polarizing plate
- 5 is a second adhesive layer
- 6 is a barrier layer such as silicon nitride.
- 7 is an organic EL layer
- 8 is a support such as polyimide
- 10 is an organic EL cell. Note that the configuration of the flexible display is not limited to that shown in FIG.
- a light-transmitting flexible substrate (cover panel) is attached to the polarizing plate via the adhesive layer (first adhesive layer 1) made of the adhesive of the present embodiment. It is attached to the organic EL cell via an adhesive layer for polarizing plate (second adhesive layer 5).
- the transparent pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive is attached to the light-transmitting flexible substrate (cover panel) and the polarizing plate, and the pressure-sensitive adhesive layer for the polarizing plate is further attached to the polarizing plate. It can be used in a form in which the laminate is attached to the organic EL via. For example, in FIG.
- the adhesive of this embodiment can be used for both the first adhesive layer 1 and the second adhesive layer 5 .
- the quality required for the pressure-sensitive adhesive layer is higher for the first pressure-sensitive adhesive layer 1.
- the pressure-sensitive adhesive is preferably used for the first pressure-sensitive adhesive layer 1 because it has good adhesion and adhesiveness to the substrate.
- the adhesive for forming the second adhesive layer 5 the adhesive of the present embodiment may be used, or a conventionally known adhesive may be used.
- organic EL televisions organic EL smartphones, organic EL tablets, and organic EL smart watches.
- the adhesive of this embodiment contains a first acrylic copolymer, a second acrylic copolymer and a curing agent,
- the first acrylic copolymer (A1) is a copolymer of a monomer mixture containing all of the following monomers (a-1) to (a-3)
- the second acrylic copolymer (A2) is a copolymer of a monomer mixture containing the following monomer (a-5), All of (1) to (7) below are satisfied.
- the first acrylic copolymer, the second acrylic copolymer and the curing agent of the present embodiment are the acrylic copolymer (A1), the acrylic copolymer (A2) and the curing agent (B), respectively. ).
- acrylic copolymer (A1) and acrylic copolymer (A2) are also referred to as copolymer (A1) and copolymer (A2), respectively.
- a storage modulus at ⁇ 20° C. and 1 Hz of 5 ⁇ 10 4 to 3 ⁇ 10 5 Pa (2) a storage modulus at 25° C. and 1 Hz of 1 ⁇ 10 4 to 5 ⁇ 10 4 Pa; (3) a storage modulus at 80° C. and 1 Hz of 5 ⁇ 10 3 to 3 ⁇ 10 4 Pa; (4) a storage modulus at 200° C. and 1 Hz of 2 ⁇ 10 3 to 3 ⁇ 10 4 Pa; (5) the loss tangent at -50°C and 1Hz is 0.5 to 3.0; (6) the loss tangent at -20°C and 1 Hz is 0.2 to 1.0; (7) Loss tangent at 25° C., 80° C., 200° C. and 1 Hz is 0.01 to 0.5.
- the acrylic copolymer (A1) is at least a copolymer of a monomer mixture containing all of the above-described monomers (a-1) to (a-3), and the monomer mixture optionally contains the monomer (a -1) to (a-3) may be included.
- the acrylic copolymer (A2) is at least a copolymer of a monomer mixture containing the monomer (a-5), and the monomer mixture optionally contains the monomers (a-1) to (a-3), and monomers (a-1) to (a-3) and other than monomer (a-5). Even if all of the monomers (a-1) to (a-3) are contained, if the monomer (a-5) is contained, it is defined as the acrylic copolymer (A2).
- the monomer (a-1) is a (meth)acrylic acid branched alkyl ester monomer having an alkyl group having 6 to 10 carbon atoms, specifically, the monomer (a-1) described in the first embodiment. things are mentioned. From the viewpoint of stress relaxation and adhesion, isooctyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred.
- the acrylic copolymer (A1) has an alkyl group with a branched structure in the side chain.
- the polymers are appropriately entangled with each other, and the stress relaxation property and adhesion to the substrate can be highly improved.
- the copolymer (A1) preferably contains 100% by mass of the monomer mixture and 25 to 80% by mass of the monomer (a-1), more preferably 35 to 80% by mass.
- the content is 25% by mass or more, it is easy to obtain sufficient stress relaxation properties.
- it is preferable that the content is 80% by mass or less because it becomes easy to achieve both cohesion and stress relaxation.
- Monomer (a-2) is a (meth)acrylic acid alkyl ester monomer having an alkyl group having 12 to 20 carbon atoms, specifically, those described in monomer (a-2) of the first embodiment. is mentioned. From the viewpoint of flexibility and winding properties, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, and icosyl (meth)acrylate are preferred from the viewpoint of rubber elasticity, and dodecyl (meth)acrylate is preferred.
- the rubber elasticity of the adhesive is improved, a tough adhesive layer is obtained, and the flexibility can be improved.
- the copolymer (A1) preferably contains 100% by mass of the monomer mixture and 10 to 50% by mass, more preferably 20 to 50% by mass of the monomer (a-2).
- the content is 10% by mass or more, sufficient rubber elasticity can be obtained, and when the content is 50% by mass or less, it becomes easy to achieve both flexibility and rubber elasticity, which is preferable.
- the monomer (a-3) is a monomer having one or more polar groups selected from the group consisting of monomers having a hydroxy group and monomers having a carboxy group.
- Examples of the hydroxy group-containing monomer and the carboxy group-containing monomer include those described in the monomer (a-3) of the first embodiment. From the viewpoint of cohesive strength and adhesive strength, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, or (meth)acrylic acid are preferred.
- the cohesive force of the adhesive is improved, a tough adhesive layer is obtained, and the adhesive strength can be improved.
- the copolymer (A1) preferably contains 100% by mass of the monomer mixture and 0.5 to 2.5% by mass, more preferably 0.5 to 2.0% by mass of the monomer (a-3).
- the content is 0.5% by mass or more, sufficient cohesive force can be obtained, and when the content is 2.5% by mass or less, cohesive force and stress relaxation properties are easily compatible, which is preferable.
- Monomer (a-5) is not limited as long as it is a (meth)acrylic acid alkyl ester monomer having a cycloalkyl group, and specifically, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylate, dicyclopentanyl acrylate, cyclododecyl (meth)acrylate, methylcyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate and the like. From the viewpoint of cohesiveness, isobornyl (meth)acrylate and cyclohexyl (meth)acrylate are preferable, and from the viewpoints of cohesiveness and flexibility, isobornyl (meth)acrylate is more preferable.
- the monomer (a-5) can improve the cohesive force of the pressure-sensitive adhesive, obtain a tough pressure-sensitive adhesive layer, and improve the adhesive strength.
- the copolymer (A2) preferably contains 100% by mass of the monomer mixture and 40 to 95% by mass of the monomer (a-5), more preferably 60 to 95% by mass, and 40 to 90% by mass. It's okay. When the content is 40% by mass or more, sufficient cohesive force can be obtained, and when the content is 95% by mass or less, cohesive force and stress relaxation properties are easily compatible, which is preferable.
- the total content of monomers other than monomer (a-5), that is, monomer (a-1), monomer (a-2), monomer (a-3), and other monomers is 100% by mass of the monomer mixture. , preferably 5 to 60% by mass.
- the content is 10% by mass or more, the adhesion is further improved.
- the content is 60% by mass or less, it is easy to achieve both cohesion and adhesion.
- Other monomers are monomers other than the monomers (a-1) to (a-3) and the monomer (a-5), and the monomer mixture constituting the acrylic copolymer (A1) is the monomer (a-1) In addition to ⁇ (a-3), it may further contain other monomers, and the monomer mixture constituting the acrylic copolymer (A2) is, in addition to the monomer (a-5), further the monomer (a-1) to (a-3), and other monomers.
- Other monomers include (meth)acrylic acid alkyl ester monomers other than monomer (a-1) and monomer (a-2), epoxy group-containing (meth)acrylic acid monomers, amino group-containing (meth)acrylic acid monomers, alkyleneoxy Examples include group-containing monomers and other vinyl monomers.
- Examples of (meth)acrylic acid alkyl ester monomers other than monomer (a-1) and monomer (a-2) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylate, ) isopropyl acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, Examples include octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, and undecyl (meth)acrylate.
- Examples of the epoxy group-containing monomer, amino group-containing monomer, alkyleneoxy group-containing monomer, and vinyl monomer include those described in the other monomers of the first embodiment. From the viewpoint of cohesive strength and adhesive strength, (meth)acrylic acid alkyl ester monomers other than monomer (a-1) and monomer (a-2), alkyleneoxy group-containing monomers are preferred, and butyl (meth)acrylate, methoxyethyl Acrylates are more preferred.
- the monomer other than the monomer (a-5) is not particularly limited in use, but the monomer (a-2) and other monomers are preferable from the viewpoint of cohesive strength and adhesive strength, and (meth)acrylic acid 2- Ethylhexyl, isooctyl (meth)acrylate, butyl (meth)acrylate, and methoxyethyl acrylate are more preferred.
- the cohesion of the adhesive is improved, a tough adhesive layer is obtained, and the adhesive strength can be improved.
- the copolymer (A1) preferably contains 100% by mass of the monomer mixture and 20 to 60% by mass of other monomers. When the content is 20% by mass or more, the adhesion can be further improved. A content of 60% by mass or less is preferable because it facilitates compatibility between cohesion and adhesion.
- the acrylic copolymer (A1) is obtained by polymerizing a copolymer containing at least the monomers (a-1) to (a-3) and optionally other monomers.
- the monomer (a-1) the stress relaxation property of the pressure-sensitive adhesive is improved, a flexible pressure-sensitive adhesive layer can be obtained, and the adhesion can be improved. With this, the rubber elasticity of the adhesive is improved, a tough adhesive layer can be obtained, and the flexibility can be improved.
- the monomer (a-3) the cohesive force of the pressure-sensitive adhesive is improved, a tough pressure-sensitive adhesive layer is obtained, and the adhesive strength can be improved.
- the acrylic copolymer (A2) is obtained by polymerizing a copolymer containing at least the monomer (a-5) and optionally the monomers (a-1) to (a-3) or other monomers. is obtained by Containing the monomer (a-5) improves the cohesive strength of the pressure-sensitive adhesive, provides a tough pressure-sensitive adhesive layer, and improves the adhesive strength.
- the acrylic copolymers (A1) and (A2) can be produced by polymerizing a monomer mixture.
- Polymerization of the monomer mixtures constituting the copolymer (A1) and the copolymer (A2) can be carried out by known polymerization methods such as solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization, but solution polymerization is preferred.
- Solvents used in solution polymerization are preferably acetone, methyl acetate, ethyl acetate, toluene, xylene, anisole, methyl ethyl ketone, cyclohexanone, and the like.
- the polymerization temperature is preferably 60 to 120°C for boiling point reaction.
- the polymerization time is preferably about 5 to 12 hours.
- the polymerization initiator used for polymerization is preferably a radical polymerization initiator.
- Radical polymerization initiators are generally peroxides and azo compounds. Peroxides and azo compounds include those described in the first embodiment.
- the polymerization initiator is preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the monomer mixture.
- the weight average molecular weight of the copolymer (A1) is preferably 800,000 to 1,800,000, more preferably 1,000,000 to 1,500,000. When it is in the range of 800,000 to 1,800,000, the cohesive force is further improved, and the wet heat resistance and heat resistance can be further improved.
- the weight average molecular weight of the copolymer (A2) is preferably 10,000 to 300,000, more preferably 10,000 to 100,000. When it is in the range of 10,000 to 300,000, the stress relaxation property is further improved, and the resistance to moist heat and heat is further improved.
- a weight average molecular weight is a value of polystyrene conversion measured by gel permeation chromatography (GPC) method.
- ⁇ Curing agent (B)> The curing agent (B) reacts with the hydroxyl groups and/or carboxyl groups of the copolymer (A1) to improve the cohesive strength of the pressure-sensitive adhesive layer, thereby further improving durability and stain resistance.
- Examples of the curing agent (B) include isocyanate compounds, epoxy compounds, aziridine compounds, carbodiimide compounds, metal chelates, and the like. Among these, it is preferable to use an isocyanate compound as the curing agent (B) because the adhesiveness and durability can be improved.
- the isocyanate compound, epoxy compound, aziridine compound, carbodiimide compound, and metal chelate include those described in the first embodiment.
- the curing agent (B) preferably contains 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight, based on a total of 100 parts by weight of the copolymer (A1) and the copolymer (A2). more preferred.
- the content is 0.01 parts by mass or more, the cohesive force is further improved, and when the content is 5 parts by mass or less, cohesive force and flexibility are easily compatible, which is preferable.
- the flexible display adhesive of the present embodiment can further contain an organic silane compound.
- organic silane compound examples include those described in the first embodiment.
- the organic silane compound is preferably used in an amount of 0.01 to 2 parts by mass, more preferably 0.05 to 1 part by mass, with respect to a total of 100 parts by mass of the copolymer (A1) and the copolymer (A2). preferable.
- the pressure-sensitive adhesive for flexible displays of the present embodiment contains various resins, oils, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, weather stabilizers, and plasticizers as optional components as long as the problems can be solved. , fillers, anti-aging agents, antistatic agents, and the like.
- the storage elastic modulus and loss tangent of the pressure-sensitive adhesive for flexible displays are determined by viscoelasticity measurement at a frequency of 1 Hz, as in the first embodiment.
- the pressure-sensitive adhesive for flexible displays has a storage modulus (hereinafter sometimes abbreviated as G'(-20)) at -20°C and 1 Hz of 5 ⁇ 10 4 to 3 ⁇ 10 5 Pa, and 6 ⁇ It is more preferably 10 4 to 2 ⁇ 10 5 Pa.
- G'(-20) is 5 ⁇ 10 4 Pa or more, rigidity in a low temperature environment is improved, and flexibility and windability are improved.
- the adhesive for flexible displays has a storage modulus (hereinafter sometimes abbreviated as G'(25)) at 25° C. and 1 Hz of 1 ⁇ 10 4 to 5 ⁇ 10 4 Pa and 2 ⁇ 10 4 . It is more preferably ⁇ 4 ⁇ 10 4 Pa. Workability improves that G' (25) is 1*10 ⁇ 4> Pa or more. Moreover, when G'(25) is 5 ⁇ 10 4 Pa or less, the adhesive strength is improved.
- G'(25) storage modulus at 25° C. and 1 Hz of 1 ⁇ 10 4 to 5 ⁇ 10 4 Pa and 2 ⁇ 10 4 . It is more preferably ⁇ 4 ⁇ 10 4 Pa. Workability improves that G' (25) is 1*10 ⁇ 4> Pa or more. Moreover, when G'(25) is 5 ⁇ 10 4 Pa or less, the adhesive strength is improved.
- the pressure-sensitive adhesive for flexible displays has a storage modulus (hereinafter sometimes abbreviated as G'(80)) at 80° C. and 1 Hz of 5 ⁇ 10 3 to 3 ⁇ 10 4 Pa and 6 ⁇ 10 3 . It is preferably ⁇ 2 ⁇ 10 4 Pa.
- G'(80) storage modulus
- rigidity in a high-temperature environment is improved, and flexibility and windability are improved.
- G'(80) is 3 ⁇ 10 4 Pa or less, flexibility in a high-temperature environment is improved, and flexibility and windability are improved.
- the adhesive for flexible displays has a storage modulus (hereinafter sometimes abbreviated as G'(200)) at 200° C. and 1 Hz of 2 ⁇ 10 3 to 3 ⁇ 10 4 Pa and 3 ⁇ 10 3 . It is preferably ⁇ 2 ⁇ 10 4 Pa.
- G'(200) storage modulus
- polymer materials soften due to thermal degradation when left in a high-temperature environment for a long period of time.
- G'(200) is correlated with the coating film strength of the pressure-sensitive adhesive under long-term high-temperature environments. That is, when G'(200) is 2 ⁇ 10 3 Pa or more, the rigidity is improved in a long-term high-temperature environment, and flexibility and windability can be maintained.
- G'(200) is 3 ⁇ 10 4 Pa or less, the flexibility can be maintained under a long-term high-temperature environment, and the flexibility and windability are improved.
- the pressure-sensitive adhesive for flexible displays has a loss tangent at -50°C and 1 Hz (hereinafter sometimes abbreviated as tan ⁇ (-50)) of 0.5 to 3.0, and 1.0 to 2.5. is more preferable.
- tan ⁇ ( ⁇ 50) is 0.5 or more, the stress relaxation property when subjected to physical deformation is improved, and the flexibility and windability are improved.
- tan ⁇ ( ⁇ 50) is 3.0 or less, the rigidity is improved when physical deformation is applied, and the flexibility and windability are improved.
- the pressure-sensitive adhesive for flexible displays has a loss tangent (hereinafter sometimes abbreviated as tan ⁇ (-20)) at ⁇ 20° C. and 1 Hz of 0.2 to 1.0 and 0.4 to 0.8. is more preferable.
- tan ⁇ ( ⁇ 20) is 0.2 or more, the stress relaxation property in a low temperature environment is improved, and the flexibility and windability are improved.
- tan ⁇ ( ⁇ 20) is 1.0 or less, the rigidity in a low temperature environment is improved, and the flexibility and windability are improved.
- the adhesive for flexible displays has a loss tangent at 25°C, 80°C, 200°C and 1 Hz of 0.01 to 0.5, preferably 0.10 to 0.4.
- the loss tangent at 25°C, 80°C, 200°C, and 1 Hz is 0.01 or more, the stress relaxation property is improved, and when it is 0.5 or less, the rigidity is improved, flexibility and winding improve sexuality.
- the loss tangent is within a constant value range of 0.01 to 0.5 over a wide temperature range, it is possible to maintain constant adhesive strength over a wide temperature range.
- the adhesive for flexible displays exhibits the flexibility required for foldable displays and the windability required for rollable displays.
- the adhesive for flexible displays preferably has a gel fraction of 55 to 90% by mass, more preferably 60 to 80% by mass.
- the gel fraction is 55% by mass or more, the cohesive force of the adhesive is improved, a tough adhesive layer is obtained, and the durability is improved, and when it is 90% by mass or less, the stress relaxation property of the adhesive is improved, a flexible pressure-sensitive adhesive layer is obtained, and adhesion is improved.
- the gel fraction can be determined as an insoluble matter in a solvent such as ethyl acetate, as in the first embodiment.
- the pressure-sensitive adhesive sheet of this embodiment is a pressure-sensitive adhesive sheet used for forming the pressure-sensitive adhesive layer in a laminate comprising a light-transmitting flexible substrate and a pressure-sensitive adhesive layer, That is, the pressure-sensitive adhesive sheet of the present embodiment is used for bonding light-transmitting flexible substrates.
- the pressure-sensitive adhesive sheet of the present embodiment has a configuration in which release films are formed on both sides of the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layers formed between the release films are acrylic It is an adhesive layer formed of a mixture of a system copolymer (A1), an acrylic copolymer (A2), and a curing agent (B).
- A1 system copolymer
- A2 acrylic copolymer
- B curing agent
- the release film is not particularly limited, but for example, a transparent plastic substrate can be preferably used. Materials for the transparent plastic substrate include those described in the first embodiment.
- the thickness of the transparent plastic substrate is not particularly limited, and is preferably 10 to 200 ⁇ m, more preferably 25 to 150 ⁇ m, for example.
- the release film may have either a single layer or multiple layers.
- the surface of the transparent substrate may be subjected to appropriate surface treatment such as physical treatment such as corona discharge treatment and plasma treatment, and chemical treatment such as undercoating treatment.
- the pressure-sensitive adhesive sheet of the present embodiment can be manufactured according to a normal pressure-sensitive adhesive sheet manufacturing method. For example, a mixture of an acrylic copolymer (A1), an acrylic copolymer (A2), and a curing agent (B) (hereinafter simply referred to as "adhesive") is applied to the release-treated surface of the release film. ) is directly coated so that the thickness after drying is a predetermined thickness to form an adhesive layer, and a release film is attached, or on the release-treated surfaces of the two release films Alternatively, the adhesive may be applied to a predetermined thickness after drying to form two adhesive layers, and then the respective adhesive layers may be adhered.
- A1 acrylic copolymer
- A2 acrylic copolymer
- B curing agent
- the adhesive may be applied to a predetermined thickness after drying to form two adhesive layers, and then the respective adhesive layers may be adhered.
- the thickness of the adhesive layer is not particularly limited, and is preferably 10 to 500 ⁇ m, more preferably 50 to 200 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer is 10 to 500 ⁇ m, it is preferable because sufficient cohesive force can be easily obtained and heat resistance, resistance to moist heat, flexibility and windability can be highly compatible.
- the one described in the first embodiment can be used.
- the adhesive sheet may be in the form of an adhesive tape wound into a roll by cutting it into a desired width and winding it into a roll.
- the laminate of this embodiment includes a light-transmitting flexible substrate, an adhesive layer, and a polarizing plate, and the adhesive layer is formed using the adhesive sheet of this embodiment.
- the laminate is formed from an adhesive sheet with excellent transparency, heat resistance, heat and humidity resistance, flexibility and windability, so it has excellent transparency, heat resistance, heat and humidity resistance, flexibility and windability.
- a light-transmissive flexible base material (cover panel) is attached to the polarizing plate via an adhesive layer made of the adhesive of the present embodiment.
- the pressure-sensitive adhesive sheet of this embodiment can be used in a form in which a transparent pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive is attached to a light-transmitting flexible substrate (cover panel) and a polarizing plate.
- the light-transmissive flexible base material cover panel
- the one described in the first embodiment can be used.
- transparent plastic substrates with excellent heat resistance, i.e., under severe conditions such as high temperature, high temperature and high humidity
- a transparent plastic substrate whose deformation is suppressed or prevented can be preferably used.
- PET Polyethylene terephthalate
- polycycloolefin polycycloolefin
- polyimide are particularly suitable as transparent plastic substrates.
- the thickness of the light-transmitting flexible substrate (cover panel) is not particularly limited, and is preferably 100 to 2000 ⁇ m, more preferably 200 to 1000 ⁇ m.
- a flexible display includes the laminate of the present embodiment and an optical element.
- the optical element is not particularly limited, and examples thereof include a liquid crystal element and an organic EL element.
- the flexible display of the present embodiment has a laminate with excellent transparency, heat resistance, resistance to moist heat, flexibility, and rollability, so it is excellent in transparency, heat resistance, resistance to humidity and heat, flexibility, and rollability.
- a light-transmitting flexible substrate (cover panel) is attached to the polarizing plate via the adhesive layer (first adhesive layer 1) made of the adhesive of the present embodiment. It is attached to the organic EL cell via an adhesive layer for polarizing plate (second adhesive layer 5).
- the transparent pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive is attached to the light-transmitting flexible substrate (cover panel) and the polarizing plate, and the pressure-sensitive adhesive layer for the polarizing plate is further attached to the polarizing plate. It can be used in a form in which the laminate is attached to the organic EL via. For example, in FIG.
- the adhesive of this embodiment can be used for both the first adhesive layer 1 and the second adhesive layer 5 .
- the quality required for the pressure-sensitive adhesive layer is higher for the first pressure-sensitive adhesive layer 1.
- the pressure-sensitive adhesive is preferably used for the first pressure-sensitive adhesive layer 1 because it has good adhesion and adhesiveness to the substrate.
- the adhesive for forming the second adhesive layer 5 the adhesive of the present embodiment may be used, or a conventionally known adhesive may be used.
- organic EL televisions organic EL smartphones, organic EL tablets, and organic EL smart watches.
- embodiments of the present invention include various embodiments not described here. For example, including configuration for:
- the acrylic copolymer is a copolymer of a monomer mixture containing all of the following monomers (a-1) to (a-3), A flexible display pressure-sensitive adhesive that satisfies all of (1) to (7) below and either or both of (i) to (ii) below.
- the acrylic copolymer further contains the following monomer (a-4).
- (ii) further includes a second acrylic copolymer containing the following monomer (a-5).
- (a-4) (meth)acrylic acid alkyl ester monomer having an alkyl group having 1 to 4 carbon atoms
- (a-5) (meth)acrylic acid alkyl ester monomer having a cycloalkyl group
- the adhesive contains an acrylic copolymer and a curing agent,
- the acrylic copolymer is a copolymer of a monomer mixture containing all of the following monomers (a-1) to (a-4), Use of an adhesive that satisfies all of (1) to (7) below.
- the acrylic copolymer contains, in 100% by mass of the monomer mixture, 20 to 60% by mass of the monomer (a-1), 10 to 50% by mass of the monomer (a-2), 0.5 to 2.5% by mass of the monomer (a-3) and 5 to 20% by mass of the monomer (a-4),
- Use of said adhesive comprising:
- an adhesive for use in a flexible display comprising: The adhesive contains a first acrylic copolymer, a second acrylic copolymer (except for the first acrylic copolymer), and a curing agent,
- the first acrylic copolymer is a copolymer of a monomer mixture containing all of the following monomers (a-1) to (a-3)
- the second acrylic copolymer is a copolymer of a monomer mixture containing the following monomer (a-5)
- Monomers having one or more polar groups selected from the group consisting of monomers having a hydroxy group and monomers having a carboxy group (a-5) (meth)acrylic acid alkyl ester monomers having a cycloalkyl group (1) Storage modulus at ⁇ 20° C.
- the first acrylic copolymer contains, in 100% by mass of the monomer mixture, 25 to 80% by mass of the monomer (a-1) 10 to 50% by mass of the monomer (a-2), and 0.5 to 2.5% by mass of the monomer (a-3) including
- the second acrylic copolymer contains, in 100% by mass of the monomer mixture, 40 to 95% by mass of the monomer (a-5) Use of said adhesive, comprising:
- a pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer that is a cured product of the pressure-sensitive adhesive.
- a laminate comprising a light-transmitting flexible substrate, an adhesive layer, and a polarizing plate, wherein the adhesive layer is a cured product of the adhesive.
- a flexible display comprising the laminate and an optical element.
- a numerical range indicated using “to” indicates a range that includes the numerical values before and after “to” as the minimum and maximum values, respectively.
- the upper limit or lower limit of the numerical range in one step can be arbitrarily combined with the upper limit or lower limit of the numerical range in another step.
- the present invention relates to the subject matter of Japanese Patent Application No. 2021-89211 filed May 27, 2021 and Japanese Patent Application No. 2021-89212 filed May 27, 2021, the entire disclosure of which is incorporated herein by reference. incorporated herein.
- the weight average molecular weight (Mw) is measured using GPC "LC-GPC system” manufactured by Shimadzu Corporation, and the weight average molecular weight (Mw) can be determined by conversion using polystyrene with a known molecular weight as a standard substance.
- Apparatus name LC-GPC system "Prominence” manufactured by Shimadzu Corporation Column: 4 GMHXL manufactured by Tosoh Corporation and 1 HXL-H manufactured by Tosoh Corporation were connected.
- Mobile phase solvent Tetrahydrofuran Flow rate: 1.0 ml/min Column temperature: 40°C
- the reaction was started by heating to 50° C. while stirring in a nitrogen atmosphere. After that, the reaction solution was reacted at 50° C. for 4 hours. After completion of the reaction, the mixture was cooled and diluted with ethyl acetate to obtain a copolymer (A-1) solution having a non-volatile content of 30% and a viscosity of 8000 mPa ⁇ s.
- the weight average molecular weight of the resulting copolymer (A-1) was 1,000,000.
- Tables 1 and 2 show the weight average molecular weights (Mw) of the obtained copolymers (A-1 to A-15, A'-1 to A'-5).
- Example 1 ⁇ Preparation of adhesive> Per 100 parts of acrylic copolymer (A-1) non-volatile matter, 0.5 parts of trimethylolpropane adduct (B-1) of tolylene diisocyanate as a curing agent (B), and 3- as an organic silane compound. 0.1 part of glycidoxypropyltrimethoxysilane (S-1) and ethyl acetate were blended so that the non-volatile content was 20%, and the mixture was stirred to obtain an adhesive.
- the resulting pressure-sensitive adhesive was applied onto a release film (polyethylene terephthalate (PET), "E7004", silicone-based release layer manufactured by Toyobo Co., Ltd.) having a thickness of 50 ⁇ m so that the thickness after drying was 50 ⁇ m. , and dried at 110°C for 3 minutes to form an adhesive layer.
- a 38 ⁇ m thick release film polyethylene terephthalate, “SP-PET3811”, silicone release layer, manufactured by Lintec Co., Ltd.
- a laminate of "sheets” was produced. Then, the obtained laminate was allowed to stand under conditions of a temperature of 25° C. and a relative humidity of 55% for one week to obtain an adhesive sheet.
- Examples 2 to 20, Comparative Examples 1 to 10 As shown in Tables 3 to 5, pressure-sensitive adhesive sheets were obtained in the same manner as in Example 1, except that the types and amounts (parts by mass) of the copolymer and curing agent were changed.
- the pressure-sensitive adhesive sheet thus obtained was cut into a size of 25 mm wide ⁇ 100 mm long.
- a release film on one side of the cut adhesive sheet was peeled off, and the adhesive sheet was attached to a 200 mesh 50 mm wide ⁇ 120 mm long piece whose mass had been measured in advance.
- peel off the other release film fold the mesh so that the adhesive is inside so that the adhesive is not exposed, and immerse the adhesive wrapped in the mesh in about 50 mL of ethyl acetate at 23 ° C. for 7 days.
- the sol component of the adhesive was eluted out of the mesh.
- the adhesive wrapped with mesh was taken out, dried at 100° C. for 1 hour, allowed to cool for about 20 minutes, and then dried mass was measured.
- the gel fraction of the adhesive was calculated by the following formula.
- the pressure-sensitive adhesive sheet for testing was obtained by peeling off the release film on one side of the pressure-sensitive adhesive sheet obtained, and exposing the exposed pressure-sensitive adhesive layer to a 100 ⁇ m thick PET film (manufactured by Toyobo Co., Ltd., A-4300) using a laminator to prepare an adhesive sheet for testing consisting of a PET film/adhesive layer/release film.
- An adhesive sheet for testing was cut into a size of 112 mm wide ⁇ 200 mm long (equivalent to a 9-inch display) to prepare an adhesive sheet for testing 1 comprising a PET film/adhesive layer/release film.
- the release film was peeled off from this test adhesive sheet 1, and the exposed adhesive layer was attached to a non-alkali glass plate (EN-A1: manufactured by AGC Co., Ltd.) at 25 ° C. and a relative humidity of 50% using a laminator, HAZE was measured.
- the HAZE was measured using a Turbidimeter NDH5000W manufactured by Nippon Denshoku Industries Co., Ltd. Evaluation criteria are as follows. [Evaluation criteria] A: HAZE is less than 1.0 (good). B: HAZE is 1.0 or more (defective).
- the pressure-sensitive adhesive sheet for test was cut into a size of 112 mm wide ⁇ 200 mm long (equivalent to a 9-inch display) to prepare a pressure-sensitive adhesive sheet 2 for test consisting of a PET film/adhesive layer/release film.
- the release film was peeled off from this test adhesive sheet 2, and the exposed adhesive layer was placed on a polarizing plate (layer structure: triacetyl cellulose film/polyvinyl alcohol film/cycloolefin film) at 25°C and a relative humidity of 50% using a laminator. to obtain a test laminate consisting of a PET film/adhesive layer/polarizing plate.
- ⁇ Dynamic bending resistance bending resistance [1], [2], [3]>
- the release film was peeled off from the separately prepared test adhesive sheet 2, and the exposed adhesive layer was placed on a polarizing plate (layer structure: triacetyl cellulose film / polyvinyl alcohol film / cycloolefin film) in an atmosphere of 25 ° C. and a relative humidity of 50%. They were attached using a laminator to obtain a test laminate consisting of a PET film/adhesive layer/polarizing plate. Then, the test laminate was subjected to bending resistance [1] at 25 ° C. and 50% relative humidity as a normal test, bending resistance [2] at 85 ° C.
- ⁇ Static bending resistance: bending resistance [1], [2], [3]> The release film was peeled off from the test pressure-sensitive adhesive sheet 2, which was prepared separately, and the exposed pressure-sensitive adhesive layer was exposed to a polarizing plate (layer structure: triacetyl cellulose film/polyvinyl alcohol film/cycloolefin film) in an atmosphere of 25°C and relative humidity of 50% RH. , using a laminator to obtain a laminate for testing consisting of a PET film/adhesive layer/polarizing plate. Then, the test laminate was subjected to bending resistance [1] in an atmosphere of 25 ° C. and 50% relative humidity as a normal test, bending resistance [2] in an atmosphere of 85 ° C.
- a polarizing plate layer structure: triacetyl cellulose film/polyvinyl alcohol film/cycloolefin film
- the release film was peeled off from the test pressure-sensitive adhesive sheet 2, which was prepared separately, and the exposed pressure-sensitive adhesive layer was exposed to a polarizing plate (layer structure: triacetyl cellulose film/polyvinyl alcohol film/cycloolefin film) in an atmosphere of 25°C and relative humidity of 50% RH. , using a laminator to obtain a laminate for testing consisting of a PET film/adhesive layer/polarizing plate. Next, the test laminate was wound around a metal bar having a radius of 3 mm in the long side direction with the PET side of the test piece facing inward, and after being formed into a roll, it was tied at three points with octopus thread and fixed.
- a polarizing plate layer structure: triacetyl cellulose film/polyvinyl alcohol film/cycloolefin film
- the roll-shaped test laminate was held in an atmosphere of 25° C. and a relative humidity of 50% RH for 240 hours.
- the static bendability was evaluated from the following viewpoints on the appearance after the test. Appearance: The presence or absence of air bubbles in the test laminate and the presence or absence of lifting and peeling of the pressure-sensitive adhesive layer were visually evaluated under the following conditions. [Evaluation criteria] AA: Absolutely no bubble generation, lifting or peeling is observed, and there is absolutely no problem in practical use. A: Bubble generation, floating and peeling are slightly observed, but there is no practical problem. B: Remarkable generation of air bubbles, floating and peeling are observed, and there is a problem in practical use.
- the pressure-sensitive adhesive sheets of Examples 1 to 20 had good transparency, heat resistance, moist heat resistance, flexibility, and windability.
- the laminate and flexible display using the pressure-sensitive adhesive sheet of the present invention are excellent in transparency, heat resistance, moist heat resistance, and flexibility.
- the flexible display of the present invention was excellent in visibility and contrast.
- the adhesive sheets of Comparative Examples 1 to 10 could not satisfy all of the above properties.
- the reaction solution was reacted at 50° C. for 4 hours. After completion of the reaction, the mixture was cooled and diluted with ethyl acetate to obtain a copolymer (A-1) solution having a non-volatile content of 30% and a viscosity of 7000 mPa ⁇ s.
- the weight average molecular weight of the resulting copolymer (A-1) was 1,200,000.
- Cyclohexyl acrylate (CHA) was added as a monomer (a-5) to a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen inlet tube (hereinafter simply referred to as the "reaction vessel”).
- reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen inlet tube
- 35 parts, 65 parts of 2-ethylhexyl acrylate (EHA) as a monomer (a-2), and 2 parts of AIBN as an initiator were charged, and the atmosphere in the reaction vessel was replaced with nitrogen gas. After that, the reaction was started by heating to 50° C. while stirring in a nitrogen atmosphere. After that, the reaction solution was reacted at 50° C. for 4 hours.
- EHA 2-ethylhexyl acrylate
- AIBN as an initiator
- copolymer (A2-1) solution having a non-volatile content of 30% and a viscosity of 100 mPa ⁇ s.
- the weight average molecular weight of the obtained copolymer (A2-1) was 20,000.
- Tables 8 and 9 show the weight average molecular weights (Mw) of the obtained copolymers (A1-1 to A1-12, A2-1 to A2-4).
- Example 1A ⁇ Preparation of adhesive> Per 100 parts of acrylic copolymer (A1-1) non-volatile matter, acrylic copolymer (A2-1) 5 parts, curing agent (B) trimethylolpropane adduct of tolylene diisocyanate (B- 1) 0.5 part, 0.1 part of 3-glycidoxypropyltrimethoxysilane (S-1) as an organic silane compound, and ethyl acetate so that the non-volatile content is 20%, are blended and stirred to form an adhesive. got
- the resulting pressure-sensitive adhesive was applied onto a release film (polyethylene terephthalate (PET), "E7004", silicone-based release layer manufactured by Toyobo Co., Ltd.) having a thickness of 50 ⁇ m so that the thickness after drying was 50 ⁇ m. , and dried at 110°C for 3 minutes to form an adhesive layer.
- a 38 ⁇ m thick release film polyethylene terephthalate, “SP-PET3811”, silicone release layer, manufactured by Lintec Co., Ltd.
- a laminate of "sheets” was produced. Then, the obtained laminate was allowed to stand under conditions of a temperature of 25° C. and a relative humidity of 55% for one week to obtain an adhesive sheet.
- Examples 2A to 20A Comparative Examples 1A to 4A
- Tables 10 to 12 pressure-sensitive adhesive sheets were obtained in the same manner as in Example 1A, except that the types and amounts (parts by mass) of the copolymer and curing agent were changed.
- the pressure-sensitive adhesive sheet thus obtained was cut into a size of 25 mm wide ⁇ 100 mm long.
- a release film on one side of the cut adhesive sheet was peeled off, and the adhesive sheet was attached to a 200 mesh 50 mm wide ⁇ 120 mm long piece whose mass had been measured in advance.
- peel off the other release film fold the mesh so that the adhesive is inside so that the adhesive is not exposed, and immerse the adhesive wrapped in the mesh in about 50 mL of ethyl acetate at 23 ° C. for 7 days.
- the sol component of the adhesive was eluted out of the mesh.
- the adhesive wrapped with mesh was taken out, dried at 100° C. for 1 hour, allowed to cool for about 20 minutes, and then dried mass was measured.
- the gel fraction of the adhesive was calculated by the following formula.
- the pressure-sensitive adhesive sheet for testing was obtained by peeling off the release film on one side of the pressure-sensitive adhesive sheet obtained, and exposing the exposed pressure-sensitive adhesive layer to a 100 ⁇ m thick PET film (manufactured by Toyobo Co., Ltd., A-4300) using a laminator to prepare an adhesive sheet for testing consisting of a PET film/adhesive layer/release film.
- An adhesive sheet for testing was cut into a size of 112 mm wide ⁇ 200 mm long (equivalent to a 9-inch display) to prepare an adhesive sheet for testing 1 comprising a PET film/adhesive layer/release film.
- the release film was peeled off from this test adhesive sheet 1, and the exposed adhesive layer was attached to a non-alkali glass plate (EN-A1: manufactured by AGC Co., Ltd.) at 25 ° C. and a relative humidity of 50% using a laminator, HAZE was measured.
- the HAZE was measured using a Turbidimeter NDH5000W manufactured by Nippon Denshoku Industries Co., Ltd. Evaluation criteria are as follows. [Evaluation criteria] A: HAZE is less than 1.0 (good). B: HAZE is 1.0 or more (defective).
- the pressure-sensitive adhesive sheet for test was cut into a size of 112 mm wide ⁇ 200 mm long (equivalent to a 9-inch display) to prepare a pressure-sensitive adhesive sheet 2 for test consisting of a PET film/adhesive layer/release film.
- the release film was peeled off from this test adhesive sheet 2, and the exposed adhesive layer was placed on a polarizing plate (layer structure: triacetyl cellulose film/polyvinyl alcohol film/cycloolefin film) at 25°C and a relative humidity of 50% using a laminator. to obtain a test laminate consisting of a PET film/adhesive layer/polarizing plate.
- ⁇ Dynamic bending resistance bending resistance [1], [2], [3]>
- the release film was peeled off from the separately prepared test adhesive sheet 2, and the exposed adhesive layer was placed on a polarizing plate (layer structure: triacetyl cellulose film / polyvinyl alcohol film / cycloolefin film) in an atmosphere of 25 ° C. and a relative humidity of 50%. They were attached using a laminator to obtain a test laminate consisting of a PET film/adhesive layer/polarizing plate. Then, the test laminate was subjected to bending resistance [1] at 25 ° C. and 50% relative humidity as a normal test, bending resistance [2] at 85 ° C.
- ⁇ Static bending resistance: bending resistance [1], [2], [3]> The release film was peeled off from the test pressure-sensitive adhesive sheet 2, which was prepared separately, and the exposed pressure-sensitive adhesive layer was exposed to a polarizing plate (layer structure: triacetyl cellulose film/polyvinyl alcohol film/cycloolefin film) in an atmosphere of 25°C and relative humidity of 50% RH. , using a laminator to obtain a laminate for testing consisting of a PET film/adhesive layer/polarizing plate. Then, the test laminate was subjected to bending resistance [1] in an atmosphere of 25 ° C. and 50% relative humidity as a normal test, bending resistance [2] in an atmosphere of 85 ° C.
- a polarizing plate layer structure: triacetyl cellulose film/polyvinyl alcohol film/cycloolefin film
- the release film was peeled off from the test pressure-sensitive adhesive sheet 2, which was prepared separately, and the exposed pressure-sensitive adhesive layer was exposed to a polarizing plate (layer structure: triacetyl cellulose film/polyvinyl alcohol film/cycloolefin film) in an atmosphere of 25°C and relative humidity of 50% RH. , using a laminator to obtain a laminate for testing consisting of a PET film/adhesive layer/polarizing plate. Next, the test laminate was wound around a metal bar having a radius of 3 mm in the long side direction with the PET side of the test piece facing inward, and after being formed into a roll, it was tied at three points with octopus thread and fixed.
- a polarizing plate layer structure: triacetyl cellulose film/polyvinyl alcohol film/cycloolefin film
- the roll-shaped test laminate was held in an atmosphere of 25° C. and a relative humidity of 50% RH for 240 hours.
- the static bendability was evaluated from the following viewpoints on the appearance after the test. Appearance: The presence or absence of air bubbles in the test laminate and the presence or absence of lifting and peeling of the pressure-sensitive adhesive layer were visually evaluated under the following conditions. [Evaluation criteria] AA: Absolutely no bubble generation, lifting or peeling is observed, and there is absolutely no problem in practical use. A: Bubble generation, floating and peeling are slightly observed, but there is no practical problem. B: Remarkable generation of air bubbles, floating and peeling are observed, and there is a problem in practical use.
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Abstract
Description
また、フレキシブル性には、ディスプレイ構成によって、動的屈曲性、静的屈曲性、巻き取り性が必要とされるが、これらフレキシブル性を個別に満足することはできても、同時に全てを満足することは困難であり、加えて、高温環境および高温高湿環境下において、動的屈曲性、静的屈曲性、巻き取り性を満たすことができていないのが現状である。
前記アクリル系共重合体は、下記モノマー(a-1)~(a-4)の全てを含むモノマー混合物の共重合体であり、
下記、(1)~(7)の全てを満たす、フレキシブルディスプレイ用粘着剤である。
(a-1)炭素数6~10のアルキル基を有する(メタ)アクリル酸分岐アルキルエステルモノマー
(a-2)炭素数12~20のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(a-3)ヒドロキシ基を有するモノマーおよびカルボキシ基を有するモノマーからなる群から選択される1種類以上の極性基を有するモノマー
(a-4)炭素数1~4のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(1)-20℃、1Hzでの貯蔵弾性率が、5×104~3×105Paであり、
(2)25℃、1Hzでの貯蔵弾性率が、1×104~5×104Paであり、
(3)80℃、1Hzでの貯蔵弾性率が、5×103~3×104Paであり、
(4)200℃、1Hzでの貯蔵弾性率が、2×103~3×104Paであり、
(5)-50℃、1Hzでの損失正接が、0.5~3.0であり、
(6)-20℃、1Hzでの損失正接が、0.2~1.0であり、
(7)25℃、80℃、200℃、1Hzでの損失正接が、0.01~0.5である。
モノマー(a-1)を20~60質量%、
モノマー(a-2)を10~50質量%、
モノマー(a-3)を0.5~2.5質量%、および
モノマー(a-4)を5~20質量%、
を含む、前記フレキシブルディスプレイ用粘着剤である。
前記第1のアクリル系共重合体は、下記モノマー(a-1)~(a-3)の全てを含むモノマー混合物の共重合体であり、
前記第2のアクリル系共重合体は、下記モノマー(a-5)を含むモノマー混合物の共重合体であり、
下記、(1)~(7)の全てを満たす、フレキシブルディスプレイ用粘着剤である。
(a-1)炭素数6~10のアルキル基を有する(メタ)アクリル酸分岐アルキルエステルモノマー
(a-2)炭素数12~20のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(a-3)ヒドロキシ基を有するモノマーおよびカルボキシ基を有するモノマーからなる群から選択される1種類以上の極性基を有するモノマー
(a-5)シクロアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(1)-20℃、1Hzでの貯蔵弾性率が、5×104~3×105Paであり、
(2)25℃、1Hzでの貯蔵弾性率が、1×104~5×104Paであり、
(3)80℃、1Hzでの貯蔵弾性率が、5×103~3×104Paであり、
(4)200℃、1Hzでの貯蔵弾性率が、2×103~3×104Paであり、
(5)-50℃、1Hzでの損失正接が、0.5~3.0であり、
(6)-20℃、1Hzでの損失正接が、0.2~1.0であり、
(7)25℃、80℃、200℃、1Hzでの損失正接が、0.01~0.5である。
モノマー(a-1)を25~80質量%
モノマー(a-2)を10~50質量%、および
モノマー(a-3)を0.5~2.5質量%
を含み、
前記第2のアクリル系共重合体は、モノマー混合物100質量%中に、
モノマー(a-5)を40~95質量%
を含む、前記フレキシブルディスプレイ用粘着剤である。
また、本実施形態の粘着シート、および積層体を用いることで、視認性とコントラストに優れるフレキシブルディスプレイを提供できる。
また、本明細書では、(a-1)炭素数6~10のアルキル基を有する(メタ)アクリル酸分岐アルキルエステルモノマー、(a-2)炭素数12~20のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー、(a-3)ヒドロキシ基を有するモノマーおよびカルボキシ基を有するモノマーからなる群から選択される1種類以上の極性基を有するモノマー、(a-4)炭素数1~4のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー、および(a-5)シクロアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー、を、それぞれモノマー(a-1)、モノマー(a-2)、モノマー(a-3)、モノマー(a-4)、およびモノマー(a-5)と称することがある。また、フレキシブルディスプレイ用粘着剤を単に粘着剤と称することがある。
なお、本明細書中に記載の各種成分は特に注釈しない限り、それぞれ独立に一種単独でも二種以上を併用してもよい。
[フレキシブルディスプレイ用粘着剤]
本実施形態のフレキシブルディスプレイ用粘着剤は、アクリル系共重合体および硬化剤を含み、
アクリル系共重合体は、下記モノマー(a-1)~(a-4)の全てを含むモノマー混合物の共重合体であり、
下記、(1)~(7)の全てを満たす。
なお、本実施形態のアクリル系共重合体及び硬化剤をそれぞれ共重合体(A)及び硬化剤(B)ともいう。
(a-2)炭素数12~20のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(a-3)ヒドロキシ基を有するモノマーおよびカルボキシ基を有するモノマーからなる群から選択される1種類以上の極性基を有するモノマー
(a-4)炭素数1~4のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(2)25℃、1Hzでの貯蔵弾性率が、1×104~5×104Paであり、
(3)80℃、1Hzでの貯蔵弾性率が、5×103~3×104Paであり、
(4)200℃、1Hzでの貯蔵弾性率が、2×103~3×104Paであり、
(5)-50℃、1Hzでの損失正接が、0.5~3.0であり、
(6)-20℃、1Hzでの損失正接が、0.2~1.0であり、
(7)25℃、80℃、200℃、1Hzでの損失正接が、0.01~0.5である。
アクリル系共重合体(A)は、少なくとも、上述のモノマー(a-1)~(a-4)の全てを含むモノマー混合物の共重合体であり、モノマー混合物は、必要に応じてモノマー(a-1)~(a-4)以外のその他モノマーを含んでもよい。
モノマー(a-1)は、炭素数6~10のアルキル基を有する(メタ)アクリル酸分岐アルキルエステルモノマーであり、具体的には、例えば、(メタ)アクリル酸イソヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸イソデシルなどが挙げられる。応力緩和性および密着力の観点から、(メタ)アクリル酸イソオクチル、および(メタ)アクリル酸2-エチルヘキシルが好ましい。
モノマー(a-1)を含有することで、粘着剤の応力緩和性が向上し、柔軟な粘着剤層が得られ、密着力を向上することができる。
モノマー(a-2)は、炭素数12~20のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマーであり、具体的には、例えば、(メタ)アクリル酸ドデシル、(メタ)アクリル酸トリデシル、(メタ)アクリル酸テトラデシル、(メタ)アクリル酸ペンタデシル、(メタ)アクリル酸ヘキサデシル、(メタ)アクリル酸ヘプタデシル、(メタ)アクリル酸オクタデシル、(メタ)アクリル酸ノナデシル、(メタ)アクリル酸イコシルなどが挙げられる。屈曲性および巻き取り性の観点から、(メタ)アクリル酸ドデシル、(メタ)アクリル酸テトラデシル、(メタ)アクリル酸イコシルがゴム弾性の観点で好ましく、(メタ)アクリル酸ドデシルが、好ましい。
モノマー(a-2)を含有することで、粘着剤の凝集力が向上し、強靭な粘着剤層が得られ、フレキシブル性を向上することができる。
モノマー(a-3)は、ヒドロキシ基を有するモノマーおよびカルボキシ基を有するモノマーからなる群から選択される1種類以上の極性基を有するモノマーである。
モノマー(a-4)は、分子内に炭素数1~4のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマーであり、具体的には、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t-ブチルなどが挙げられる。凝集力および接着力における観点から、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチルが好ましい。
モノマー(a-4)を含有することで、粘着剤の凝集力が向上し、強靭な粘着剤層が得られ、接着力を向上することができる。
その他モノマーは、モノマー(a-1)~(a-4)以外のモノマーであり、アクリル系共重合体(A)は、モノマー(a-1)~(a-4)に加えて、さらにその他モノマーを含んでもよい。
その他モノマーは、モノマー(a-1)、モノマー(a-2)、およびモノマー(a-4)以外の(メタ)アクリル酸アルキルエステルモノマー、エポキシ基を有する(メタ)アクリル酸モノマー、アミノ基を有する(メタ)アクリル酸モノマー、アルキレンオキシ基を有するモノマー、その他ビニルモノマーなどが挙げられる。
アクリル系共重合体(A)は、モノマー混合物を重合し、製造することができる。
重合は、溶液重合、塊状重合、乳化重合、懸濁重合など公知の重合方法が可能であるが、溶液重合が好ましい。溶液重合で使用する溶媒は、例えば、アセトン、酢酸メチル、酢酸エチル、トルエン、キシレン、アニソール、メチルエチルケトン、シクロヘキサノンなどが好ましい。
重合温度は、60~120℃が好ましい。重合時間は、5~12時間程度が好ましい。
過酸化物は、例えば、ジ-t-ブチルパーオキサイド、ジクミルパーオキサイド、t-ブチルクミルパーオキサイド、α,α’-ビス(t-ブチルパーオキシ-m-イソプロピル)ベンゼン、2,5-ジ(t-ブチルパーオキシ)ヘキシン-3などのジアルキルパーオキサイド;t-ブチルパーオキシベンゾエート、t-ブチルパーオキシアセテート、2,5-ジメチル-2,5-ジ(ベンゾイルパーオキシ)ヘキサンなどのパーオキシエステル;
シクロヘキサノンパーオキサイド、3,3,5-トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイドなどのケトンパーオキサイド;
2,2-ビス(4,4-ジ-t-ブチルパーオキシシクロヘキシル)プロパン、1,1-ビス(t-ブチルパーオキシ)3,3,5-トリメチルシクロヘキサン、1,1-ビス(t-ブチルパーオキシ)シクロヘキサン、n-ブチル-4,4-ビス(t-ブチルパーオキシ)バレート、などのパーオキシケタール;
クメンヒドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、2,5-ジメチルシクロヘキサン-2,5-ジハイドロパーオキサイドなどのハイドロパーオキサイド;
ベンゾイルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、2,4-ジクロロベンゾイルパーオキサイドなどのジアシルパーオキサイド;
ビス(t-ブチルシクロヘキシル)パーオキシジカーボネートなどのパーオキシジカーボネート等が挙げられる。
2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、2,2’-アゾビス(2,4-ジメチルバレロニトリル)などの2,2’-アゾビスバレロニトリル;2,2’-アゾビス(2-ヒドロキシメチルプロピオニトリル)などの2,2’-アゾビスプロピオニトリル;
1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)などの1,1’-アゾビス-1-アルカンニトリル等が挙げられる。
共重合体(A)の重量平均分子量は、80万~180万が好ましく、100万~150万がより好ましい。80万~180万の範囲にあると凝集力がより向上し、耐湿熱性、耐熱性がより向上する。なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法により測定するポリスチレン換算の値である。
硬化剤(B)は、共重合体(A)が有するヒドロキシ基および/または、カルボキシ基と反応することで、粘着剤層の凝集力が向上し、耐久性、耐汚染性が向上する。
これらのうち、硬化剤(B)として、イソシアネート化合物を使用することで、接着性および、耐久性が向上できるために好ましい。
本実施形態のフレキシブルディスプレイ用粘着剤は、さらに有機シラン化合物を含有できる。
有機シラン化合物は、例えば、3-(メタ)アクリロキシプロピルトリメトキシシラン、3-(メタ)アクリロキシプロピルトリエトキシシラン、3-(メタ)アクリロキシプロピルトリプロポキシシラン、3-(メタ)アクリロキシプロピルトリブトキシシラン、3-(メタ)アクリロキシプロピルメチルジメトキシシラン、3-(メタ)アクリロキシプロピルメチルジエトキシシランなどの(メタ)アクリロキシ基を有するアルコキシシラン化合物;
ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリイソプロポキシシラン、ビニルトリブトキシシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシランなどのビニル基を有するアルコキシシラン化合物;
3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリプロポキシシラン、3-アミノプロピルメチルジメトキシシラン、3-アミノプロピルメチルジエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルメチルジエトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシランなどのアミノ基を有するアルコキシシラン化合物;
3-メルカプトプロピルトリメトキシシラン、3-メルカプトプロピルトリエトキシシラン、3-メルカプトプロピルトリプロポキシシラン、3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルメチルジエトキシシランなどのメルカプト基を有するアルコキシシラン化合物;
3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルトリプロポキシシラン、3-グリシドキシプロピルトリブトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランなどのエポキシ基を有するアルコキシシラン化合物;
テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシランなどのテトラアルコキシシラン化合物;
3-クロロプロピルトリメトキシシラン、n-ヘキシルトリメトキシシラン、n-ヘキシルトリエトキシシラン、n-デシルトリメトキシシラン、n-デシルトリエトキシシラン、スチリルトリメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチルブチリデン)プロピルアミン、1,3,5-トリス(3-トリメトキシシリルプロピル)イソシアヌレート、3-イソシアネートプロピルトリメトキシシラン、3-イソシアネートプロピルトリエトキシシラン、ヘキサメチルジシラザン、分子内にアルコキシシリル基を有するシリコーンレジンなどが挙げられる。
フレキシブルディスプレイ用粘着剤の貯蔵弾性率および損失正接は、周波数1Hzの粘弾性測定により求められる。損失正接は、貯蔵弾性率と損失弾性率の比、損失弾性率/貯蔵弾性率である。貯蔵弾性率は、材料が変形する際に弾性エネルギーとして貯蔵される部分に相当し、硬さの程度を表す指標である。すなわち、貯蔵弾性率の値が高いほど、粘着剤は硬く、貯蔵弾性率の値が低いほど柔らかいことになる。
貯蔵弾性率および損失正接は、用いる共重合体のモノマー組成、配合量、および合成条件等と、硬化剤の種類、配合量等により制御することができる。
フレキシブルディスプレイ用粘着剤は、-20℃、1Hzでの貯蔵弾性率(以下、G’(-20)と略記することがある)が、5×104~3×105Paであり、6×104~2×105Paであることがより好ましい。G’(-20)が5×104Pa以上であると、低温環境下での剛直性が向上し、屈曲性および巻き取り性が向上する。
フレキシブルディスプレイ用粘着剤は、-50℃、1Hzでの損失正接(以下、tanδ(-50)と略記することがある)が、0.5~3.0であり、1.0~2.5であることがより好ましい。一般にポリマー材料は、屈曲、巻き取り等の物理変形を加えらと、摩耗して破損する。本発明者らが鋭意検討を重ねたところ、tanδ(-50)は、物理変形における粘着剤の塗膜強度と相関があることを見出した。すなわち、tanδ(-50)が0.5以上であると、物理変形を加えられた際の、応力緩和性が向上し、屈曲性および巻き取り性が向上する。tanδ(-50)が3.0以下であると、物理変形を加えられた際の、剛直性が向上し、屈曲性および巻き取り性が向上する。
乾燥させた粘着剤を積層して厚み約1.0mmとしたものを測定用サンプルとした。
TA Insturument-Waters LL.C.社製「Discovery HR-2(DHR-2)」を用いて、以下の条件により、粘弾性測定を行うことにより、測定結果から、各温度における貯蔵弾性率および損失正接を読み取ることができる。
(測定条件)
変形モード:ねじり
測定周波数:1Hz
昇温速度:10℃/分
治具形状:パラレルプレート 8.0mmφ
法線荷重:1N
フレキシブルディスプレイ用粘着剤は、ゲル分率が55~90質量%であることが好ましく、60~80質量%がより好ましい。ゲル分率が55質量%以上であると、粘着剤の凝集力が向上し、強靭な粘着剤層が得られ、耐久性が向上し、90%質量以下であると、粘着剤の応力緩和性が向上し、柔軟な粘着剤層が得られ、密着力が向上する。
ゲル分率は、酢酸エチル等の溶媒に対する不溶分として求めることができる。具体的には、下記式1によって表されるように、粘着剤層を酢酸エチル中に50℃で1日間浸漬した後の不溶成分の、浸漬前の粘着剤層に対する質量分率(単位:質量%)として求められる。
(式1)
ゲル分率(質量%)=((X-Y)/X)×100
X=浸漬前の粘着剤層の質量(g)
Y=浸漬後の粘着剤層の質量(g)
本実施形態の粘着シートは、光透過性可撓性基材と粘着剤層からなる積層体における、前記粘着剤層を形成するために用いられる粘着シートであり、すなわち、本実施形態の粘着シートは、光透過性可撓性基材を接合するために用いられる。
図1に、粘着シートを部分的に示す概略断面図の例を示す。図1において、1は第1の粘着剤層、2は剥離フィルムである。
剥離フィルムとしては、特に制限されないが、例えば、透明プラスチック基材を好適に用いることができる。透明プラスチック基材の素材としては、例えば、ポリエチレンテレフタレート(PET)等のポリエステル、ポリメチルメタクリレート(PMMA)等のアクリル系樹脂;ポリカーボネート、トリアセチルセルロース、ポリサルフォン、ポリアリレート、ポリシクロオレフィン等のプラスチック材料などが挙げられる。なお、プラスチック材料は単独でまたは2種以上組み合わせて使用することができる。
本実施形態の粘着シートは、通常の粘着シートの製造方法に従って製造することができる。例えば、剥離フィルムの剥離処理面に、アクリル系共重合体(A)と硬化剤(B)の混合物(以下、単に「粘着剤」と記述する場合がある。)を、乾燥後の厚さが所定の厚さとなるように直接塗工して粘着剤層を形成し、剥離フィルムを貼付する方法、または、2枚の剥離フィルムの剥離処理面に、粘着剤を乾燥後の厚さが所定の厚さとなるように塗工して、2つの粘着剤層をそれぞれ形成した後、各粘着剤層を貼付する方法等により作製することができる。
本実施形態の積層体は、光透過性可撓性基材、粘着剤層、および偏光板を備え、粘着剤層は、本実施形態の粘着シートを用いて形成されてなる。
フレキシブルディスプレイは、本実施形態の積層体、および光学素子を備える。光学素子としては、特に限定されず、例えば、液晶素子、有機EL素子等が挙げられる。
例えば、図3において、本実施形態の粘着剤は、第1の粘着剤層1、および第2の粘着剤層5のいずれにも用いることができる。
一般に、第1の粘着剤層1と第2の粘着剤層5を比較した場合、粘着剤層に要求される要求品質は第1の粘着剤層1の方が要求は高く、本実施形態の粘着剤は、基材への密着性および、接着性が良好であることから、第1の粘着剤層1に用いられることが好ましい。このとき、第2の粘着剤層5を形成するための粘着剤は、本実施形態の粘着剤を用いてもよく、従来公知の粘着剤を用いてもよい。
[フレキシブルディスプレイ用粘着剤]
本実施形態の粘着剤は、第1のアクリル系共重合体、第2のアクリル系共重合体および硬化剤を含み、
第1のアクリル系共重合体(A1)は、下記モノマー(a-1)~(a-3)の全てを含むモノマー混合物の共重合体であり、
第2のアクリル系共重合体が(A2)は、下記モノマー(a-5)を含むモノマー混合物の共重合体であり、
下記、(1)~(7)の全てを満たす。
なお、本実施形態の第1のアクリル系共重合体、第2のアクリル系共重合体及び硬化剤をそれぞれアクリル系共重合体(A1)、アクリル系共重合体(A2)及び硬化剤(B)ともいう。さらにアクリル系共重合体(A1)及びアクリル系共重合体(A2)をそれぞれ共重合体(A1)及び共重合体(A2)ともいう。
(a-2)炭素数12~20のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(a-3)ヒドロキシ基を有するモノマーおよびカルボキシ基を有するモノマーからなる群から選択される1種類以上の極性基を有するモノマー
(a-5)シクロアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(2)25℃、1Hzでの貯蔵弾性率が、1×104~5×104Paであり、
(3)80℃、1Hzでの貯蔵弾性率が、5×103~3×104Paであり、
(4)200℃、1Hzでの貯蔵弾性率が、2×103~3×104Paであり、
(5)-50℃、1Hzでの損失正接が、0.5~3.0であり、
(6)-20℃、1Hzでの損失正接が、0.2~1.0であり、
(7)25℃、80℃、200℃、1Hzでの損失正接が、0.01~0.5である。
アクリル系共重合体(A1)は、少なくとも、上述のモノマー(a-1)~(a-3)の全てを含むモノマー混合物の共重合体であり、モノマー混合物は、必要に応じてモノマー(a-1)~(a-3)以外のその他を含んでもよい。
アクリル系共重合体(A2)は、少なくとも、モノマー(a-5)を含むモノマー混合物の共重合体であり、モノマー混合物は、必要に応じてモノマー(a-1)~(a-3)、およびモノマー(a-1)~(a-3)およびモノマー(a-5)以外のその他を含んでもよい。
なお、モノマー(a-1)~(a-3)の全てを含んでいても、モノマー(a-5)を含む場合は、アクリル系共重合体(A2)に該当するものと定義する。
モノマー(a-1)は、炭素数6~10のアルキル基を有する(メタ)アクリル酸分岐アルキルエステルモノマーであり、具体的には、第1の実施形態のモノマー(a-1)に記載のものが挙げられる。応力緩和性および密着力の観点から、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸2-エチルヘキシルが好ましい。
モノマー(a-2)は、炭素数12~20のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマーであり、具体的には、第1の実施形態のモノマー(a-2)に記載のものが挙げられる。屈曲性および巻き取り性の観点から、(メタ)アクリル酸ドデシル、(メタ)アクリル酸テトラデシル、(メタ)アクリル酸イコシルがゴム弾性の観点で好ましく、(メタ)アクリル酸ドデシルが好ましい。
モノマー(a-3)は、ヒドロキシ基を有するモノマーおよびカルボキシ基を有するモノマーからなる群から選択される1種類以上の極性基を有するモノマーである。
モノマー(a-5)は、シクロアルキル基を有する(メタ)アクリル酸アルキルエステルモノマーであれば制限されず、具体的には、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸ジシクロペンタニル、(メタ)アクリル酸シクロドデシル、(メタ)アクリル酸メチルシクロヘキシル、(メタ)アクリル酸トリメチルシクロヘキシルなどが挙げられる。凝集性の観点から、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸シクロヘキシルが好ましく、凝集性およびフレキシブル性の観点から、(メタ)アクリル酸イソボルニルがより好ましい。
その他モノマーは、モノマー(a-1)~(a-3)およびモノマー(a-5)以外のモノマーであり、アクリル系共重合体(A1)を構成するモノマー混合物は、モノマー(a-1)~(a-3)に加えて、さらにその他モノマーを含んでもよく、アクリル系共重合体(A2)を構成するモノマー混合物は、モノマー(a-5)に加えて、さらにモノマー(a-1)~(a-3)、およびその他モノマーを含んでもよい。
モノマー(a-1)を含有することで、粘着剤の応力緩和性が向上し、柔軟な粘着剤層が得られ、密着力を向上することができ、モノマー(a-2)を含有することで、粘着剤のゴム弾性が向上し、強靭な粘着剤層が得られ、フレキシブル性を向上することができる。
また、モノマー(a-3)を含有することで、粘着剤の凝集力が向上し、強靭な粘着剤層が得られ、接着力を向上することができる。
モノマー(a-5)を含有することで、粘着剤の凝集力が向上し、強靭な粘着剤層が得られ、接着力を向上することができる。
アクリル系共重合体(A1)および(A2)は、モノマー混合物を重合し、製造することができる。
重合温度は、60~120℃の沸点反応が好ましい。重合時間は、5~12時間程度が好ましい。
共重合体(A1)の重量平均分子量は、80万~180万が好ましく、100万~150万がより好ましい。80万~180万の範囲にあると凝集力がより向上し、耐湿熱性、耐熱性がより向上できる。
共重合体(A2)の重量平均分子量は、1万~30万が好ましく、1万~10万がより好ましい。1万~30万の範囲にあると応力緩和性がより向上し、耐湿熱性、耐熱性がより向上する。なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法により測定するポリスチレン換算の値である。
硬化剤(B)は、共重合体(A1)が有する水酸基および/または、カルボキシル基と反応することで、粘着剤層の凝集力が向上し、耐久性、耐汚染性がより向上する。
これらのうち、硬化剤(B)として、イソシアネート化合物を使用することで、接着性および、耐久性が向上できるために好ましい。
本実施形態のフレキシブルディスプレイ用粘着剤は、さらに有機シラン化合物を含有できる。有機シラン化合物は、第1の実施形態に記載のものが挙げられる。
フレキシブルディスプレイ用粘着剤の貯蔵弾性率および損失正接は、第1の実施形態と同様に、周波数1Hzの粘弾性測定により求められる。
フレキシブルディスプレイ用粘着剤は、-20℃、1Hzでの貯蔵弾性率(以下、G’(-20)と略記することがある)が、5×104~3×105Paであり、6×104~2×105Paであることがより好ましい。G’(-20)が5×104Pa以上であると、低温環境下での剛直性が向上し、屈曲性および巻き取り性が向上する。
フレキシブルディスプレイ用粘着剤は、-50℃、1Hzでの損失正接(以下、tanδ(-50)と略記することがある)が、0.5~3.0であり、1.0~2.5であることがより好ましい。tanδ(-50)が0.5以上であると、物理変形を加えられた際の、応力緩和性が向上し、屈曲性および巻き取り性が向上する。tanδ(-50)が3.0以下であると、物理変形を加えられた際の、剛直性が向上し、屈曲性および巻き取り性が向上する。
乾燥させた粘着剤を積層して厚み約1.0mmとしたものを測定用サンプルとした。
TA Insturument-Waters LL.C.社製「Discovery HR-2(DHR-2)」を用いて、以下の条件により、粘弾性測定を行うことにより、測定結果から、各温度における貯蔵弾性率および損失正接を読み取ることができる。
(測定条件)
変形モード:ねじり
測定周波数:1Hz
昇温速度:10℃/分
治具形状:パラレルプレート 8.0mmφ
法線荷重:1N
フレキシブルディスプレイ用粘着剤は、ゲル分率が55~90質量%であることが好ましく、60~80質量%がより好ましい。ゲル分率が55質量%以上であると、粘着剤の凝集力が向上し、強靭な粘着剤層が得られ、耐久性が向上し、90%質量以下であると、粘着剤の応力緩和性が向上し、柔軟な粘着剤層が得られ、密着力が向上する。
ゲル分率は、第1の実施形態と同様、酢酸エチル等の溶媒に対する不溶分として求めることができる。
本実施形態の粘着シートは、第1の実施形態と同様、光透過性可撓性基材と粘着剤層からなる積層体における、前記粘着剤層を形成するために用いられる粘着シートであり、すなわち、本実施形態の粘着シートは、光透過性可撓性基材を接合するために用いられる。
剥離フィルムとしては、特に制限されないが、例えば、透明プラスチック基材を好適に用いることができる。透明プラスチック基材の素材としては、第1の実施形態に記載のものが挙げられる。
本実施形態の粘着シートは、通常の粘着シートの製造方法に従って製造することができる。例えば、剥離フィルムの剥離処理面に、アクリル系共重合体(A1)と、アクリル系共重合体(A2)と、硬化剤(B)と、の混合物(以下、単に「粘着剤」と記述する場合がある。)を、乾燥後の厚さが所定の厚さとなるように直接塗工して粘着剤層を形成し、剥離フィルムを貼付する方法、または2枚の剥離フィルムの剥離処理面に、粘着剤を乾燥後の厚さが所定の厚さとなるように塗工して、2つの粘着剤層をそれぞれ形成した後、各粘着剤層を貼付する方法等により作製することができる。
本実施形態の積層体は、光透過性可撓性基材、粘着剤層、および偏光板を備え、粘着剤層は、本実施形態の粘着シートを用いて形成されてなる。
フレキシブルディスプレイは、本実施形態の積層体、および光学素子を備える。光学素子としては、特に限定されず、例えば、液晶素子、有機EL素子等が挙げられる。
例えば、図3において、本実施形態の粘着剤は、第1の粘着剤層1、および第2の粘着剤層5のいずれにも用いることができる。
一般に、第1の粘着剤層1と第2の粘着剤層5を比較した場合、粘着剤層に要求される要求品質は第1の粘着剤層1の方が要求は高く、本実施形態の粘着剤は、基材への密着性および、接着性が良好であることから、第1の粘着剤層1に用いられることが好ましい。このとき、第2の粘着剤層5を形成するための粘着剤は、本実施形態の粘着剤を用いてもよく、従来公知の粘着剤を用いてもよい。
前記アクリル系共重合体は、下記モノマー(a-1)~(a-3)の全てを含むモノマー混合物の共重合体であり、
下記、(1)~(7)の全てを満たし、さらに下記、(i)~(ii)いずれか又は両方を満たす、フレキシブルディスプレイ用粘着剤。
(a-1)炭素数6~10アルキル基を有する(メタ)アクリル酸分岐アルキルエステルモノマー
(a-2)炭素数12~20アルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(a-3)ヒドロキシ基を有するモノマーおよびカルボキシ基を有するモノマーからなる群から選択される1種類以上の極性基を有するモノマー
(1)-20℃、1Hzでの貯蔵弾性率が、5×104~3×105Pa
(2)25℃、1Hzでの貯蔵弾性率が、1×104~5×104Pa
(3)80℃、1Hzでの貯蔵弾性率が、5×103~3×104Pa
(4)200℃、1Hzでの貯蔵弾性率が、2×103~3×104Pa
(5)-50℃、1Hzでの損失正接が、0.5~3.0
(6)-20℃、1Hzでの損失正接が、0.2~1.0
(7)25℃、80℃、200℃、1Hzでの損失正接が、0.01~0.5
(i)前記アクリル系共重合体が下記モノマー(a-4)をさらに含む。
(ii)下記モノマー(a-5)を含む第2のアクリル系共重合体をさらに含む。
(a-4)炭素数1~4のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(a-5)シクロアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
前記接着剤は、アクリル系共重合体および硬化剤を含み、
前記アクリル系共重合体は、下記モノマー(a-1)~(a-4)の全てを含むモノマー混合物の共重合体であり、
下記、(1)~(7)の全てを満たす、接着剤の使用。
(a-1)炭素数6~10アルキル基を有する(メタ)アクリル酸分岐アルキルエステルモノマー
(a-2)炭素数12~20アルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(a-3)ヒドロキシ基を有するモノマーおよびカルボキシ基を有するモノマーからなる群から選択される1種類以上の極性基を有するモノマー
(a-4)炭素数1~4のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(1)-20℃、1Hzでの貯蔵弾性率が、5×104~3×105Pa
(2)25℃、1Hzでの貯蔵弾性率が、1×104~5×104Pa
(3)80℃、1Hzでの貯蔵弾性率が、5×103~3×104Pa
(4)200℃、1Hzでの貯蔵弾性率が、2×103~3×104Pa
(5)-50℃、1Hzでの損失正接が、0.5~3.0
(6)-20℃、1Hzでの損失正接が、0.2~1.0
(7)25℃、80℃、200℃、1Hzでの損失正接が、0.01~0.5
モノマー(a-1)を20~60質量%、
モノマー(a-2)を10~50質量%、
モノマー(a-3)を0.5~2.5質量%、および
モノマー(a-4)を5~20質量%、
を含む、前記接着剤の使用。
前記接着剤は、第1のアクリル系共重合体、第2のアクリル系共重合体(ただし、前記第1のアクリル系共重合体である場合を除く)、および硬化剤を含み、
前記第1のアクリル系共重合体は、下記モノマー(a-1)~(a-3)の全てを含むモノマー混合物の共重合体であり、
前記第2のアクリル系共重合体は、下記モノマー(a-5)を含むモノマー混合物の共重合体であり、
下記、(1)~(7)の全てを満たす、接着剤の使用。
(a-1)炭素数6~10のアルキル基を有する(メタ)アクリル酸分岐アルキルエステルモノマー
(a-2)炭素数12~20のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(a-3)ヒドロキシ基を有するモノマーおよびカルボキシ基を有するモノマーからなる群から選択される1種類以上の極性基を有するモノマー
(a-5)シクロアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(1)-20℃、1Hzでの貯蔵弾性率が、5×104~3×105Pa
(2)25℃、1Hzでの貯蔵弾性率が、1×104~5×104Pa
(3)80℃、1Hzでの貯蔵弾性率が、5×103~3×104Pa
(4)200℃、1Hzでの貯蔵弾性率が、2×103~3×104Pa
(5)-50℃、1Hzでの損失正接が、0.5~3.0
(6)-20℃、1Hzでの損失正接が、0.2~1.0
(7)25℃、80℃、200℃、1Hzでの損失正接が、0.01~0.5
モノマー(a-1)を25~80質量%
モノマー(a-2)を10~50質量%、および
モノマー(a-3)を0.5~2.5質量%
を含み、
前記第2のアクリル系共重合体は、モノマー混合物100質量%中に、
モノマー(a-5)を40~95質量%
を含む、前記接着剤の使用。
なお、共重合体の重量平均分子量の測定方法は、下記に示す通りである。
重量平均分子量(Mw)の測定は、島津製作所社製GPC「LC-GPCシステム」を用い、重量平均分子量(Mw)の決定は、分子量既知のポリスチレンを標準物質とした換算で行うことができる。
装置名:株式会社島津製作所製、LC-GPCシステム「Prominence」
カラム:東ソー株式会社製GMHXL 4本、東ソー株式会社製HXL-H 1本を連結した。
移動相溶媒 : テトラヒドロフラン
流量 : 1.0ml/分
カラム温度 : 40℃
<アクリル系共重合体の製造例>
(アクリル系共重合体(A-1))
撹拌機、温度計、還流冷却管、滴下装置、窒素導入管を備えた反応容器(以下、単に「反応容器」と記述する。)に、モノマー(a-1)として、アクリル酸2-エチルヘキシル(EHA)40部、モノマー(a-2)として、アクリル酸ドデシル(DOA)30部、モノマー(a-3)として、アクリル酸4-ヒドロキシブチル1部、モノマー(a-4)として、アクリル酸メチル(MA)4部、その他モノマーとして、アクリル酸オクチル25部、開始剤として、2,2'-アゾビスイソブチロニトリル(以下、単に「AIBN」と記述する。)0.2部を仕込み、この反応容器内の雰囲気を窒素ガスで置換した。その後、窒素雰囲気下で撹拌しながら、50℃まで加熱し反応を開始した。その後、反応溶液を50℃で4時間反応させた。反応終了後、冷却し、酢酸エチルで希釈して不揮発分30%、粘度8000mPa・sの共重合体(A-1)溶液を得た。得られた共重合体(A-1)の重量平均分子量は100万であった。
表1、2記載の組成および配合量(質量部)に変更した以外は、アクリル系共重合体(A-1)の製造と同様の方法で共重合体(A-2~A-15、A’-1~A’-5)を製造した。
(モノマー(a-1))
EHA:アクリル酸2-エチルヘキシル(炭素数8)
IOA:アクリル酸イソオクチル(炭素数8)
(モノマー(a-2))
DOA:アクリル酸ドデシル(炭素数12)
IKA:アクリル酸イコシル(炭素数20)
(モノマー(a-3))
HBA:アクリル酸4-ヒドロキシブチル
AA:アクリル酸
(モノマー(a-4))
MA:アクリル酸メチル(炭素数1)
EA:アクリル酸エチル(炭素数2)
(その他モノマー)
OA:アクリル酸オクチル(炭素数8、直鎖アルキル基を有する)
MEA:アクリル酸メトキシエチル(式(1)において、R1が水素原子、nが1のモノマー)
<粘着剤の調製>
アクリル系共重合体(A-1)不揮発分100部に対して、硬化剤(B)としてトリレンジイソシアネートのトリメチロールプロパンのアダクト体(B-1)0.5部、有機シラン化合物として3-グリシドキシプロピルトリメトキシシラン(S-1)0.1部、さらに不揮発分が20%となるように酢酸エチルを配合し撹拌して粘着剤を得た。
得られた粘着剤を、厚み50μmの剥離フィルム(ポリエチレンテレフタレート(PET)、「E7004」、シリコーン系剥離層、東洋紡株式会社製)上に、乾燥後の厚さが50μmになるように塗工し、110℃で3分間乾燥することで粘着剤層を形成した。次いで、この粘着剤層に、厚み38μmの剥離フィルム(ポリエチレンテレフタレート、「SP-PET3811」、シリコーン系剥離層、リンテック株式会社製)の片面を貼り合せ、「剥離性シート/粘着剤層/剥離性シート」の積層体を作製した。次いで、得られた積層体を温度25℃相対湿度55%の条件で1週間静置させて、粘着シートを得た。
表3~5に示す通り、共重合体および硬化剤の種類と配合量(質量部)を変更した以外は実施例1と同様にして、粘着シートを得た。
<硬化剤(B)>
B-1 : トリレンジイソシアネートのトリメチロールプロパンアダクト体
B-2 : ヘキサメチレンジイソシアネートのトリメチロールプロパンアダクト体
B-3 : キシリレンジイソシアネートのトリメチロールプロパンアダクト体
B-4 : N,N,N’,N’-テトラグリシジル-m-キシリレンジアミン
B-5 : 4,4’-ビス(エチレンイミノカルボニルアミノ)ジフェニルメタン
<有機シラン化合物>
S-1 : 3-グリシドキシプロピルトリメトキシシラン
得られた粘着シートを用いて、ゲル分率、貯蔵弾性率、損失正接、および、以下の透明性、耐熱性、耐湿熱性、動的耐屈曲性、静的屈曲性を評価した。結果を表6、7に示す。
得られた粘着シートを、幅25mm×長さ100mmのサイズに切り出した。切り出した粘着シートの一方の剥離フィルムを剥がし、あらかじめ質量を測定しておいた、幅50mm×長さ120mmの200メッシュに貼着した。次いで、他方の剥離フィルムを剥がし、粘着剤が露出しないよう、メッシュを粘着剤が内側になるよう折りたたんだメッシュで包まれた粘着剤を、約50mLの酢酸エチル中に、23℃で7日間浸漬し、粘着剤のゾル成分をメッシュ外へ溶出させた。浸漬後、メッシュで包まれた粘着剤を取出し、100℃で1時間乾燥させ、約20分間放冷した後、乾燥質量を測定した。粘着剤のゲル分率は、次式により算出した。
X=浸漬前の粘着剤層の質量(g)
Y=浸漬後の粘着剤層の質量(g)
TA Insturument-Waters LL.C.社製「Discovery HR-2(DHR-2)」を用い、温度分散測定を、周波数1Hz、昇温度10℃/分、冶具として8.0mmφを使用し、法線荷重1Nで測定した。得られた測定グラフから、-20℃、25℃、80℃、200℃での貯蔵弾性率、および、-50℃、-20℃、25℃、80℃、200℃での損失正接を読み取った。
試験用粘着シートを幅112mm×長さ200mm(9インチ型ディスプレイに相当)のサイズに切り出してPETフィルム/粘着剤層/剥離フィルムからなる試験用粘着シート1を作製した。
この試験用粘着シート1から剥離フィルムを剥がし、露出した粘着剤層を25℃、相対湿度50%雰囲気で無アルカリガラス板(EN-A1:AGC株式会社製)にラミネーターを用いて貼着し、HAZEを測定した。なお、HAZEは日本電色工業株式会社製Turbidimeter NDH5000Wを用いて測定した。評価基準は以下の通りである。
[評価基準]
A:HAZEが1.0未満(良好)。
B:HAZEが1.0以上(不良)。
試験用粘着シートを幅112mm×長さ200mm(9インチ型ディスプレイに相当)のサイズに切り出してPETフィルム/粘着剤層/剥離フィルムからなる試験用粘着シート2を作製した。
この試験用粘着シート2から剥離フィルムを剥がし、露出した粘着剤層を25℃、相対湿度50%雰囲気で偏光板(層構成:トリアセチルセルロースフィルム/ポリビニルアルコールフィルム/ シクロオレフィンフィルム)にラミネーターを用いて貼着し、PETフィルム/粘着剤層/偏光板からなる試験用積層体を得た。次いで、耐熱性試験として105℃の条件下に500時間放置し、25℃、相対湿度50%RH雰囲気にて冷却した後、気泡の発生および試験用積層体の浮きや剥がれを以下の条件で目視評価した。又、耐湿熱性の評価として、上記試験用積層体を60℃、相対湿度95%RH雰囲気で500時間放置し、25℃、相対湿度50%RH雰囲気にて冷却した後、気泡の発生および粘着シートの浮きおよび剥がれを以下の条件で目視評価した。耐熱性、耐湿熱性について、下記の3段階の評価基準に基づいて評価を行った。
[評価基準]
AA:気泡の発生、浮き・ハガレが全く認められず、実用上全く問題がない。
A:気泡の発生、浮き・ハガレがわずかに認められるが、実用上問題がない。
B:気泡の発生、浮き・ハガレが顕著に認められ、実用上問題がある。
別途作製した、試験用粘着シート2から剥離フィルムを剥がし、露出した粘着剤層を25℃、相対湿度50%雰囲気で偏光板(層構成:トリアセチルセルロースフィルム/ポリビニルアルコールフィルム/シクロオレフィンフィルム)にラミネーターを用いて貼着し、PETフィルム/粘着剤層/偏光板からなる試験用積層体を得た。次いで試験用積層体を、常態試験として25℃、相対湿度50%雰囲気にて耐屈曲性[1]、耐熱試験として85℃雰囲気下にて耐屈曲性[2]、また、耐湿熱試験として60℃、相対湿度95%RH雰囲気下にて耐屈曲性[3]、それぞれ折り曲げ試験機(ユアサシステム機器株式会社製)にて折り曲げた時の内径(直径)が6mmになるように条件設定し、折り曲げと180°開放とを1サイクルとして30万サイクル繰り返し行った。動的屈曲性は、試験後の外観を下記観点で評価した。
外観:試験用積層体の気泡の有無および粘着剤層の浮きおよび剥がれの有無を以下の条件で目視評価した。
[評価基準]
AA:気泡の発生、浮き・ハガレが全く認められず、実用上全く問題がない。
A:気泡の発生、浮き・ハガレがわずかに認められるが、実用上問題がない。
B:気泡の発生、浮き・ハガレが顕著に認められ、実用上問題がある。
別途作製した、試験用粘着シート2から剥離フィルムを剥がし、露出した粘着剤層を25℃、相対湿度50%RH雰囲気で偏光板(層構成:トリアセチルセルロースフィルム/ポリビニルアルコールフィルム/シクロオレフィンフィルム)にラミネーターを用いて貼着し、PETフィルム/粘着剤層/偏光板からなる試験用積層体を得た。次いで試験用積層体を、常態試験として25℃、相対湿度50%RH雰囲気にて耐屈曲性[1]、耐熱試験として85℃雰囲気下にて耐屈曲性[2]、また、耐湿熱試験として60℃、相対湿度95%RH雰囲気下にて耐屈曲性[3]、それぞれ面状体無負荷U字伸縮試験機により、試験片の偏光板側の面を内側として、曲げ半径3mm、曲げ角度180°の屈曲状態で保持して、240時間保持した。静的屈曲性は、試験後の外観を下記観点で評価した。
外観:試験用積層体の気泡の有無および粘着剤層の浮きおよび剥がれの有無を以下の条件で目視評価した。
[評価基準]
AA:気泡の発生、浮き・ハガレが全く認められず、実用上全く問題がない。
A:気泡の発生、浮き・ハガレがわずかに認められるが、実用上問題がない。
B:気泡の発生、浮き・ハガレが顕著に認められ、実用上問題がある。
別途作製した、試験用粘着シート2から剥離フィルムを剥がし、露出した粘着剤層を25℃、相対湿度50%RH雰囲気で偏光板(層構成:トリアセチルセルロースフィルム/ポリビニルアルコールフィルム/シクロオレフィンフィルム)にラミネーターを用いて貼着し、PETフィルム/粘着剤層/偏光板からなる試験用積層体を得た。次いで、試験用積層体を半径3mmの金属棒に、試験片のPET側の面を内側として、長辺方向に巻き取り、ロール状にした後、タコ糸で3カ所結んで固定した。巻き取り試験として、ロール状の試験用積層体を25℃、相対湿度50%RH雰囲気に240時間保持した。静的屈曲性は、試験後の外観を下記観点で評価した。
外観:試験用積層体の気泡の有無および粘着剤層の浮きおよび剥がれの有無を以下の条件で目視評価した。
[評価基準]
AA:気泡の発生、浮き・ハガレが全く認められず、実用上全く問題がない。
A:気泡の発生、浮き・ハガレがわずかに認められるが、実用上問題がない。
B:気泡の発生、浮き・ハガレが顕著に認められ、実用上問題がある。
[A];PETフィルム/粘着剤層/ガラス
[B];PETフィルム/粘着剤層/偏光板
試験条件
耐屈曲性[1];25℃、相対湿度50%雰囲気
耐屈曲性[2];85℃雰囲気
耐屈曲性[3];60℃、相対湿度95%雰囲気
一方、比較例1~10の粘着シートは、前記特性の全てを満たすことはできなかった。
<アクリル系共重合体の製造例>
(アクリル系共重合体(A1-1))
撹拌機、温度計、還流冷却管、滴下装置、窒素導入管を備えた反応容器(以下、単に「反応容器」と記述する。)に、モノマー(a-1)として、アクリル酸2-エチルヘキシル(EHA)20部、モノマー(a-2)として、アクリル酸ドデシル(DOA)30部、モノマー(a-3)として、アクリル酸4-ヒドロキシブチル1部、その他モノマーとして、アクリル酸ブチル49部、開始剤として、2,2'-アゾビスイソブチロニトリル(以下、単に「AIBN」と記述する。)0.2部を仕込み、この反応容器内の雰囲気を窒素ガスで置換した。その後、窒素雰囲気下で撹拌しながら、50℃まで加熱し反応を開始した。その後、反応溶液を50℃で4時間反応させた。反応終了後、冷却し、酢酸エチルで希釈して不揮発分30%、粘度7000mPa・sの共重合体(A-1)溶液を得た。得られた共重合体(A-1)の重量平均分子量は120万であった。
表8、9記載の組成および配合量(質量部)に変更した以外は、アクリル系共重合体(A1-1)の製造と同様の方法で共重合体(A1-2~A1-12)を合成した。
撹拌機、温度計、還流冷却管、滴下装置、窒素導入管を備えた反応容器(以下、単に「反応容器」と記述する。)に、モノマー(a-5)として、アクリル酸シクロヘキシル(CHA)35部、モノマー(a-2)として、アクリル酸2-エチルヘキシル(EHA)65部、開始剤として、AIBN2部を仕込み、この反応容器内の雰囲気を窒素ガスで置換した。その後、窒素雰囲気下で撹拌しながら、50℃まで加熱し反応を開始した。その後、反応溶液を50℃で4時間反応させた。反応終了後、冷却し、酢酸エチルで希釈して不揮発分30%、粘度100mPa・sの共重合体(A2-1)溶液を得た。得られた共重合体(A2-1)の重量平均分子量は2万であった。
表9記載の組成および配合量(質量部)に変更した以外は、アクリル系共重合体(A2-1)の製造と同様の方法で共重合体(A2-2~A2-4)を合成した。
(モノマー(a-1))
EHA:アクリル酸2-エチルヘキシル(炭素数8)
IOA:アクリル酸イソオクチル(炭素数8)
(モノマー(a-2))
DOA:アクリル酸ドデシル(炭素数12)
IKA:アクリル酸イコシル(炭素数20)
(モノマー(a-3))
HBA:アクリル酸4-ヒドロキシブチル
AA:アクリル酸
(モノマー(a-5))
CHA:アクリル酸シクロヘキシル(脂環式)
IBXA:アクリル酸イソボルニル(脂環式)
(その他モノマー)
BA:アクリル酸ブチル
MEA:アクリル酸メトキシエチル(式(1)において、R1が水素原子、nが1のモノマー)
<粘着剤の調製>
アクリル系共重合体(A1-1)不揮発分100部に対して、アクリル系共重合体(A2-1)5部、硬化剤(B)としてトリレンジイソシアネートのトリメチロールプロパンのアダクト体(B-1)0.5部、有機シラン化合物として3-グリシドキシプロピルトリメトキシシラン(S-1)0.1部、さらに不揮発分が20%となるように酢酸エチルを配合し撹拌して粘着剤を得た。
得られた粘着剤を、厚み50μmの剥離フィルム(ポリエチレンテレフタレート(PET)、「E7004」、シリコーン系剥離層、東洋紡株式会社製)上に、乾燥後の厚さが50μmになるように塗工し、110℃で3分間乾燥することで粘着剤層を形成した。次いで、この粘着剤層に、厚み38μmの剥離フィルム(ポリエチレンテレフタレート、「SP-PET3811」、シリコーン系剥離層、リンテック株式会社製)の片面を貼り合せ、「剥離性シート/粘着剤層/剥離性シート」の積層体を作製した。次いで、得られた積層体を温度25℃相対湿度55%の条件で1週間静置させて、粘着シートを得た。
表10~12に示す通り、共重合体および硬化剤の種類と配合量(質量部)を変更した以外は実施例1Aと同様にして、粘着シートを得た。
<硬化剤(B)>
B-1 : トリレンジイソシアネートのトリメチロールプロパンアダクト体
B-2 : ヘキサメチレンジイソシアネートのトリメチロールプロパンアダクト体
B-3 : キシリレンジイソシアネートのトリメチロールプロパンアダクト体
B-4 : N,N,N’,N’-テトラグリシジル-m-キシリレンジアミン
B-5 : 4,4’-ビス(エチレンイミノカルボニルアミノ)ジフェニルメタン
<有機シラン化合物>
S-1 : 3-グリシドキシプロピルトリメトキシシラン
得られた粘着シートを用いて、ゲル分率、貯蔵弾性率、損失正接、および、以下の透明性、耐熱性、耐湿熱性、動的耐屈曲性、静的屈曲性を評価した。結果を表13、14に示す。
得られた粘着シートを、幅25mm×長さ100mmのサイズに切り出した。切り出した粘着シートの一方の剥離フィルムを剥がし、あらかじめ質量を測定しておいた、幅50mm×長さ120mmの200メッシュに貼着した。次いで、他方の剥離フィルムを剥がし、粘着剤が露出しないよう、メッシュを粘着剤が内側になるよう折りたたんだメッシュで包まれた粘着剤を、約50mLの酢酸エチル中に、23℃で7日間浸漬し、粘着剤のゾル成分をメッシュ外へ溶出させた。浸漬後、メッシュで包まれた粘着剤を取出し、100℃で1時間乾燥させ、約20分間放冷した後、乾燥質量を測定した。粘着剤のゲル分率は、次式により算出した。
X=浸漬前の粘着剤層の質量(g)
Y=浸漬後の粘着剤層の質量(g)
TA Insturument-Waters LL.C.社製「Discovery HR-2(DHR-2)」を用い、温度分散測定を、周波数1Hz、昇温度10℃/分、冶具として8.0mmφを使用し、法線荷重1Nで測定した。得られた測定グラフから、-20℃、25℃、80℃、200℃での貯蔵弾性率、および、-50℃、-20℃、25℃、80℃、200℃での損失正接を読み取った。
試験用粘着シートを幅112mm×長さ200mm(9インチ型ディスプレイに相当)のサイズに切り出してPETフィルム/粘着剤層/剥離フィルムからなる試験用粘着シート1を作製した。
この試験用粘着シート1から剥離フィルムを剥がし、露出した粘着剤層を25℃、相対湿度50%雰囲気で無アルカリガラス板(EN-A1:AGC株式会社製)にラミネーターを用いて貼着し、HAZEを測定した。なお、HAZEは日本電色工業株式会社製Turbidimeter NDH5000Wを用いて測定した。評価基準は以下の通りである。
[評価基準]
A:HAZEが1.0未満(良好)。
B:HAZEが1.0以上(不良)。
試験用粘着シートを幅112mm×長さ200mm(9インチ型ディスプレイに相当)のサイズに切り出してPETフィルム/粘着剤層/剥離フィルムからなる試験用粘着シート2を作製した。
この試験用粘着シート2から剥離フィルムを剥がし、露出した粘着剤層を25℃、相対湿度50%雰囲気で偏光板(層構成:トリアセチルセルロースフィルム/ポリビニルアルコールフィルム/ シクロオレフィンフィルム)にラミネーターを用いて貼着し、PETフィルム/粘着剤層/偏光板からなる試験用積層体を得た。次いで、耐熱性試験として105℃の条件下に500時間放置し、25℃、相対湿度50%RH雰囲気にて冷却した後、気泡の発生および試験用積層体の浮きや剥がれを以下の条件で目視評価した。又、耐湿熱性の評価として、上記試験用積層体を60℃、相対湿度95%RH雰囲気で500時間放置し、25℃、相対湿度50%RH雰囲気にて冷却した後、気泡の発生および粘着シートの浮きおよび剥がれを以下の条件で目視評価した。耐熱性、耐湿熱性について、下記の3段階の評価基準に基づいて評価を行った。
[評価基準]
AA:気泡の発生、浮き・ハガレが全く認められず、実用上全く問題がない。
A:気泡の発生、浮き・ハガレがわずかに認められるが、実用上問題がない。
B:気泡の発生、浮き・ハガレが顕著に認められ、実用上問題がある。
別途作製した、試験用粘着シート2から剥離フィルムを剥がし、露出した粘着剤層を25℃、相対湿度50%雰囲気で偏光板(層構成:トリアセチルセルロースフィルム/ポリビニルアルコールフィルム/シクロオレフィンフィルム)にラミネーターを用いて貼着し、PETフィルム/粘着剤層/偏光板からなる試験用積層体を得た。次いで試験用積層体を、常態試験として25℃、相対湿度50%雰囲気にて耐屈曲性[1]、耐熱試験として85℃雰囲気下にて耐屈曲性[2]、また、耐湿熱試験として60℃、相対湿度95%RH雰囲気下にて耐屈曲性[3]、それぞれ折り曲げ試験機(ユアサシステム機器株式会社製)にて折り曲げた時の内径(直径)が6mmになるように条件設定し、折り曲げと180°開放とを1サイクルとして30万サイクル繰り返し行った。動的屈曲性は、試験後の外観を下記観点で評価した。
外観:試験用積層体の気泡の有無および粘着剤層の浮きおよび剥がれの有無を以下の条件で目視評価した。
[評価基準]
AA:気泡の発生、浮き・ハガレが全く認められず、実用上全く問題がない。
A:気泡の発生、浮き・ハガレがわずかに認められるが、実用上問題がない。
B:気泡の発生、浮き・ハガレが顕著に認められ、実用上問題がある。
別途作製した、試験用粘着シート2から剥離フィルムを剥がし、露出した粘着剤層を25℃、相対湿度50%RH雰囲気で偏光板(層構成:トリアセチルセルロースフィルム/ポリビニルアルコールフィルム/シクロオレフィンフィルム)にラミネーターを用いて貼着し、PETフィルム/粘着剤層/偏光板からなる試験用積層体を得た。次いで試験用積層体を、常態試験として25℃、相対湿度50%RH雰囲気にて耐屈曲性[1]、耐熱試験として85℃雰囲気下にて耐屈曲性[2]、また、耐湿熱試験として60℃、相対湿度95%RH雰囲気下にて耐屈曲性[3]、それぞれ面状体無負荷U字伸縮試験機により、試験片の偏光板側の面を内側として、曲げ半径3mm、曲げ角度180°の屈曲状態で保持して、240時間保持した。静的屈曲性は、試験後の外観を下記観点で評価した。
外観:試験用積層体の気泡の有無および粘着剤層の浮きおよび剥がれの有無を以下の条件で目視評価した。
[評価基準]
AA:気泡の発生、浮き・ハガレが全く認められず、実用上全く問題がない。
A:気泡の発生、浮き・ハガレがわずかに認められるが、実用上問題がない。
B:気泡の発生、浮き・ハガレが顕著に認められ、実用上問題がある。
別途作製した、試験用粘着シート2から剥離フィルムを剥がし、露出した粘着剤層を25℃、相対湿度50%RH雰囲気で偏光板(層構成:トリアセチルセルロースフィルム/ポリビニルアルコールフィルム/シクロオレフィンフィルム)にラミネーターを用いて貼着し、PETフィルム/粘着剤層/偏光板からなる試験用積層体を得た。次いで、試験用積層体を半径3mmの金属棒に、試験片のPET側の面を内側として、長辺方向に巻き取り、ロール状にした後、タコ糸で3カ所結んで固定した。巻き取り試験として、ロール状の試験用積層体を25℃、相対湿度50%RH雰囲気に240時間保持した。静的屈曲性は、試験後の外観を下記観点で評価した。
外観:試験用積層体の気泡の有無および粘着剤層の浮きおよび剥がれの有無を以下の条件で目視評価した。
[評価基準]
AA:気泡の発生、浮き・ハガレが全く認められず、実用上全く問題がない。
A:気泡の発生、浮き・ハガレがわずかに認められるが、実用上問題がない。
B:気泡の発生、浮き・ハガレが顕著に認められ、実用上問題がある。
[A];PETフィルム/粘着剤層/ガラス
[B];PETフィルム/粘着剤層/偏光板
試験条件
耐屈曲性[1];25℃、相対湿度50%雰囲気
耐屈曲性[2];85℃雰囲気
耐屈曲性[3];60℃、相対湿度95%雰囲気
一方、比較例1A~4Aの粘着シートは、前記特性の全てを満たすことはできなかった。
2 剥離フィルム
3 光透過性可撓性基材(カバーパネル)
4 偏光板
5 第2の粘着剤層
6 バリア層
7 有機EL層
8 支持体
9 有機ELセル
Claims (11)
- アクリル系共重合体および硬化剤を含み、
前記アクリル系共重合体は、下記モノマー(a-1)~(a-4)の全てを含むモノマー混合物の共重合体であり、
下記、(1)~(7)の全てを満たす、フレキシブルディスプレイ用粘着剤。
(a-1)炭素数6~10アルキル基を有する(メタ)アクリル酸分岐アルキルエステルモノマー
(a-2)炭素数12~20アルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(a-3)ヒドロキシ基を有するモノマーおよびカルボキシ基を有するモノマーからなる群から選択される1種類以上の極性基を有するモノマー
(a-4)炭素数1~4のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(1)-20℃、1Hzでの貯蔵弾性率が、5×104~3×105Pa
(2)25℃、1Hzでの貯蔵弾性率が、1×104~5×104Pa
(3)80℃、1Hzでの貯蔵弾性率が、5×103~3×104Pa
(4)200℃、1Hzでの貯蔵弾性率が、2×103~3×104Pa
(5)-50℃、1Hzでの損失正接が、0.5~3.0
(6)-20℃、1Hzでの損失正接が、0.2~1.0
(7)25℃、80℃、200℃、1Hzでの損失正接が、0.01~0.5 - 前記アクリル系共重合体は、モノマー混合物100質量%中に、
モノマー(a-1)を20~60質量%、
モノマー(a-2)を10~50質量%、
モノマー(a-3)を0.5~2.5質量%、および
モノマー(a-4)を5~20質量%、
を含む、請求項1記載のフレキシブルディスプレイ用粘着剤。 - 第1のアクリル系共重合体、第2のアクリル系共重合体(ただし、前記第1のアクリル系共重合体である場合を除く)、および硬化剤を含み、
前記第1のアクリル系共重合体は、下記モノマー(a-1)~(a-3)の全てを含むモノマー混合物の共重合体であり、
前記第2のアクリル系共重合体は、下記モノマー(a-5)を含むモノマー混合物の共重合体であり、
下記、(1)~(7)の全てを満たす、フレキシブルディスプレイ用粘着剤。
(a-1)炭素数6~10のアルキル基を有する(メタ)アクリル酸分岐アルキルエステルモノマー
(a-2)炭素数12~20のアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(a-3)ヒドロキシ基を有するモノマーおよびカルボキシ基を有するモノマーからなる群から選択される1種類以上の極性基を有するモノマー
(a-5)シクロアルキル基を有する(メタ)アクリル酸アルキルエステルモノマー
(1)-20℃、1Hzでの貯蔵弾性率が、5×104~3×105Pa
(2)25℃、1Hzでの貯蔵弾性率が、1×104~5×104Pa
(3)80℃、1Hzでの貯蔵弾性率が、5×103~3×104Pa
(4)200℃、1Hzでの貯蔵弾性率が、2×103~3×104Pa
(5)-50℃、1Hzでの損失正接が、0.5~3.0
(6)-20℃、1Hzでの損失正接が、0.2~1.0
(7)25℃、80℃、200℃、1Hzでの損失正接が、0.01~0.5 - 前記第1のアクリル系共重合体は、モノマー混合物100質量%中に、
モノマー(a-1)を25~80質量%
モノマー(a-2)を10~50質量%、および
モノマー(a-3)を0.5~2.5質量%
を含み、
前記第2のアクリル系共重合体は、モノマー混合物100質量%中に、
モノマー(a-5)を40~95質量%
を含む、請求項3記載のフレキシブルディスプレイ用粘着剤。 - 前記第1のアクリル系共重合体100質量部に対し、前記第2のアクリル系共重合体を4~40質量部含む、請求項3または4記載のフレキシブルディスプレイ用粘着剤。
- ゲル分率が55~90質量%である、請求項1~5いずれか1項に記載のフレキシブルディスプレイ用粘着剤。
- 前記モノマー(a-2)は、(メタ)アクリル酸ドデシルを含む、請求項1~6いずれか1項に記載のフレキシブルディスプレイ用粘着剤。
- 前記硬化剤がイソシアネート系化合物を含む、請求項1~7いずれか1項に記載のフレキシブルディスプレイ用粘着剤。
- 請求項1~8いずれか1項に記載のフレキシブルディスプレイ用粘着剤の硬化物である粘着剤層を備えた、粘着シート。
- 光透過性可撓性基材、粘着剤層、および偏光板を備え、前記粘着剤層は、請求項1~8いずれか1項に記載のフレキシブルディスプレイ用粘着剤の硬化物である、積層体。
- 請求項10記載の積層体、および光学素子を備える、フレキシブルディスプレイ。
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JP7464194B1 (ja) | 2022-12-23 | 2024-04-09 | artience株式会社 | 粘着剤層、それを用いた粘着シート、積層体及びフレキシブル画像表示装置 |
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JP2019218470A (ja) * | 2018-06-20 | 2019-12-26 | 東洋インキScホールディングス株式会社 | 粘着剤溶液および粘着シート |
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JP2021195552A (ja) * | 2020-06-15 | 2021-12-27 | 日東電工株式会社 | フレキシブル画像表示装置内の積層体に用いる粘着シート、フレキシブル画像表示装置に用いる積層体、及びフレキシブル画像表示装置 |
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CN113242790A (zh) | 2018-12-14 | 2021-08-10 | 三菱化学株式会社 | 粘合剂树脂组合物、粘合剂树脂固化物、粘合片及图像显示装置层叠体 |
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JP2018168305A (ja) * | 2017-03-30 | 2018-11-01 | リンテック株式会社 | 粘着シート、積層体、及びデバイス |
JP2019108502A (ja) * | 2017-12-19 | 2019-07-04 | リンテック株式会社 | 繰り返し屈曲デバイス用粘着剤、粘着シート、繰り返し屈曲積層部材および繰り返し屈曲デバイス |
JP2019218470A (ja) * | 2018-06-20 | 2019-12-26 | 東洋インキScホールディングス株式会社 | 粘着剤溶液および粘着シート |
JP2020076069A (ja) * | 2018-10-15 | 2020-05-21 | 大塚化学株式会社 | 粘着フィルムおよび表面保護フィルム |
JP2020122140A (ja) * | 2019-01-30 | 2020-08-13 | 日東電工株式会社 | 粘着シート、粘着層付き光学フィルム、積層体、および画像表示装置 |
JP2021195552A (ja) * | 2020-06-15 | 2021-12-27 | 日東電工株式会社 | フレキシブル画像表示装置内の積層体に用いる粘着シート、フレキシブル画像表示装置に用いる積層体、及びフレキシブル画像表示装置 |
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