WO2018174012A1 - 光学積層体 - Google Patents
光学積層体 Download PDFInfo
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- WO2018174012A1 WO2018174012A1 PCT/JP2018/010830 JP2018010830W WO2018174012A1 WO 2018174012 A1 WO2018174012 A1 WO 2018174012A1 JP 2018010830 W JP2018010830 W JP 2018010830W WO 2018174012 A1 WO2018174012 A1 WO 2018174012A1
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- WIPO (PCT)
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- meth
- sensitive adhesive
- optical laminate
- acrylate
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- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000012192 staining solution Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 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
- 150000004072 triols Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- C09J175/02—Polyureas
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
Definitions
- the present invention relates to an optical laminate.
- an image display device is manufactured by bonding a resin film including a polarizing plate to a substrate of a display element via an adhesive, and then further bonding glass on the resin film via an adhesive or an adhesive. .
- a bonding defect misalignment of bonding position, entrapment of foreign matter, etc.
- the adhesive or adhesive between the glass and the resin film is frozen and cut. Then, the resin film is often peeled from the substrate of the display element.
- the operation is complicated and complicated, resulting in a problem that the productivity of the image display device is deteriorated.
- Patent Document 1 An optical laminated body made of thinner glass
- the present invention has been made in order to solve the above-described conventional problems, and an object of the present invention is to provide an optical laminate having excellent reworkability while being provided with a glass film.
- the optical layered body of the present invention includes a glass film, a polarizer, and a pressure-sensitive adhesive layer in this order, and the adhesive force to the glass plate is 5 N / 25 mm or less.
- the pressure-sensitive adhesive layer has a thickness of 5 ⁇ m to 100 ⁇ m.
- the glass film has a thickness of 20 ⁇ m to 200 ⁇ m.
- the pressure-sensitive adhesive layer contains a (meth) acrylic pressure-sensitive adhesive.
- the pressure-sensitive adhesive layer contains a urethane-based pressure-sensitive adhesive.
- an image display device is provided.
- the image display device includes the optical laminate.
- the image display device includes the optical layered body on the outermost side on the viewing side.
- the optical laminate 100 includes a glass film 10, a polarizer 20, and an adhesive layer 30 in this order.
- the optical laminate 100 may further include a protective film 40 that protects the polarizer 20 between the glass film 10 and the polarizer 20 as necessary.
- a protective film between the polarizer 20 and the adhesive layer 30 as needed.
- the glass film 10, the polarizer 20, and the protective film 40 can be bonded together through any appropriate pressure-sensitive adhesive or adhesive.
- the optical laminated body 100 of the present invention includes the glass film 10, the hardness is high. Moreover, the optical laminated body 100 of this invention can prevent the damage of the glass film 10 by providing the polarizer 20 on the one side of the glass film 10, and is excellent in impact resistance. In the present invention, since the impact applied to the surface of the glass film 10 (surface opposite to the polarizer) can be effectively released to the polarizer 20 side, the impact resistance is excellent as described above. Conceivable. Further, the glass film 10 has a function of protecting the polarizer 20. That is, in the present invention, the glass film 10 and the polarizer 20 protect each other. Therefore, it is possible to reduce the number of protective members, and a lightweight and thin optical laminate can be obtained.
- the glass film 10 has high gas barrier property, deterioration of the polarizer 20 is prevented. Furthermore, since the glass film 10 has a small dimensional change, the expansion or contraction of the optical laminate 100 of the present invention is suppressed. As a result, it is possible to obtain the optical layered body 100 that has high durability and is prevented from peeling or floating.
- the adhesive strength of the optical laminate of the present invention to the glass plate is preferably 5 N / 25 mm or less, more preferably 3 N / 25 mm or less, and even more preferably 1.5 N / 25 mm or less.
- the adhesive strength is determined by bonding the optical layer of the optical laminate to the glass plate, and then peeling the optical laminate at a peel angle of 90 ° and a peel rate in an environment of a temperature of 23 ° C./humidity of 55%. Measured by peeling at 300 mm / min. A detailed measurement method will be described later.
- the optical laminate of the present invention is excellent in reworkability because the adhesive strength to the glass plate is in the above range. More specifically, when the optical laminated body is bonded to an adherend (for example, a member constituting an image display device such as a display element substrate), any trouble (for example, misalignment, entrapment of foreign matter, etc.) If this occurs, the optical laminate needs to be peeled off. At this time, if the optical laminate has an adhesive strength to the glass plate within the above range, the glass film is prevented from being broken and easily peeled off from the adherend. can do.
- an adherend for example, a member constituting an image display device such as a display element substrate
- any trouble for example, misalignment, entrapment of foreign matter, etc.
- the lower limit value of the adhesive strength of the optical laminate of the present invention to the glass plate is preferably 0.005 N / 25 mm or more, more preferably 0.01 N / 25 mm or more, and further preferably 0.1 N / 25 mm or more. is there. Within such a range, problems such as peeling and floating can be prevented even under high heat and / or high humidity.
- the thickness of the optical laminate of the present invention is preferably 50 ⁇ m to 500 ⁇ m, more preferably 100 ⁇ m to 300 ⁇ m.
- the optical layered body of the present invention may further include other layers.
- other layers include an antireflection layer, an antiglare layer, an antistatic layer, and a conductive layer.
- a separator may be disposed on the surface of the pressure-sensitive adhesive layer. The separator can protect the pressure-sensitive adhesive layer until the optical laminate is put into practical use.
- the optical layered body of the present invention is suitably used for an image display device. More specifically, the optical layered body of the present invention can be used for a substrate of a display element of an image display device. In another aspect of the present invention, an image display device including the optical laminate is provided. In one embodiment, the optical layered body of the present invention may be arranged on the outermost side on the viewing side of the image display device. The optical layered body thus arranged can function as a front protective plate of the image display device.
- the glass film Any appropriate film can be adopted as the glass film.
- the glass film include soda-lime glass, borate glass, aluminosilicate glass, and quartz glass according to the classification according to the composition.
- category by an alkali component an alkali free glass and a low alkali glass are mentioned.
- the content of alkali metal components (for example, Na 2 O, K 2 O, Li 2 O) in the glass is preferably 15% by weight or less, and more preferably 10% by weight or less.
- the thickness of the glass film is preferably 20 ⁇ m to 200 ⁇ m, more preferably 50 ⁇ m to 150 ⁇ m. If it is such a range, the optical laminated body which is excellent in flexibility, and a glass film is hard to crack and is excellent in productivity can be obtained.
- the light transmittance at a wavelength of 550 nm of the glass film is preferably 85% or more.
- the refractive index of the glass film at a wavelength of 550 nm is preferably 1.4 to 1.65.
- the density of the glass film is preferably 2.3 g / cm 3 to 3.0 g / cm 3 , more preferably 2.3 g / cm 3 to 2.7 g / cm 3 . If it is a glass film of the said range, a lightweight optical laminated body will be obtained.
- the glass film is obtained by melting a mixture containing main raw materials such as silica and alumina, an antifoaming agent such as sodium nitrate and antimony oxide, and a reducing agent such as carbon at a temperature of 1400 ° C to 1600 ° C. Then, after forming into a thin plate shape, it is produced by cooling.
- the glass film forming method include a slot down draw method, a fusion method, and a float method.
- the glass film formed into a plate shape by these methods may be chemically polished with a solvent such as hydrofluoric acid, if necessary, in order to reduce the thickness or improve the smoothness.
- the thickness of the polarizer is not particularly limited, and an appropriate thickness can be adopted depending on the purpose.
- the thickness is typically about 1 ⁇ m to 80 ⁇ m.
- a thin polarizer is used, and the thickness of the polarizer is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, further preferably 10 ⁇ m or less, and particularly preferably 6 ⁇ m or less. It is. By using such a thin polarizer, a thin optical laminate can be obtained.
- the polarizer preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm.
- the single transmittance of the polarizer is preferably 40.0% or more, more preferably 41.0% or more, further preferably 42.0% or more, and particularly preferably 43.0% or more.
- the polarization degree of the polarizer is preferably 99.8% or more, more preferably 99.9% or more, and further preferably 99.95% or more.
- the polarizer is an iodine-based polarizer. More specifically, the polarizer may be composed of a polyvinyl alcohol resin (hereinafter referred to as “PVA resin”) film containing iodine.
- PVA resin polyvinyl alcohol resin
- any appropriate resin can be adopted as the PVA resin for forming the PVA resin film.
- Examples thereof include polyvinyl alcohol and ethylene-vinyl alcohol copolymer.
- Polyvinyl alcohol is obtained by saponifying polyvinyl acetate.
- the ethylene-vinyl alcohol copolymer can be obtained by saponifying an ethylene-vinyl acetate copolymer.
- the degree of saponification of the PVA resin is usually 85 mol% to 100 mol%, preferably 95.0 mol% to 99.95 mol%, more preferably 99.0 mol% to 99.93 mol%. It is.
- the degree of saponification can be determined according to JIS K 6726-1994. By using a PVA-based resin having such a saponification degree, a polarizer having excellent durability can be obtained. If the degree of saponification is too high, there is a risk of gelation.
- the average degree of polymerization of the PVA resin can be appropriately selected according to the purpose.
- the average degree of polymerization is usually 1000 to 10,000, preferably 1200 to 5000, and more preferably 1500 to 4500.
- the average degree of polymerization can be determined according to JIS K 6726-1994.
- unit the method of extending
- the production method (II) preferably, a laminate (i) having a resin base material and a polyvinyl alcohol resin layer formed on one side of the resin base material is stretched and dyed, A step of producing a polarizer.
- the laminate (i) can be formed by applying and drying a coating liquid containing a polyvinyl alcohol-based resin on a resin substrate.
- the laminate (i) may be formed by transferring a polyvinyl alcohol-based resin film onto a resin base material. Details of the production method (II) are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580, which is incorporated herein by reference.
- the protective film Any appropriate resin film may be employed as the protective film.
- the protective film forming material include polyester resins such as polyethylene terephthalate (PET), cellulose resins such as triacetyl cellulose (TAC), cycloolefin resins such as norbornene resins, and olefins such as polyethylene and polypropylene.
- polyester resins such as polyethylene terephthalate (PET)
- cellulose resins such as triacetyl cellulose (TAC)
- cycloolefin resins such as norbornene resins
- olefins such as polyethylene and polypropylene.
- resins and (meth) acrylic resins include resins and (meth) acrylic resins. Of these, polyethylene terephthalate (PET) is preferable.
- the “(meth) acrylic resin” refers to an acrylic resin and / or a methacrylic resin.
- a (meth) acrylic resin having a glutarimide structure is used as the (meth) acrylic resin.
- (meth) acrylic resins having a glutarimide structure include, for example, JP-A-2006-309033, JP-A-2006-317560, JP-A-2006-328329, and JP-A-2006-328329.
- the protective film and the polarizer are laminated via any appropriate adhesive layer.
- the resin base material used at the time of producing the polarizer can be peeled off before or after the protective film and the polarizer are laminated.
- the thickness of the protective film is preferably 5 ⁇ m to 55 ⁇ m, more preferably 10 ⁇ m to 50 ⁇ m, and still more preferably 15 ⁇ m to 45 ⁇ m.
- the thickness of the adhesive layer adhesive layer is preferably 5 [mu] m ⁇ 100 [mu] m, more preferably 10 [mu] m ⁇ 70 [mu] m. If it is in such a range, the adhesive strength is appropriately adjusted, the glass film is hardly broken at the time of peeling, it can be easily peeled off from the adherend, and the optical layer is excellent in the durability of the pressure-sensitive adhesive layer. You can get a body.
- the pressure-sensitive adhesive layer contains any appropriate pressure-sensitive adhesive as long as the effects of the present invention can be obtained.
- the pressure-sensitive adhesive layer contains a (meth) acrylic pressure-sensitive adhesive and / or a urethane pressure-sensitive adhesive.
- (meth) acrylic pressure-sensitive adhesive contains a (meth) acrylic polymer.
- the content ratio of the (meth) acrylic polymer in the (meth) acrylic pressure-sensitive adhesive is preferably 40% by weight to 99.9% by weight, more preferably 50% by weight to 99.5% by weight, Preferably, it is 60 to 99% by weight.
- (Meth) acrylic polymer is a polymer containing a (meth) acrylic monomer as a constituent monomer component. Only one type of (meth) acrylic polymer may be used, or two or more types may be used. Only one (meth) acrylic monomer may be used, or two or more may be used.
- the (meth) acrylic polymer preferably contains (meth) acrylic acid alkyl ester as a monomer component constituting the polymer.
- (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and hexyl.
- (meth) acrylic acid alkyl esters having an alkyl group having 4 to 13 carbon atoms are preferred, more preferably 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, and n-tridecyl (meth) acrylate. Only one (meth) acrylic acid alkyl ester may be used, or two or more may be used.
- the content ratio of the (meth) acrylic acid alkyl ester to the total monomer components (100 wt%) constituting the (meth) acrylic polymer is preferably 70 wt% to 98 wt%, more preferably 80 wt% to 98 wt%. % By weight, more preferably 85% by weight to 98% by weight, and particularly preferably 90% by weight to 98% by weight.
- the monomer component constituting the (meth) acrylic polymer may further contain a hydroxyl group-containing monomer.
- the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2- Examples thereof include hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. Only one kind of hydroxyl group-containing monomer may be used, or two or more kinds thereof may be used.
- the content ratio of the hydroxyl group-containing monomer to the total monomer component (100% by weight) constituting the (meth) acrylic polymer is preferably 0.1% by weight to 15% by weight, more preferably 0.5% by weight to It is 13% by weight, more preferably 0.5% by weight to 10% by weight, and particularly preferably 1% by weight to 8% by weight.
- the monomer component constituting the (meth) acrylic polymer contains, for example, a polyfunctional monomer from the viewpoint that a crosslinked structure can be introduced into the (meth) acrylic polymer and appropriate cohesive force can be obtained. May be.
- the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6 hexanediol di (meta).
- the content ratio of the polyfunctional monomer to the total monomer component (100 wt%) constituting the (meth) acrylic polymer is preferably 0.1 wt% to 30 wt%, more preferably 0.1 wt% to 10 wt%. % By weight. Within such a range, it is possible to obtain an optical laminate in which the adhesive strength is appropriately adjusted and the glass film is not particularly easily broken during peeling.
- the monomer component constituting the (meth) acrylic polymer may further contain other monomers.
- examples of other monomers include cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, vinyl ether monomers, and N-acryloylmorpholine. Is mentioned. Among these, a cyano group-containing monomer, a vinyl ester monomer, and an aromatic vinyl monomer are preferable from the viewpoint of improving cohesion and heat resistance.
- amide group-containing monomers imide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, vinyl ether monomers, and N-acryloylmorpholine are preferred. Only one type of other monomer may be used, or two or more types may be used.
- Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
- vinyl ester monomer examples include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate.
- aromatic vinyl monomer examples include styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene, and other substituted styrene.
- amide group-containing monomers include acrylamide, methacrylamide, diethyl acrylamide, N-vinyl pyrrolidone, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethyl acrylamide, N, N-diethyl methacryl.
- examples thereof include amide, N, N′-methylenebisacrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, and diacetone acrylamide.
- Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconimide.
- amino group-containing monomer examples include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like.
- epoxy group-containing monomer examples include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and allyl glycidyl ether.
- vinyl ether monomer examples include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.
- the content ratio of other monomers to the total monomer components (100% by weight) constituting the (meth) acrylic polymer is preferably 0 to 40% by weight, more preferably more than 0% by weight and 40% by weight or less. More preferably, it is more than 0% by weight and 35% by weight or less, and particularly preferably more than 0% by weight and 30% by weight or less.
- the monomer component constituting the (meth) acrylic polymer has a carboxyl group-containing monomer, a sulfo group-containing monomer, a phosphate group-containing monomer, and an acid anhydride group-containing from the viewpoint of suppressing an increase in adhesion to an adherend. It is preferable that no monomer is contained. That is, it is preferable that the other monomer does not include a carboxyl group-containing monomer, a sulfo group-containing monomer, a phosphate group-containing monomer, and an acid anhydride group-containing monomer.
- (Meth) acrylic polymer can be obtained by polymerizing monomer components constituting the (meth) acrylic polymer.
- the polymerization method include solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, photopolymerization (active energy ray polymerization), and the like. Among these, solution polymerization is preferable from the viewpoint of cost and productivity.
- the (meth) acrylic polymer to be obtained may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.
- the weight average molecular weight of the (meth) acrylic polymer is preferably 100,000 to 5,000,000, more preferably 200,000 to 4,000,000, and further preferably 300,000 to 3,000,000.
- the glass transition temperature (Tg) of the (meth) acrylic polymer is preferably 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower.
- Tg (° C.) is the glass transition temperature of the copolymer
- Wn is the weight fraction of each monomer
- Tgn (° C.) is the glass transition temperature of the homopolymer obtained from each monomer
- n is the type of each monomer. .
- the (meth) acrylic pressure-sensitive adhesive may contain a cross-linking agent from the viewpoint that an appropriate cohesive force can be obtained.
- the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent.
- an isocyanate type crosslinking agent and an epoxy type crosslinking agent are preferable in that the effects of the present invention can be sufficiently exhibited.
- One type of crosslinking agent may be sufficient and 2 or more types may be sufficient as it.
- isocyanate-based crosslinking agent examples include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, and 2,4-tolylene diene.
- lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate
- alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate
- 2,4-tolylene diene examples include 2,4-tolylene diene.
- Isocyanates aromatic isocyanates such as 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name “Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / Hexamethylene diisocyanate trimer adduct (trade name “Coronate HL” manufactured by Nippon Polyurethane Industry Co., Ltd.), Isocyanate of hexamethylene diisocyanate Rate body (trade name "Coronate HX” manufactured by Nippon Polyurethane Industry Co., Ltd.), and the like isocyanate adducts such as.
- epoxy crosslinking agent examples include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, and trimethylol.
- the amount of the crosslinking agent is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, with respect to 100 parts by weight of the (meth) acrylic polymer.
- the amount is preferably 0.1 to 8 parts by weight, particularly preferably 0.5 to 5 parts by weight.
- (Meth) acrylic pressure-sensitive adhesive may contain a crosslinking catalyst.
- the cross-linking catalyst include metal-based cross-linking catalysts (particularly tin-based cross-linking catalysts) such as tetra-n-butyl titanate, tetraisopropyl titanate, nasec ferric acid, butyl tin oxide, and dioctyl tin dilaurate. Only one type of crosslinking catalyst may be used, or two or more types may be used.
- the amount of the crosslinking catalyst is preferably 0.001 to 0.05 parts by weight, more preferably 0.003 to 0.04 parts by weight per 100 parts by weight of the (meth) acrylic polymer. More preferably, it is 0.005 to 0.03 parts by weight.
- (Meth) acrylic adhesive may contain a crosslinking retarder.
- the crosslinking retarder include ⁇ -ketoesters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, acetylacetone, 2,4-hexanedione, benzoylacetone, etc. ⁇ -diketone.
- acetylacetone is preferable in that the effects of the present invention can be sufficiently exhibited. Only one type of crosslinking retarder may be used, or two or more types may be used.
- the amount of the crosslinking retarder is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. More preferably, it is 0.1 to 3 parts by weight.
- the (meth) acrylic pressure-sensitive adhesive contains additives such as a plasticizer, an anti-aging agent, a colorant (such as a pigment and a dye), an antistatic agent, and a tackifying resin as long as the effects of the present invention are not impaired. Also good.
- the (meth) acrylic pressure-sensitive adhesive may contain any appropriate solvent.
- Urethane adhesive contains a polyurethane resin.
- the polyurethane resin content in the urethane pressure-sensitive adhesive is preferably 40% by weight to 99% by weight, more preferably 50% by weight to 95% by weight, and still more preferably 60% by weight to 90% by weight. is there.
- Only one type of polyurethane resin may be used, or two or more types may be used.
- the polyurethane resin can be obtained by reacting the polyol (A) with the polyfunctional isocyanate compound (B).
- polyol (A) As a polyol (A), only 1 type may be sufficient and 2 or more types may be sufficient.
- polyol (A) examples include polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and castor oil-based polyol.
- Polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.
- polyol component examples include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1 , 3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl -1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol and the like.
- the acid component examples include succinic acid, methyl succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, acid anhydrides thereof Etc.
- polyether polyols examples include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzenes (catechol, resorcin, hydroquinone, etc.), etc. And polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
- polycaprolactone polyol examples include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ⁇ -caprolactone and ⁇ -valerolactone.
- polycarbonate polyol examples include a polycarbonate polyol obtained by polycondensation reaction of the polyol component and phosgene; the polyol component, dimethyl carbonate, diethyl carbonate, diprovir carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, Polycarbonate polyol obtained by ester exchange condensation with carbonic acid diesters such as propylene carbonate, diphenyl carbonate and dibenzyl carbonate; copolymerized polycarbonate polyol obtained by using two or more of the above polyol components in combination; Polycarbonate polyol obtained by esterification reaction with a compound; the above-mentioned various polycarbonate polyols and a hydroxyl group-containing compound; Polycarbonate polyol obtained by etherification reaction; polycarbonate polyol obtained by transesterification of the various polycarbonate polyols and ester compounds; polycarbonate polyol obtained by trans
- castor oil-based polyol examples include castor oil-based polyol obtained by reacting castor oil fatty acid with the above polyol component. Specific examples include castor oil-based polyols obtained by reacting castor oil fatty acid with polypropylene glycol.
- a polyol (triol) having three OH groups is used as the polyol (A).
- triol an optical laminate can be obtained in which the adhesive force is appropriately adjusted and the glass film is hardly broken at the time of peeling.
- the content ratio of the polyol (triol) having 3 OH groups in the polyol (A) is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, and still more preferably. It is 80 to 100% by weight, more preferably 90 to 100% by weight, particularly preferably 95 to 100% by weight, and most preferably substantially 100% by weight.
- the polyol (A) preferably contains a polyol having a number average molecular weight Mn of 400 to 20000.
- the content ratio of the polyol having a number average molecular weight Mn of 400 to 20000 in the polyol (A) is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, and still more preferably. It is 90% to 100% by weight, particularly preferably 95% to 100% by weight, and most preferably substantially 100% by weight.
- a triol having a number average molecular weight Mn of 7000 to 20000 and a number average molecular weight Mn of 2000 to 6000 are used.
- a triol having a number average molecular weight Mn of 400 to 1900 more preferably a triol having a number average molecular weight Mn of 8000 to 15000, a triol having a number average molecular weight Mn of 2000 to 5000, and a number average molecular weight.
- a triol having a Mn of 500 to 1800 more preferably a triol having a number average molecular weight Mn of 8000 to 12000, a triol having a number average molecular weight Mn of 2000 to 4000, and a triol having a number average molecular weight Mn of 500 to 1500 And in combination.
- the adhesive strength is appropriately adjusted, and an optical laminate that is particularly difficult to break the glass film at the time of peeling can be obtained.
- 1 type of polyfunctional isocyanate compounds (B) may be sufficient, and 2 or more types may be sufficient as them.
- polyfunctional isocyanate compound (B) any suitable polyfunctional isocyanate compound that can be used for the urethanization reaction can be adopted.
- examples of such a polyfunctional isocyanate compound (B) include polyfunctional aliphatic isocyanate compounds, polyfunctional alicyclic isocyanate compounds, polyfunctional aromatic isocyanate compounds, and the like.
- polyfunctional aliphatic isocyanate compound examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4 Examples include 4-trimethylhexamethylene diisocyanate.
- polyfunctional alicyclic isocyanate compound examples include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, Examples include hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate.
- polyfunctional aromatic diisocyanate compound examples include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2 ′ monodiphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4 Examples include '-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, and xylylene diisocyanate.
- polyfunctional isocyanate compound (B) examples include trimethylolpropane adducts of various polyfunctional isocyanate compounds as described above, burettes reacted with water, and trimers having an isocyanurate ring. These may be used in combination.
- the equivalent ratio of the NCO group to the OH group is more than 1.0 and not more than 5.0 as the NCO group / OH group, preferably 1.1 to 5.0, more preferably 1.2 to 4.0, still more preferably 1.5 to 3.5, and particularly preferably 1.8 to 3.0.
- the polyurethane-based pressure-sensitive adhesive preferably contains a deterioration preventing agent such as an antioxidant, an ultraviolet absorber, and a light stabilizer. Only one type of deterioration preventing agent may be used, or two or more types may be used. As the deterioration preventing agent, an antioxidant is particularly preferable.
- the urethane-based pressure-sensitive adhesive can contain any appropriate other component as long as the effects of the present invention are not impaired.
- other components include other resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, and anti-aging agents.
- Urethane adhesive may contain a modified silicone oil.
- the content ratio is preferably 0.001 to 50 parts by weight, more preferably 0.01 parts by weight to 100 parts by weight of the polyurethane resin. 40 parts by weight, more preferably 0.01 parts by weight to 30 parts by weight, particularly preferably 0.01 parts by weight to 20 parts by weight, and most preferably 0.01 parts by weight to 10 parts by weight. .
- modified silicone oil any appropriate modified silicone oil can be adopted as long as the effects of the present invention are not impaired.
- modified silicone oil include modified silicone oil available from Shin-Etsu Chemical Co., Ltd.
- the modified silicone oil is preferably a polyether-modified silicone oil.
- the polyether-modified silicone oil include a side chain-type polyether-modified silicone oil and a both-end-type polyether-modified silicone oil.
- PET Amorphous polyethylene terephthalate (hereinafter also referred to as “PET”) (IPA copolymerized PET) film (thickness: 100 ⁇ m) having 7 mol% of isophthalic acid unit as a thermoplastic resin substrate. ) And the surface was subjected to corona treatment (58 W / m 2 / min).
- PET Amorphous polyethylene terephthalate
- acetoacetyl-modified PVA manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Gohsephimer Z200 (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%)
- a PVA added with 1 wt% (polymerization degree 4200, saponification degree 99.2%) was prepared, and a coating solution of PVA aqueous solution with a PVA resin of 5.5 wt% was prepared, and the film thickness after drying was 12 ⁇ m. And dried for 10 minutes by hot air drying in an atmosphere of 60 ° C. to prepare a laminate in which a PVA resin layer was provided on the substrate.
- this laminate was first stretched 1.8 times in air at 130 ° C. (air-assisted stretching) to produce a stretched laminate.
- a step of insolubilizing the PVA layer in which the PVA molecules contained in the stretched laminate were oriented was performed by immersing the stretched laminate in a boric acid insolubilized aqueous solution having a liquid temperature of 30 ° C. for 30 seconds.
- the boric acid insolubilized aqueous solution in this step had a boric acid content of 3 parts by weight with respect to 100 parts by weight of water.
- a colored laminate was produced by dyeing this stretched laminate.
- the stretched laminate is applied to a dye solution containing iodine and potassium iodide at a liquid temperature of 30 ° C. so that the single transmittance of the PVA layer constituting the finally produced polarizer is 40 to 44%.
- the PVA layer contained in the stretched laminate is dyed with iodine by immersing it in an arbitrary time.
- the staining solution was prepared using water as a solvent and an iodine concentration in the range of 0.1 to 0.4% by weight and a potassium iodide concentration in the range of 0.7 to 2.8% by weight.
- the concentration ratio of iodine and potassium iodide is 1 to 7.
- the colored laminated body was immersed in a 30 ° C.
- boric acid crosslinking aqueous solution for 60 seconds to perform a crosslinking treatment between PVA molecules of the PVA layer on which iodine was adsorbed.
- the boric acid crosslinking aqueous solution in this step had a boric acid content of 3 parts by weight with respect to 100 parts by weight of water and a potassium iodide content of 3 parts by weight with respect to 100 parts by weight of water.
- the obtained colored laminate was stretched in a boric acid aqueous solution at a stretching temperature of 70 ° C. and stretched 3.05 times in the same direction as the stretching in the air (boric acid-water stretching), and finally An optical film laminate having a draw ratio of 5.50 was obtained.
- the optical film laminate was removed from the boric acid aqueous solution, and the boric acid adhering to the surface of the PVA layer was washed with an aqueous solution having a potassium iodide content of 4 parts by weight with respect to 100 parts by weight of water.
- the washed optical film laminate was dried by a drying process using hot air at 60 ° C.
- the thickness of the polarizer A contained in the obtained optical film laminate was 5 ⁇ m.
- a (meth) acrylic polymer solution (A2) having a weight average molecular weight of 1,600,000.
- an isocyanate crosslinking agent manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Takenate D110N, trimethylolpropane xylylene diisocyanate
- a (meth) acrylic pressure-sensitive adhesive D was prepared by blending 1 part by weight of a polyether compound (manufactured by Asahi Glass Urethane Co., Ltd., trade name: Excestar 2420).
- Example 1 A glass film (manufactured by Nippon Electric Glass Co., Ltd., trade name: OA10, size: 400 mm ⁇ 40 mm, thickness: 100 ⁇ m), protective film (40 ⁇ m thick acrylic resin film), and polarizer A in this order are adhesives To obtain a laminate a.
- the (meth) acrylic adhesive A was applied to the silicone-treated surface of a polyethylene terephthalate film having a silicone treatment on one side, and heated at 110 ° C. for 3 minutes to form an adhesive layer A having a thickness of 25 ⁇ m.
- the pressure-sensitive adhesive layer A was transferred to the polarizer A side of the laminate a to obtain an optical laminate A.
- Example 2 (Production of optical laminate) A glass film (manufactured by Nippon Electric Glass Co., Ltd., trade name: OA10, size: 400 mm ⁇ 40 mm, thickness: 100 ⁇ m) and polarizer A were bonded together with an adhesive to obtain a laminate b.
- the (meth) acrylic adhesive A was applied to the silicone-treated surface of a polyethylene terephthalate film having a silicone treatment on one side, and heated at 110 ° C. for 3 minutes to form an adhesive layer A having a thickness of 25 ⁇ m.
- the pressure-sensitive adhesive layer A was transferred to the polarizer A side of the laminate b to obtain an optical laminate B.
- Example 3 Glass film (manufactured by Nippon Electric Glass Co., Ltd., trade name: OA10, size: 400 mm ⁇ 40 mm, thickness: 100 ⁇ m), protective film (40 ⁇ m thick acrylic resin film), polarizer B, protective film (thickness) 40 ⁇ m acrylic resin film) was laminated in this order via an adhesive to obtain a laminate c.
- the (meth) acrylic adhesive A was applied to the silicone-treated surface of a polyethylene terephthalate film having a silicone treatment on one side, and heated at 110 ° C. for 3 minutes to form an adhesive layer A having a thickness of 25 ⁇ m.
- the pressure-sensitive adhesive layer A was transferred to the polarizer B side of the laminate c to obtain an optical laminate C.
- Example 4 In the same manner as in Example 1, a laminate a was obtained.
- the (meth) acrylic adhesive B was applied to the silicone-treated surface of the polyethylene terephthalate film subjected to silicone treatment and heated at 110 ° C. for 3 minutes to form an adhesive layer B having a thickness of 12 ⁇ m.
- the pressure-sensitive adhesive layer B was transferred to the polarizer A side of the laminate a to obtain an optical laminate D.
- Example 5 In the same manner as in Example 1, a laminate a was obtained. Urethane pressure-sensitive adhesive C was applied to the silicone-treated surface of a polyethylene terephthalate film having a silicone treatment on one side, and heated at 110 ° C. for 3 minutes to form a pressure-sensitive adhesive layer C having a thickness of 25 ⁇ m. The pressure-sensitive adhesive layer C was transferred to the polarizer A side of the laminate a to obtain an optical laminate E.
- Example 6 In the same manner as in Example 1, a laminate a was obtained.
- the (meth) acrylic adhesive D was applied to the silicone-treated surface of the polyethylene terephthalate film subjected to silicone treatment, and heated at 110 ° C. for 3 minutes to form an adhesive layer D having a thickness of 25 ⁇ m.
- the pressure-sensitive adhesive layer D was transferred to the polarizer A side of the laminate a to obtain an optical laminate F.
- Example 7 In the same manner as in Example 1, a laminate a was obtained. (Meth) acrylic pressure-sensitive adhesive E was applied to the silicone-treated surface of a polyethylene terephthalate film subjected to silicone treatment, and heated at 110 ° C. for 3 minutes to form a pressure-sensitive adhesive layer E having a thickness of 50 ⁇ m. The pressure-sensitive adhesive layer E was transferred to the polarizer A side of the laminate a to obtain an optical laminate G.
- Example 1 In the same manner as in Example 1, a laminate a was obtained.
- the (meth) acrylic pressure-sensitive adhesive F was applied to a silicone-treated surface of a polyethylene terephthalate film subjected to silicone treatment, and heated at 110 ° C. for 3 minutes to form a pressure-sensitive adhesive layer F having a thickness of 25 ⁇ m.
- the pressure-sensitive adhesive layer F was transferred to the polarizer A side of the laminate a to obtain an optical laminate H.
- the optical laminate was cut into 150 mm ⁇ 25 mm, and attached to a non-alkali glass plate having a thickness of 0.7 mm (product name: EG-XG) using a laminator, and then 50 ° C. A sample for evaluation was produced by autoclaving at 5 atm for 15 minutes to ensure complete adhesion. Using the tensile tester (Autograph SHIMAZU AG-1 10KN), the optical laminate was removed from the glass plate using the tensile tester (autograph SHIMAZU AG-1 10KN) under the conditions of 23 ° C./humidity 55%, peeling angle 90 °, peeling speed 300 mm / min. It peeled and the adhesive force of the optical laminated body was measured. The measurement was sampled at an interval of 1 time / 0.5 s, and the average value was taken as the measurement value.
- the optical laminate was attached to non-alkali glass (trade name: EG-XG, manufactured by Corning) having a size of 15 inches (diagonal line) with a thickness of 0.7 mm using a laminator. Next, autoclaving was performed at 50 ° C. and 0.5 MPa for 15 minutes, and the optical laminate was brought into close contact with the acrylic-free glass to prepare a sample for evaluation. About the said sample for evaluation, the optical laminated body was peeled from the glass in the diagonal direction from one corner of the optical laminated body, and the crack of the glass film and the fracture
- ⁇ The optical laminate has slight cracks but can be easily reworked. There is no practical problem. (Triangle
- A No change in appearance such as foaming or peeling.
- ⁇ Slightly peeled off or foamed at the end, but no problem in practical use.
- ⁇ There is peeling or foaming at the end, but there is no practical problem unless it is a special use.
- X Remarkably peeled off at the end, causing practical problems.
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Abstract
Description
1つの実施形態においては、上記粘着剤層の厚みが、5μm~100μmである。
1つの実施形態においては、上記ガラスフィルムの厚みが、20μm~200μmである。
1つの実施形態においては、上記粘着剤層が、(メタ)アクリル系粘着剤を含む。
1つの実施形態においては、上記粘着剤層が、ウレタン系粘着剤を含む。
本発明の別の局面によれば、画像表示装置が提供される。この画像表示装置は、上記光学積層体を含む。
1つの実施形態においては、上記画像表示装置は、視認側における最外側に、前記光学積層体を備える。
図1は、本発明のひとつの実施形態による光学積層体の概略断面図である。この光学積層体100は、ガラスフィルム10と、偏光子20と、粘着剤層30とをこの順に備える。光学積層体100は、必要に応じて、ガラスフィルム10と偏光子20との間に、偏光子20を保護する保護フィルム40をさらに備えていてもよい。また、図示していないが、必要に応じて、偏光子20と粘着剤層30との間に保護フィルムを配置してもよい。ガラスフィルム10、偏光子20および保護フィルム40は、任意の適切な粘着剤または接着剤を介して貼り合わされ得る。
上記ガラスフィルムは、任意の適切なものが採用され得る。上記ガラスフィルムは、組成による分類によれば、例えば、ソーダ石灰ガラス、ホウ酸ガラス、アルミノ珪酸ガラス、石英ガラス等が挙げられる。また、アルカリ成分による分類によれば、無アルカリガラス、低アルカリガラスが挙げられる。上記ガラスのアルカリ金属成分(例えば、Na2O、K2O、Li2O)の含有量は、好ましくは15重量%以下であり、さらに好ましくは10重量%以下である。
C-1.偏光子
上記偏光子の厚みは特に制限されず、目的に応じて適切な厚みが採用され得る。当該厚みは、代表的には、1μm~80μm程度である。1つの実施形態においては、薄型の偏光子が用いられ、当該偏光子の厚みは、好ましくは20μm以下であり、より好ましくは15μm以下であり、さらに好ましくは10μm以下であり、特に好ましくは6μm以下である。このように薄い偏光子を用いることにより、薄型の光学積層体を得ることができる。
上記保護フィルムとしては、任意の適切な樹脂フィルムが採用され得る。保護フィルムの形成材料としては、例えば、ポリエチレンテレフタレート(PET)等のポリエステル系樹脂、トリアセチルセルロース(TAC)等のセルロース系樹脂、ノルボルネン系樹脂等のシクロオレフィン系樹脂、ポリエチレン、ポリプロピレン等のオレフィン系樹脂、(メタ)アクリル系樹脂等が挙げられる。なかでも好ましくは、ポリエチレンテレフタレート(PET)である。なお、「(メタ)アクリル系樹脂」とは、アクリル系樹脂および/またはメタクリル系樹脂をいう。
粘着剤層の厚みは、好ましくは5μm~100μmであり、より好ましくは10μm~70μmである。このような範囲であれば、接着力が適切に調整され、剥離時のガラスフィルムの破断が特に生じ難く、被着体から容易に剥離し得、かつ、粘着剤層の耐久性に優れる光学積層体を得ることができる。
(メタ)アクリル系粘着剤は(メタ)アクリル系ポリマーを含む。
1/(Tg+273)=Σ〔Wn/(Tgn+273)〕
式中、Tg(℃)は共重合体のガラス転移温度、Wnは各モノマーの重量分率、Tgn(℃)は各モノマーから得られるホモポリマーのガラス転移温度、nは各モノマーの種類を表す。
ウレタン系粘着剤はポリウレタン系樹脂を含む。
熱可塑性樹脂基材として、イソフタル酸ユニットを7モル%有するアモルファスのポリエチレンテレフタレート(以下、「PET」ともいう。)(IPA共重合PET)フィルム(厚み:100μm)を用意し、表面にコロナ処理(58W/m2/min)を施した。一方、アセトアセチル変性PVA(日本合成化学工業(株)製、商品名:ゴーセファイマーZ200(平均重合度:1200,ケン化度:98.5モル%,アセトアセチル化度:5モル%)を1wt%添加したPVA(重合度4200、ケン化度99.2%)を用意して、PVA系樹脂が5.5wt%であるPVA水溶液の塗工液を準備し、乾燥後の膜厚が12μmになるように塗工し、60℃の雰囲気下において熱風乾燥により10分間乾燥して、基材上にPVA系樹脂の層を設けた積層体を作製した。
次いで、この積層体をまず空気中130℃で1.8倍に自由端延伸して(空中補助延伸)、延伸積層体を生成した。次に、延伸積層体を液温30℃のホウ酸不溶化水溶液に30秒間浸漬することによって、延伸積層体に含まれるPVA分子が配向されたPVA層を不溶化する工程を行った。本工程のホウ酸不溶化水溶液は、ホウ酸含有量を水100重量部に対して3重量部とした。この延伸積層体を染色することによって着色積層体を生成した。着色積層体は、延伸積層体を液温30℃のヨウ素およびヨウ化カリウムを含む染色液に、最終的に生成される偏光子を構成するPVA層の単体透過率が40~44%になるように任意の時間、浸漬することによって、延伸積層体に含まれるPVA層をヨウ素により染色させたものである。本工程において、染色液は、水を溶媒として、ヨウ素濃度を0.1~0.4重量%の範囲内とし、ヨウ化カリウム濃度を0.7~2.8重量%の範囲内とした。ヨウ素とヨウ化カリウムの濃度の比は1対7である。次に、着色積層体を30℃のホウ酸架橋水溶液に60秒間浸漬することによって、ヨウ素を吸着させたPVA層のPVA分子同士に架橋処理を施す工程を行った。本工程のホウ酸架橋水溶液は、ホウ酸含有量を水100重量部に対して3重量部とし、ヨウ化カリウム含有量を水100重量部に対して3重量部とした。
さらに、得られた着色積層体をホウ酸水溶液中で延伸温度70℃として、先の空気中での延伸と同様の方向に3.05倍に延伸して(ホウ酸水中延伸)、最終的な延伸倍率は5.50倍である光学フィルム積層体を得た。光学フィルム積層体をホウ酸水溶液から取り出し、PVA層の表面に付着したホウ酸を、ヨウ化カリウム含有量が水100重量部に対して4重量部とした水溶液で洗浄した。洗浄された光学フィルム積層体を60℃の温風による乾燥工程によって乾燥した。得られた光学フィルム積層体に含まれる偏光子Aの厚みは5μmであった。
厚さ60μmのポリビニルアルコールフィルムを、速度比の異なるロール間において、30℃、0.3%濃度のヨウ素溶液中で1分間染色しながら、3倍まで延伸した。その後、60℃、4%濃度のホウ酸、10%濃度のヨウ化カリウムを含む水溶液中に0.5分間浸漬しながら総合延伸倍率が6倍まで延伸した。次いで、30℃、1.5%濃度のヨウ化カリウムを含む水溶液中に10秒間浸漬することで洗浄した後、50℃で4分間乾燥を行い、厚さ22μmの偏光子Bを得た。
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに2-エチルヘキシルアクリレート200重量部、2-ヒドロキシエチルアクリレート10重量部、重合開始剤として2,2’-アゾビスイソブチロニトリル0.4重量部、酢酸エチル312重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を65℃付近に保って約6時間重合反応を行い、重量平均分子量は50万の(メタ)アクリル系ポリマー溶液(A1)を調製した。
得られた(メタ)アクリル系ポリマー溶液(A1)(固形分100重量部)に、架橋剤としてヘキサメチレンジイソシアネートのイソシアヌレート体(日本ポリウレタン工業社製、商品名:コロネートHX)0.6重量部、架橋触媒としてジラウリン酸ジブチルスズ(1重量%酢酸エチル溶液)0.6重量部、シランカップリング剤として(信越化学工業(株)製、商品名:KBM403)0.1重量部を加えて25℃付近に保って約1分間混合撹拌を行い、(メタ)アクリル系粘着剤Aを調製した。
製造例3で作製した(メタ)アクリル系ポリマー溶液(A1)(固形分100重量部)に、架橋剤としてヘキサメチレンジイソシアネートのイソシアヌレート体(日本ポリウレタン工業社製、商品名:コロネートHX)1.0重量部、架橋触媒としてジラウリン酸ジブチルスズ(1重量%酢酸エチル溶液)0.6重量部、シランカップリング剤(信越化学工業(株)製、商品名:KBM403)0.1重量部を配合して、(メタ)アクリル系粘着剤Bを調製した。
ポリオール(A)として、トリオール(旭硝子株式会社製、商品名:プレミノールS3011、Mn=10000):85重量部、トリオール(三洋化成株式会社製、サンニックスGP-3000、Mn=3000):13重量部、トリオール(三洋化成株式会社製、商品名:サンニックスGP-1000、Mn=1000):2重量部を用い、多官能イソシアネート化合物(B)として多官能脂環族系イソシアネート化合物(日本ポリウレタン工業株式会社、商品名:コロネートHX):18重量部、触媒(日本化学産業株式会社製、商品名:ナーセム第2鉄):0.04重量部、劣化防止剤としてIrganox1010(BASF製):0.50重量部、脂肪酸エステル(ミリスチン酸イソプロピル、花王製、商品名:エキセパールIPM、Mn=270):30重量部、1-エチル-3-メチルイミダゾリウムビス(フルオロメタンスルホニル)イミド(第一工業製薬社製、商品名:AS110):1.5重量部、両末端型のポリエーテル変性シリコーンオイル(信越化学工業株式会社製、KF-6004):0.01重量部、希釈溶剤として酢酸エチル:241重量部を配合し、ディスパーで撹拌し、ウレタン系粘着剤Cを得た。
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、ブチルアクリレート99重量部、4-ヒドロキシブチルアクリレート1重量部、重合開始剤として2,2’-アゾビスイソブチロニトリル0.1重量部を酢酸エチル100重量部と共に仕込み、緩やかに攪拌しながら窒素ガスを導入して窒素置換した後、フラスコ内の液温を55℃付近に保って8時間重合反応を行い、重量平均分子量160万の(メタ)アクリル系ポリマー溶液(A2)を調製した。
得られた(メタ)アクリル系ポリマー溶液(A2)(固形分100重量部)に対して、イソシアネート架橋剤(三井武田ケミカル社製、商品名:タケネートD110N,トリメチロールプロパンキシリレンジイソシアネート)0.1重量部、ポリエーテル化合物(旭ガラスウレタン社製、商品名:Excestar2420)1重量部を配合して、(メタ)アクリル系粘着剤Dを調製した。
製造例6で調製した(メタ)アクリル系ポリマー溶液(A2)(固形分100重量部)に対して、イソシアネート架橋剤(三井武田ケミカル社製、商品名:タケネートD110N,トリメチロールプロパンキシリレンジイソシアネート)0.3重量部、シランカップリング剤(信越化学工業(株)製、商品名:KBM403)0.1重量部を配合して、(メタ)アクリル系粘着剤Eを調製した。
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、ブチルアクリレート100重量部、アクリル酸3重量部、2-ヒドロキシエチルアクリレート1重量部、重合開始剤として2,2’-アゾビスイソブチロニトリル0.1重量部を酢酸エチル100重量部と共に仕込み、緩やかに攪拌しながら窒素ガスを導入して窒素置換した後、フラスコ内の液温を55℃付近に保って8時間重合反応を行い、重量平均分子量180万の(メタ)アクリル系ポリマー溶液(A3)を調製した。
得られた(メタ)アクリル系ポリマー溶液(A3)(固形分100重量部)に対して、イソシアネート架橋剤(日本ポリウレタン工業社製、商品名:コロネートL,トリメチロールプロパンのトリレンジイソシアネートのアダクト体)0.5重量部、シランカップリング剤(信越化学工業(株)製、商品名:KBM403)0.1重量部を配合して、(メタ)アクリル系粘着剤Fを調製した。
ガラスフィルム(日本電気硝子社製、商品名:OA10、サイズ:400mm×40mm、厚み:100μm)と、保護フィルム(厚さ40μmのアクリル系樹脂フィルム)と、偏光子Aとを、この順に接着剤を介して貼り合せて積層体aを得た。
(メタ)アクリル系粘着剤Aを、片面にシリコーン処理を施したポリエチレンテレフタレートフィルムのシリコーン処理面に塗布し、110℃で3分間加熱して、厚さ25μmの粘着剤層Aを形成した。この粘着剤層Aを上記積層体aの偏光子A側に転写して、光学積層体Aを得た。
(光学積層体の作製)
ガラスフィルム(日本電気硝子社製、商品名:OA10、サイズ:400mm×40mm、厚み:100μm)と、偏光子Aとを、接着剤を介して貼り合せて積層体bを得た。
(メタ)アクリル系粘着剤Aを、片面にシリコーン処理を施したポリエチレンテレフタレートフィルムのシリコーン処理面に塗布し、110℃で3分間加熱して、厚さ25μmの粘着剤層Aを形成した。この粘着剤層Aを上記積層体bの偏光子A側に転写して、光学積層体Bを得た。
ガラスフィルム(日本電気硝子社製、商品名:OA10、サイズ:400mm×40mm、厚み:100μm)と、保護フィルム(厚さ40μmのアクリル系樹脂フィルム)と、偏光子Bと、保護フィルム(厚さ40μmのアクリル系樹脂フィルム)とを、この順に接着剤を介して貼り合せて積層体cを得た。
(メタ)アクリル系粘着剤Aを、片面にシリコーン処理を施したポリエチレンテレフタレートフィルムのシリコーン処理面に塗布し、110℃で3分間加熱して、厚さ25μmの粘着剤層Aを形成した。この粘着剤層Aを上記積層体cの偏光子B側に転写して、光学積層体Cを得た。
実施例1と同様にして、積層体aを得た。
(メタ)アクリル系粘着剤Bを、シリコーン処理を施したポリエチレンテレフタレートフィルムのシリコーン処理面に塗布し、110℃で3分間加熱して、厚さ12μmの粘着剤層Bを形成した。この粘着剤層Bを上記積層体aの偏光子A側に転写して、光学積層体Dを得た。
実施例1と同様にして、積層体aを得た。
ウレタン系粘着剤Cを、片面にシリコーン処理を施したポリエチレンテレフタレートフィルムのシリコーン処理面に塗布し、110℃で3分間加熱して、厚さ25μmの粘着剤層Cを形成した。この粘着剤層Cを上記積層体aの偏光子A側に転写して、光学積層体Eを得た。
実施例1と同様にして、積層体aを得た。
(メタ)アクリル系粘着剤Dを、シリコーン処理を施したポリエチレンテレフタレートフィルムムのシリコーン処理面に塗布し、110℃で3分間加熱して、厚さ25μmの粘着剤層Dを形成した。この粘着剤層Dを上記積層体aの偏光子A側に転写して、光学積層体Fを得た。
実施例1と同様にして、積層体aを得た。
(メタ)アクリル系粘着剤Eを、シリコーン処理を施したポリエチレンテレフタレートフィルムムのシリコーン処理面に塗布し、110℃で3分間加熱して、厚さ50μmの粘着剤層Eを形成した。この粘着剤層Eを上記積層体aの偏光子A側に転写して、光学積層体Gを得た。
実施例1と同様にして、積層体aを得た。
上記(メタ)アクリル系粘着剤Fを、シリコーン処理を施したポリエチレンテレフタレートフィルムムのシリコーン処理面に塗布し、110℃で3分間加熱して、厚さ25μmの粘着剤層Fを形成した。この粘着剤層Fを上記積層体aの偏光子A側に転写して、光学積層体Hを得た。
ガラスフィルムを厚さ100μmのポリエチレンテレフタレートフィルムに変えたこと以外は、実施例1と同様にして光学積層体Iを得た。
実施例および比較例で得られた光学積層体を下記の評価に供した。結果を表1に示す。
光学積層体を、150mm×25mmに裁断し、厚さ0.7mmの無アルカリガラス板(コーニング社製、商品名:EG-XG)に、ラミネーターを用いて貼り付け、次いで50℃、5atmで15分間オートクレーブ処理して完全に密着させて、評価用サンプルを作製した。
上記評価用サンプルについて、引張り試験機(オートグラフSHIMAZU AG-1 10KN)を用い、23℃/湿度55%、剥離角度90°、剥離速度300mm/minの条件にて、ガラス板から光学積層体を剥離して、光学積層体の接着力を測定した。測定は、1回/0.5sの間隔でサンプリングし、その平均値を測定値とした。
光学積層体を、15インチ(対角線)サイズとし、厚さ0.7mmの無アルカリガラス(コーニング社製、商品名:EG-XG)にラミネーターを用いて貼着した。次いで、50℃、0.5MPaで15分間オートクレーブ処理して、光学積層体を完全に無アクリルガラスに密着させて評価用サンプルを作製した。
上記評価用サンプルについて、光学積層体の1角から対角方向に光学積層体をガラスから剥離し、ガラスフィルムの割れ、破断を評価した。
◎:光学積層体に割れが全くなく、容易にリワーク可
○:わずかながら光学積層体に割れがあるが容易にリワーク可。実用上問題なし。
△:光学積層体に割れがあるが破断することなくリワーク可。実用上問題なし。
×:光学積層体が破断してリワーク不可
光学積層体を、15インチ(対角線)サイズとし、厚さ0.7mmの無アルカリガラス(コーニング社製,EG-XG)にラミネーターを用いて貼着した。次いで、50℃、0.5MPaで15分間オートクレーブ処理して、光学積層体を完全に無アクリルガラスに密着させて評価用サンプルを作製した。
上記評価用サンプルを、80℃の雰囲気下で500時間処理を施した後(加熱試験)、外観を下記基準で目視にて評価した。
また、上記評価用サンプルを、60℃/90%RHの雰囲気下で500時間処理を施した後(加湿試験)、外観を下記基準で目視にて評価した。
◎:発泡、剥がれなどの外観上の変化が全くなし。
○:わずかながら端部に剥がれ、または発泡があるが、実用上問題なし。
△:端部に剥がれ、または発泡があるが、特別な用途でなければ、実用上問題なし。
×:端部に著しい剥がれあり、実用上問題あり。
20 偏光子
30 粘着剤層
100 光学積層体
Claims (7)
- ガラスフィルムと、偏光子と、粘着剤層とをこの順に備え、
ガラス板に対する接着力が、5N/25mm以下である、
光学積層体。 - 前記粘着剤層の厚みが、5μm~100μmである、請求項1に記載の光学積層体。
- 前記ガラスフィルムの厚みが、20μm~200μmである、請求項1に記載の光学積層体。
- 前記粘着剤層が、(メタ)アクリル系粘着剤を含む、請求項1に記載の光学積層体。
- 前記粘着剤層が、ウレタン系粘着剤を含む、請求項1に記載の光学積層体。
- 請求項1に記載の光学積層体を含む、画像表示装置。
- 視認側における最外側に、前記光学積層体を備える、請求項6に記載の画像表示装置。
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JP7069065B2 (ja) | 2019-02-27 | 2022-05-17 | リンテック株式会社 | 繰り返し屈曲ディスプレイ |
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WO2020203647A1 (ja) * | 2019-03-29 | 2020-10-08 | 日東電工株式会社 | 光学フィルム |
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Also Published As
Publication number | Publication date |
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KR20210066022A (ko) | 2021-06-04 |
TW201842129A (zh) | 2018-12-01 |
JP2021131540A (ja) | 2021-09-09 |
KR20190120255A (ko) | 2019-10-23 |
JPWO2018174012A1 (ja) | 2019-12-12 |
JP7523404B2 (ja) | 2024-07-26 |
CN110446956A (zh) | 2019-11-12 |
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