WO2012086465A1 - 活性エネルギー線硬化型接着剤組成物、偏光板、光学フィルムおよび画像表示装置 - Google Patents
活性エネルギー線硬化型接着剤組成物、偏光板、光学フィルムおよび画像表示装置 Download PDFInfo
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- WO2012086465A1 WO2012086465A1 PCT/JP2011/078772 JP2011078772W WO2012086465A1 WO 2012086465 A1 WO2012086465 A1 WO 2012086465A1 JP 2011078772 W JP2011078772 W JP 2011078772W WO 2012086465 A1 WO2012086465 A1 WO 2012086465A1
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- energy ray
- active energy
- value
- adhesive composition
- polymerizable compound
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- 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
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- 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
- G02B5/3041—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 comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—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 comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/1306—Details
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/1306—Details
- G02F1/1309—Repairing; Testing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
Definitions
- the present invention relates to an active energy ray-curable adhesive composition for forming an adhesive layer for adhering two or more members, particularly an active energy ray-curable adhesive for forming an adhesive layer between a polarizer and a transparent protective film.
- the present invention relates to a composition and a polarizing plate.
- the polarizing plate can form an image display device such as a liquid crystal display device (LCD), an organic EL display device, a CRT, or a PDP alone or as an optical film in which the polarizing plate is laminated.
- Liquid crystal display devices are rapidly expanding in the market for watches, mobile phones, PDAs, notebook computers, personal computer monitors, DVD players, TVs, etc.
- the liquid crystal display device visualizes the polarization state by switching of the liquid crystal, and a polarizer is used from the display principle.
- polarizing plates are also required to have higher transmittance, higher degree of polarization, and higher color reproducibility.
- an iodine-based polarizer having a stretched structure by adsorbing iodine to polyvinyl alcohol (hereinafter also simply referred to as “PVA”) is most widely used. in use.
- PVA polyvinyl alcohol
- a polarizing plate is used in which a transparent protective film is bonded to both surfaces of a polarizer with a so-called aqueous adhesive in which a polyvinyl alcohol-based material is dissolved in water (Patent Document 1 and Patent Document 2 below).
- the transparent protective film triacetyl cellulose having a high moisture permeability is used.
- a drying step is required after the polarizer and the transparent protective film are bonded together. .
- the water content of the polarizer in order to enhance the adhesion with the polarizer, the water content of the polarizer must be relatively high (usually the water content of the polarizer is about 30%). A polarizing plate with good adhesion cannot be obtained. However, the polarizing plate thus obtained has problems such as large dimensional change and poor optical characteristics under high temperature and high temperature and high humidity.
- the moisture content of a polarizer in order to suppress a dimensional change, the moisture content of a polarizer can be reduced or a transparent protective film with low moisture permeability can be used.
- drying efficiency decreases, polarization characteristics decrease, or appearance defects occur, and a substantially useful polarizing plate is obtained. I can't.
- an active energy ray-curable adhesive that does not contain water or an organic solvent has been proposed.
- Patent Document 3 (A) a radical polymerizable compound containing a polar group and having a molecular weight of 1,000 or less, and (B) a radical polymerizable compound containing no polar group and having a molecular weight of 1,000 or less,
- An active energy ray curable adhesive containing (D) a photopolymerization initiator is disclosed.
- the combination of radically polymerizable compounds (monomers) constituting such an adhesive is designed particularly for the purpose of improving the adhesion to norbornene-based resin films, and therefore tends to have poor adhesion to the polarizing film. It was.
- Patent Document 4 listed below discloses an active energy ray-curable adhesive having a photopolymerization initiator having a molar extinction coefficient of 400 or more at a wavelength of 360 to 450 nm and an ultraviolet curable compound as essential components.
- the combination of monomers constituting such an adhesive is designed mainly for the purpose of preventing warpage and deformation when adhering an optical disk or the like, when used for a polarizing film, There was a tendency to be inferior in adhesiveness.
- Patent Document 5 (a) a (meth) acrylic compound having two or more (meth) acryloyl groups in the molecule in a total amount of 100 parts by weight of the (meth) acrylic compound, and (b) a hydroxyl group in the molecule. And an active energy ray-curable adhesive containing (meth) acrylic compound having only one polymerizable double bond and (c) phenolethylene oxide-modified acrylate or nonylphenolethylene oxide-modified acrylate ing.
- an active energy ray-curable adhesive containing (meth) acrylic compound having only one polymerizable double bond and (c) phenolethylene oxide-modified acrylate or nonylphenolethylene oxide-modified acrylate ing.
- an adhesive is intended to improve adhesion by softening a cured product (adhesive layer) (lowering Tg), and there is a concern that durability such as crack resistance is deteriorated.
- the crack resistance can be evaluated by a thermal shock test (heat shock test).
- Patent Document 6 and Patent Document 7 below a radical polymerization type active energy ray-curable adhesive using an N-substituted amide monomer as a curable component.
- Such an adhesive exhibits excellent durability under harsh environments under high humidity and high temperature.
- Patent Document 7 a demand for an adhesive that can further improve adhesiveness and / or water resistance. There was a real situation.
- JP 2006-220732 A JP 2001-296427 A JP 2008-009329 A JP 09-31416 A JP 2008-174667 A JP 2008-287207 A JP 2010-78700 A
- the present invention has been made in view of the above circumstances, and its purpose is to improve adhesion between two or more members, particularly a polarizer and a transparent protective film layer, and to improve durability and water resistance.
- An active energy ray-curable adhesive composition capable of forming an agent layer, a polarizing plate, an optical film, and an image display device are provided.
- the present inventors paid attention to the SP value (solubility parameter) of the curable component in the active energy ray-curable adhesive composition in order to solve the above problems.
- SP value solubility parameter
- substances having close SP values have high affinity. Therefore, for example, when the SP values of the radical polymerizable compounds are close to each other, the compatibility thereof increases, and when the SP values of the radical polymerizable compound and the polarizer in the active energy ray-curable adhesive composition are close, Adhesiveness between the adhesive layer and the polarizer is enhanced.
- each SP value of at least three types of radical polymerizable compounds is designed within a specific range, And it discovered that the said subject could be solved by setting it as the optimal composition ratio.
- the present invention has been made as a result of the above-described studies, and achieves the above-described object with the following configuration.
- the active energy ray-curable adhesive composition according to the present invention is an active energy ray-curable adhesive composition containing radically polymerizable compounds (A), (B) and (C) as curable components.
- the radically polymerizable compound (B) having an SP value of 18.0 (kJ / m 3 ) 1/2 or more and less than 21.0 (kJ / m 3 ) 1/2 is 10 to 30% by weight and 20 to 60% by weight of a radically polymerizable compound (C) having an SP value of 21.0 (kJ / m 3 ) 1/2 or more and 23.0 (kJ / m 3 ) 1/2 or less
- the SP value of the radical polymerizable compound (A) is 29.0 (kJ / m 3 ) 1/2 or more and 32.0 or less (kJ / m 3 ) 1 / 2, when the total amount of the composition as 100 wt%, the composition ratio is 20 to 60 wt%.
- a radical polymerizable compound (A) has a high SP value, for example, a PVA polarizer (for example, SP value 32.8), a saponified triacetyl cellulose (for example, SP value 32.7) as a transparent protective film, and an adhesive. This greatly contributes to improving the adhesion with the layer.
- the radically polymerizable compound (A) has an SP value relatively close to water (SP value 47.9), if the composition ratio of the radically polymerizable compound (A) in the composition is too large, There is concern about deterioration of the water resistance of the agent layer. Therefore, in consideration of adhesion to a polarizer, saponified triacetyl cellulose, and water resistance, it is important that the composition ratio of the radical polymerizable compound (A) is 20 to 60% by weight. In consideration of adhesiveness, the composition ratio of the radical polymerizable compound (A) is preferably 25% by weight or more, and more preferably 30% by weight or more. In consideration of water resistance, the composition ratio of the radical polymerizable compound (A) is preferably 55% by weight or less, and more preferably 50% by weight or less.
- the SP value of the radical polymerizable compound (B) is 18.0 (kJ / m 3 ) 1/2 or more and less than 21.0 (kJ / m 3 ) 1/2 , and the composition ratio is 10 to 30% by weight. is there.
- Such radically polymerizable compound (A) has a low SP value and is far away from water (SP value 47.9), which greatly contributes to improving the water resistance of the adhesive layer.
- the SP value of the radical polymerizable compound (B) is, for example, the SP value (for example, SP value 18.6) of a cyclic polyolefin resin (for example, trade name “ZEONOR” manufactured by Nippon Zeon Co., Ltd.) as a transparent protective film.
- the SP value of the radical polymerizable compound (B) is preferably less than 20.0 (kJ / m 3 ) 1/2 .
- the radically polymerizable compound (B) has a large SP value from the radically polymerizable compound (A)
- the compatibility balance between the radically polymerizable compounds is lost.
- the transparency of the adhesive layer may deteriorate. Therefore, considering the water resistance and the transparency of the adhesive layer, it is important that the composition ratio of the radical polymerizable compound (B) is 10 to 30% by weight.
- the composition ratio of the radical polymerizable compound (B) is preferably 10% by weight or more, and more preferably 15% by weight or more.
- the composition ratio of the radical polymerizable compound (B) is preferably 25% by weight or less, more preferably 20% by weight or less, and its SP value is 19 0.0 (kJ / m 3 ) 1/2 or more is preferable.
- the SP value of the radical polymerizable compound (C) is 21.0 (kJ / m 3 ) 1/2 or more and less than 23.0 (kJ / m 3 ) 1/2 , and the composition ratio is 20 to 60% by weight. is there.
- the radically polymerizable compound (A) and the radically polymerizable compound (B) have a large SP value and are not compatible with each other.
- the SP value of the radical polymerizable compound (C) is located between the SP value of the radical polymerizable compound (A) and the SP value of the radical polymerizable compound (B), the radical polymerizable compound (A) In addition to the radically polymerizable compound (B) and the radically polymerizable compound (C), the compatibility of the composition as a whole is improved in a well-balanced manner. Furthermore, the SP value of the radical polymerizable compound (C) is close to the SP value (for example, 23.3) of unsaponified triacetyl cellulose as a transparent protective film and the SP value (for example, 22.2) of an acrylic film, for example. It also contributes to the improvement of adhesion with these transparent protective films.
- the composition ratio of the radical polymerizable compound (C) is 20 to 60% by weight.
- the composition ratio of the radical polymerizable compound (C) is preferably 25% by weight or more, and more preferably 29% by weight or more.
- the composition ratio of the radical polymerizable compound (C) is preferably 55% by weight or less, and more preferably 50% by weight or less.
- heat shock crack means, for example, a phenomenon in which when a polarizer contracts, it tears in the stretching direction, and in order to prevent this, polarized light is generated in a heat shock temperature range ( ⁇ 40 ° C. to 60 ° C.). It is important to suppress the expansion / contraction of the child.
- the glass transition temperature (Tg) of each of the radical polymerizable compounds (A), (B), and (C) is 60 ° C. or higher, when the adhesive layer is formed, the Tg is Get higher. As a result, a rapid change in elastic modulus of the adhesive layer in the heat shock temperature range can be suppressed, and the expansion / contraction force acting on the polarizer can be reduced, so that the occurrence of heat shock cracks can be prevented. .
- solubility parameter (SP value) the solubility parameter (SP value) of a radically polymerizable compound, a polarizer, various transparent protective films and the like is calculated by the Fedors calculation method ["Polymer Engineering &Sci.” Vol. 14, No. 2 (1974), pages 148-154]
- the radical polymerizable compounds (A), (B) and Radical polymerization containing 85 to 100 parts by weight of (C) and having an SP value of more than 23.0 (kJ / m 3 ) 1/2 and less than 29.0 (kJ / m 3 ) 1/2 It is preferable to contain 0 to 15 parts by weight of the active compound (D). According to such a configuration, since the ratio of the radical polymerizable compounds (A), (B) and (C) in the adhesive composition can be sufficiently ensured, the adhesiveness of the adhesive layer is improved, and the durability and Water resistance can be further improved.
- the radically polymerizable compounds (A), (B) and (C) are preferably contained in a total amount of 90 to 100 parts by weight, It is more preferable to contain parts by weight.
- the radical polymerizable compound (A) is preferably hydroxyethyl acrylamide and / or N-methylol acrylamide.
- the radical polymerizable compound (B) is preferably tripropylene glycol diacrylate.
- the radical polymerizable compound (C) is preferably acryloylmorpholine and / or N-methoxymethylacrylamide.
- the active energy ray-curable adhesive composition as a photopolymerization initiator, a compound represented by the following general formula (1); (Wherein R 1 and R 2 represent —H, —CH 2 CH 3 , —iPr or Cl, and R 1 and R 2 may be the same or different).
- the photopolymerization initiator of the general formula (1) can start polymerization by light having a long wavelength that passes through a transparent protective film having UV absorbing ability, the adhesive can be cured even through a UV absorbing film. Specifically, for example, even when laminating a transparent protective film having UV absorption ability on both sides, such as triacetylcellulose-polarizer-triacetylcellulose, when containing a photopolymerization initiator of the general formula (1), Curing of the adhesive composition is possible.
- the compound represented by following General formula (2) in addition to the photoinitiator of General formula (1) as a photoinitiator, the compound represented by following General formula (2); Wherein R 3 , R 4 and R 5 represent —H, —CH 3 , —CH 2 CH 3 , —iPr or Cl, and R 3 , R 4 and R 5 may be the same or different. It is preferable to contain.
- the polarizing plate according to the present invention is a polarizing plate in which a transparent protective film having a light transmittance of a wavelength of 365 nm of less than 5% is provided on at least one surface of a polarizer via an adhesive layer.
- the adhesive layer is formed of a cured product layer formed by irradiating the active energy ray-curable adhesive composition according to any one of the above with active energy rays.
- the polarizer has a high SP value (the SP value of the PVA polarizer is 32.8, for example), while the transparent protective film generally has a low SP value (the SP value is about 18 to 24).
- the polarizing plate according to the present invention includes a radically polymerizable compound (A) in an active energy ray-curable adhesive composition that forms an adhesive layer that adheres a polarizer having a high SP value and a transparent protective film having a low SP value. ), (B) and (C) are designed to optimize the SP value and blending amount.
- the polarizer and the transparent protective film are firmly bonded via the adhesive layer, and the durability and water resistance of the adhesive layer are excellent.
- the Tg of the adhesive layer is 60 ° C. or higher, more preferably 70 ° C. or higher, particularly preferably 90 ° C. or higher, the durability is particularly excellent, and the occurrence of heat shock cracks can be prevented.
- the optical film according to the present invention is characterized in that at least one polarizing plate described above is laminated.
- the transparent protective film preferably has an SP value of 29.0 (kJ / m 3 ) 1/2 or more and less than 33.0 (kJ / m 3 ) 1/2 .
- the SP value of the transparent protective film is within the above range, it is very close to the SP value of the radical polymerizable compound (A) in the active energy ray-curable adhesive composition. Adhesion is greatly improved.
- the transparent protective film having an SP value of 29.0 (kJ / m 3 ) 1/2 or more and less than 33.0 (kJ / m 3 ) 1/2 for example, saponified triacetyl cellulose (for example, SP value 32.7). ).
- the transparent protective film preferably has an SP value of 18.0 (kJ / m 3 ) 1/2 or more and less than 24.0 (kJ / m 3 ) 1/2 . If the SP value of the transparent protective film is within the above range, it is very close to the SP value of the radical polymerizable compound (B) and the radical polymerizable compound (C) in the active energy ray-curable adhesive composition. The adhesion between the protective film and the adhesive layer is greatly improved.
- a transparent protective film whose SP value is 18.0 (kJ / m 3 ) 1/2 or more and less than 24.0 (kJ / m 3 ) 1/2 , for example, unsaponified triacetyl cellulose (for example, SP value 23.30). 3).
- the image display device is characterized by using the polarizing plate and / or the optical film described above.
- the polarizer of the polarizing plate and the transparent protective film are firmly bonded via the adhesive layer, and the durability and water resistance of the adhesive layer are excellent.
- the adhesive layer is formed from the cured product of the active energy ray-curable adhesive composition according to the present invention, the adhesion between two or more members, particularly the polarizer and the transparent protective film layer, is improved and the durability is improved. In addition, an adhesive layer with improved water resistance can be formed.
- the adhesive layer according to the present invention When the adhesive layer according to the present invention is provided, a polarizing plate with a small dimensional change can be produced, so that it is possible to easily cope with an increase in the size of the polarizing plate, and it is possible to suppress the production cost from the viewpoint of yield and number of production. Further, since the polarizing plate according to the present invention has good dimensional stability, it is possible to suppress the occurrence of unevenness in the image display device due to the external heat of the backlight.
- the active energy ray-curable adhesive composition according to the present invention has an SP value of 29.0 (kJ / m 3 ) 1/2 or more and 32.0 when the total amount of the composition is 100% by weight as the curable component.
- the following (kJ / m 3 ) 1/2 of the radical polymerizable compound (A) is 20 to 60% by weight, and the SP value is 18.0 (kJ / m 3 ) 1/2 or more and 21.0 (kJ / m 3 ) 10-30% by weight of the radically polymerizable compound (B) which is less than 1/2 , and the SP value is 21.0 (kJ / m 3 ) 1/2 or more and 23.0 (kJ / m 3 ) 1/2 20 to 60% by weight of the following radically polymerizable compound (C) is contained.
- the “composition total amount” means the total amount including various initiators and additives in addition to the radical polymerizable compound.
- the radical polymerizable compound (A) has a radical polymerizable group such as a (meth) acrylate group and has an SP value of 29.0 (kJ / m 3 ) 1/2 or more and 32.0 or less (kJ / m 3 ) Any compound that is 1 ⁇ 2 can be used without limitation.
- Specific examples of the radical polymerizable compound (A) include hydroxyethyl acrylamide (SP value 29.6), N-methylol acrylamide (SP value 31.5) and the like.
- the (meth) acrylate group means an acrylate group and / or a methacrylate group.
- the radically polymerizable compound (B) has a radically polymerizable group such as a (meth) acrylate group and has an SP value of 18.0 (kJ / m 3 ) 1/2 or more and 21.0 (kJ / m 3 ). Any compound that is less than 1 ⁇ 2 can be used without limitation.
- Specific examples of the radically polymerizable compound (B) include, for example, tripropylene glycol diacrylate (SP value 19.0), 1,9-nonanediol diacrylate (SP value 19.2), tricyclodecane dimethanol dimer.
- Aronix M-220 (manufactured by Toagosei Co., Ltd., SP value 19.0), light acrylate 1,9ND-A (Kyoeisha Chemical Co., Ltd.) Manufactured, SP value 19.2), light acrylate DGE-4A (manufactured by Kyoeisha Chemical Co., SP value 20.9), light acrylate DCP-A (manufactured by Kyoeisha Chemical Co., SP value 20.3), SR-531 (Sartomer) And SP-value 19.1), CD-536 (Sartomer, SP value 19.4), and the like.
- the radical polymerizable compound (C) has a radical polymerizable group such as a (meth) acrylate group and has an SP value of 21.0 (kJ / m 3 ) 1/2 or more and 23.0 (kJ / m 3 ). Any compound that is 1 ⁇ 2 or less can be used without limitation.
- Specific examples of the radical polymerizable compound (C) include, for example, acryloylmorpholine (SP value 22.9), N-methoxymethylacrylamide (SP value 22.9), N-ethoxymethylacrylamide (SP value 22.3). Etc.
- a commercial item can also be used suitably, for example, ACMO (the Kojin company make, SP value 22.9), Wasmer 2MA (the Kasano Kosan company make, SP value 22.9). , Wasmer EMA (manufactured by Kasano Kosan Co., Ltd., SP value 22.3), Wasmer 3MA (manufactured by Kasano Kosan Co., Ltd., SP value 22.4), and the like.
- the glass transition temperature (Tg) of each of the radical polymerizable compounds (A), (B), and (C) is 60 ° C. or higher, the Tg of the adhesive layer is increased and the durability is particularly excellent. It will be. As a result, for example, when an adhesive layer of a polarizer and a transparent protective film is used, occurrence of heat shock cracks in the polarizer can be prevented.
- the Tg of the homopolymer of the radical polymerizable compound means Tg when the radical polymerizable compound is cured (polymerized) alone. A method for measuring Tg will be described later.
- the active energy ray-curable adhesive composition according to the present invention contains 85 to 100 parts by weight of radically polymerizable compounds (A), (B) and (C) in total, and further has an SP value of 23.0 (kJ). / M 3 ) 1/2 may be contained in an amount of 0 to 15 parts by weight of the radical polymerizable compound (D) which is less than 29.0 (kJ / m 3 ) 1/2 .
- radical polymerizable compound (D) examples include, for example, 4-hydroxybutyl acrylate (SP value 23.8), 2-hydroxyethyl acrylate (SP value 25.5), N-vinylcaprolactam (trade name V- CAP, manufactured by ISP, SP value 23.4), 2-hydroxypropyl acrylate (SP value 24.5), and the like.
- the active energy ray curable adhesive composition according to the present invention is used in an electron beam curable type, it is not particularly necessary to include a photopolymerization initiator in the composition, but when used in an ultraviolet curable type, It is preferable to use a photopolymerization initiator, and it is particularly preferable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more. A photopolymerization initiator that is highly sensitive to light of 380 nm or more will be described later.
- a photopolymerization initiator a compound represented by the following general formula (1); (Wherein R 1 and R 2 represent —H, —CH 2 CH 3 , —iPr or Cl, and R 1 and R 2 may be the same or different), respectively, or a general formula ( It is preferable to use together the compound represented by 1) and a photopolymerization initiator that is highly sensitive to light of 380 nm or more, which will be described later.
- the compound represented by the general formula (1) is used, the adhesiveness is excellent as compared with a case where a photopolymerization initiator having high sensitivity to light of 380 nm or more is used alone.
- the composition ratio of the compound represented by the general formula (1) in the composition is preferably 0.1 to 5.0% by weight when the total amount of the composition is 100% by weight, and preferably 0.5 to 4%. It is more preferably 0.0% by weight, and even more preferably 0.9 to 3.0% by weight.
- polymerization initiators include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, etc. Among them, ethyl 4-dimethylaminobenzoate is particularly preferable.
- a polymerization initiation assistant its addition amount is usually 0 to 5% by weight, preferably 0 to 4% by weight, most preferably 0 to 3% by weight, when the total amount of the composition is 100% by weight. .
- a known photopolymerization initiator can be used in combination as necessary. Since the transparent protective film having UV absorbing ability does not transmit light of 380 nm or less, it is preferable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more as the photopolymerization initiator.
- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine Oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) 1-yl) -phenyl) titanium and the like.
- a photopolymerization initiator in addition to the photopolymerization initiator of the general formula (1), a compound represented by the following general formula (2); Wherein R 3 , R 4 and R 5 represent —H, —CH 3 , —CH 2 CH 3 , —iPr or Cl, and R 3 , R 4 and R 5 may be the same or different. It is preferable to use it.
- the compound represented by the general formula (2) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE907 manufacturer: BASF) which is also a commercial product is suitable. Can be used.
- 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369 manufacturer: BASF)
- 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379 manufacturer: BASF) is preferred because of its high sensitivity.
- additives can be blended as other optional components as long as the objects and effects of the present invention are not impaired.
- additives include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, Polymers or oligomers such as silicone oligomers and polysulfide oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; Agents; Plasticizers; UV absorbers; Silane coupling agents; Inorganic fillers; Pigments;
- the silane coupling agent acts on the surface of the polarizer and can impart further water resistance.
- a silane coupling agent when used, its addition amount is usually 0 to 10% by weight, preferably 0 to 5% by weight, most preferably 0 to 3% by weight, when the total amount of the composition is 100% by weight. .
- an active energy ray-curable compound is preferably used, but the same water resistance can be imparted even if it is not active energy ray-curable.
- silane coupling agents include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycid as active energy ray-curable compounds.
- Xylpropyltrimethoxysilane 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Examples thereof include silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.
- the active energy ray curable adhesive composition according to the present invention can be used in an electron beam curable type or an ultraviolet curable type.
- the acceleration voltage is preferably 5 kV to 300 kV, and more preferably 10 kV to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the adhesive and may be insufficiently cured. If the acceleration voltage exceeds 300 kV, the penetration force through the sample is too strong and damages the transparent protective film and the polarizer. There is a risk of giving.
- the irradiation dose is 5 to 100 kGy, more preferably 10 to 75 kGy.
- the adhesive becomes insufficiently cured, and when it exceeds 100 kGy, the transparent protective film and the polarizer are damaged, resulting in a decrease in mechanical strength and yellowing, thereby obtaining predetermined optical characteristics. I can't.
- the electron beam irradiation is usually performed in an inert gas, but if necessary, it may be performed in the atmosphere or under a condition where a little oxygen is introduced. Depending on the material of the transparent protective film, by appropriately introducing oxygen, the transparent protective film surface where the electron beam first hits can be obstructed to prevent oxygen damage and prevent damage to the transparent protective film. An electron beam can be irradiated efficiently.
- the ultraviolet curable type when employed in the present invention, it is preferable to use an apparatus that does not emit light having a wavelength shorter than 380 nm as the ultraviolet ray generating apparatus.
- the ratio with the integrated illuminance in the range of 250 to 370 nm is preferably 100: 0 to 100: 50, and more preferably 100: 0 to 100: 40.
- a gallium-filled metal halide lamp and an LED light source that emits light in the wavelength range of 380 to 440 nm are preferable.
- low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight as the light source It is also possible to use a light having a wavelength shorter than 380 nm by using a band pass filter.
- the ultraviolet curable type it is preferable to warm the active energy ray-curable adhesive composition before irradiation with ultraviolet rays (heating before irradiation), in which case it is preferable to warm to 40 ° C. or higher, and 50 ° C. or higher. It is more preferable to heat the sample. In addition, it is also preferable to heat the active energy ray-curable adhesive composition after irradiation with ultraviolet rays (heating after irradiation), in which case it is preferable to heat to 40 ° C. or higher, and to warm to 50 ° C. or higher. Is more preferable.
- the active energy ray-curable adhesive composition according to the present invention can be suitably used particularly when forming an adhesive layer that bonds a polarizer and a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm. It is.
- the active energy ray-curable adhesive composition according to the present invention irradiates ultraviolet rays through the transparent protective film having UV absorption ability by containing the photopolymerization initiator of the general formula (1) described above.
- the adhesive layer can be cured and formed. Therefore, an adhesive bond layer can be hardened also in the polarizing plate which laminated the transparent protective film which has UV absorption ability on both sides of a polarizer.
- the adhesive layer can be cured also in a polarizing plate on which a transparent protective film having no UV absorbing ability is laminated.
- the transparent protective film which has UV absorption ability means the transparent protective film whose transmittance
- Examples of the method for imparting UV absorbing ability to the transparent protective film include a method of containing an ultraviolet absorber in the transparent protective film and a method of laminating a surface treatment layer containing an ultraviolet absorber on the surface of the transparent protective film.
- ultraviolet absorber examples include conventionally known oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like.
- the adhesive layer formed with the active energy ray-curable adhesive composition has higher durability than the aqueous adhesive layer.
- the thickness of the adhesive layer is preferably controlled to be 0.01 to 7 ⁇ m.
- the active energy ray-curable adhesive composition is preferably selected so that the Tg of the adhesive layer formed thereby is 60 ° C. or higher, and more preferably 70 ° C. or higher. Further, it is preferably 75 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher. On the other hand, if the Tg of the adhesive layer becomes too high, the flexibility of the polarizing plate is lowered. Therefore, the Tg of the adhesive layer is preferably 300 ° C. or lower, more preferably 240 ° C. or lower, and further preferably 180 ° C. or lower.
- the thickness of the adhesive layer is preferably 0.01 to 7 ⁇ m, more preferably 0.01 to 5 ⁇ m, still more preferably 0.01 to 2 ⁇ m, and most preferably 0.01 to 1 ⁇ m.
- the thickness of the adhesive layer is smaller than 0.01 ⁇ m, the cohesive force of the adhesive force itself cannot be obtained, and the adhesive strength may not be obtained.
- the thickness of the adhesive layer exceeds 7 ⁇ m, the polarizing plate cannot satisfy the durability.
- the active energy ray-curable adhesive composition is applied to the surface of the polarizer that forms the adhesive layer and / or the surface of the transparent protective film that forms the adhesive layer. And a step of bonding the transparent protective film, and then a step of curing the active energy ray-curable adhesive composition by active energy ray irradiation to form an adhesive layer.
- the polarizer and the transparent protective film may be subjected to a surface modification treatment before applying the active energy ray-curable adhesive composition.
- a surface modification treatment include corona treatment, plasma treatment, and saponification treatment.
- the coating method of the active energy ray-curable adhesive composition is appropriately selected depending on the viscosity of the composition and the target thickness.
- coating methods include reverse coaters, gravure coaters (direct, reverse and offset), bar reverse coaters, roll coaters, die coaters, bar coaters, rod coaters and the like.
- a method such as a dapping method can be appropriately used.
- the polarizer and the transparent protective film are bonded together through the adhesive applied as described above. Bonding of the polarizer and the transparent protective film can be performed with a roll laminator or the like.
- the active energy ray (electron beam, ultraviolet ray, etc.) is irradiated to cure the active energy ray-curable adhesive composition to form an adhesive layer.
- the irradiation direction of active energy rays can be irradiated from any appropriate direction. Preferably, it irradiates from the transparent protective film side.
- the polarizer may be deteriorated by active energy rays (electron beams, ultraviolet rays, etc.).
- the line speed depends on the curing time of the adhesive, but is preferably 1 to 500 m / min, more preferably 5 to 300 m / min, and still more preferably 10 to 100 m / min. min.
- productivity is poor, or damage to the transparent protective film is too great, and a polarizing plate that can withstand a durability test or the like cannot be produced.
- the line speed is too high, the adhesive is not sufficiently cured, and the target adhesiveness may not be obtained.
- a polarizer and a transparent protective film are bonded together via an adhesive layer formed of a cured product layer of the active energy ray-curable adhesive composition.
- An easily adhesive layer can be provided between the adhesive layer and the adhesive layer.
- the easy adhesion layer can be formed of, for example, various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone-based, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, and the like. These polymer resins can be used alone or in combination of two or more. Moreover, you may add another additive for formation of an easily bonding layer. Specifically, a stabilizer such as a tackifier, an ultraviolet absorber, an antioxidant, and a heat resistance stabilizer may be used.
- the easy-adhesion layer is usually provided in advance on a transparent protective film, and the easy-adhesion layer side of the transparent protective film and the polarizer are bonded together with an adhesive layer.
- the easy-adhesion layer is formed by coating and drying the material for forming the easy-adhesion layer on the transparent protective film by a known technique.
- the material for forming the easy-adhesion layer is usually adjusted as a solution diluted to an appropriate concentration in consideration of the thickness after drying and the smoothness of coating.
- the thickness of the easy-adhesion layer after drying is preferably 0.01 to 5 ⁇ m, more preferably 0.02 to 2 ⁇ m, and still more preferably 0.05 to 1 ⁇ m. Note that a plurality of easy-adhesion layers can be provided, but also in this case, the total thickness of the easy-adhesion layers is preferably in the above range.
- a transparent protective film is bonded to at least one surface of a polarizer via an adhesive layer formed of a cured product layer of the active energy ray-curable adhesive composition.
- the polarizer is not particularly limited, and various types can be used.
- the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and two colors such as iodine and dichroic dye.
- polyene-based oriented films such as those obtained by adsorbing a functional material and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
- a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable.
- the thickness of these polarizers is not particularly limited, but is generally about 80 ⁇ m or less.
- a polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of boric acid or potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there.
- Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching.
- the film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.
- a thin polarizer having a thickness of 10 ⁇ m or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 ⁇ m. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing plate can be reduced.
- the thin polarizer typically, JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917, PCT / JP2010 / 001460, or Japanese Patent Application No. 2010- And a thin polarizing film described in Japanese Patent Application No. 269002 and Japanese Patent Application No. 2010-263692.
- These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state and a step of dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.
- PVA-based resin polyvinyl alcohol-based resin
- the thin polarizing film among the production methods including the step of stretching in the state of a laminate and the step of dyeing, WO2010 / 100917 pamphlet, PCT / PCT / PCT / JP 2010/001460 specification, or Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692, the one obtained by a production method including a step of stretching in a boric acid aqueous solution is preferable. What is obtained by the manufacturing method including the process of extending
- the thin high-performance polarizing film described in the specification of PCT / JP2010 / 001460 is a thin film having a thickness of 7 ⁇ m or less made of a PVA-based resin oriented with a dichroic material, which is integrally formed on a resin base material. It is a high-functional polarizing film, and has optical properties such as a single transmittance of 42.0% or more and a degree of polarization of 99.95% or more.
- the thin high-performance polarizing film generates a PVA-based resin layer by applying and drying a PVA-based resin on a resin substrate having a thickness of at least 20 ⁇ m, and the generated PVA-based resin layer is used as a dichroic dyeing solution. So that the dichroic substance is adsorbed on the PVA resin layer, and the PVA resin layer on which the dichroic substance is adsorbed is integrated with the resin base material in the boric acid aqueous solution so that the total draw ratio is the original length. It can manufacture by extending
- a method for producing a laminate film including a thin high-performance polarizing film in which a dichroic substance is oriented and includes a resin base material having a thickness of at least 20 ⁇ m and a PVA resin on one side of the resin base material.
- surface of the resin base material A step of adsorbing the dichroic substance to the PVA resin layer contained in the laminate film by immersing the film in a dye solution containing the dichroic substance, and a PVA resin adsorbing the dichroic substance
- the above-mentioned Japanese Patent Application Nos. 2010-269002 and 2010-263692 are thin polarizing films, which are polarizing films of a continuous web made of a PVA-based resin in which a dichroic material is oriented.
- a laminate including a PVA-based resin layer formed on a thermoplastic resin base material is stretched in a two-stage stretching process consisting of air-assisted stretching and boric acid-water stretching to a thickness of 10 ⁇ m or less. It is.
- Such a thin polarizing film has P> ⁇ (100.929T ⁇ 42.4-1) ⁇ 100 (where T ⁇ 42.3) and P ⁇ 99, where T is the single transmittance and P is the polarization degree. .9 (where T ⁇ 42.3) is preferable.
- the thin polarizing film is a stretch intermediate formed of an oriented PVA resin layer by high-temperature stretching in the air with respect to the PVA resin layer formed on the amorphous ester thermoplastic resin substrate of the continuous web.
- a colored intermediate product comprising a PVA-based resin layer in which a dichroic material (preferably iodine or a mixture of iodine and an organic dye) is oriented by adsorption of the dichroic material to the stretched intermediate product and a step of generating the product.
- a thin polarizing film comprising a step of forming a product, and a step of generating a polarizing film having a thickness of 10 ⁇ m or less comprising a PVA-based resin layer in which a dichroic material is oriented by stretching in a boric acid solution with respect to a colored intermediate product It can be manufactured by a manufacturing method.
- the total draw ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material by high-temperature drawing in air and drawing in boric acid solution should be 5 times or more. desirable.
- stretching can be 60 degreeC or more.
- the colored intermediate product is added to the aqueous boric acid solution whose liquid temperature does not exceed 40 ° C. It is desirable to do so by dipping.
- the amorphous ester-based thermoplastic resin base material is amorphous polyethylene containing copolymerized polyethylene terephthalate copolymerized with isophthalic acid, copolymerized polyethylene terephthalate copolymerized with cyclohexanedimethanol, or other copolymerized polyethylene terephthalate. It can be terephthalate and is preferably made of a transparent resin, and the thickness thereof can be 7 times or more the thickness of the PVA resin layer to be formed.
- the draw ratio of high-temperature drawing in the air is preferably 3.5 times or less, and the drawing temperature of high-temperature drawing in the air is preferably not less than the glass transition temperature of the PVA resin, specifically in the range of 95 ° C to 150 ° C.
- the total stretching ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material is preferably 5 to 7.5 times .
- the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin base material is 5 times or more and 8.5 times or less. Is preferred. More specifically, a thin polarizing film can be produced by the following method.
- a base material for a continuous web of isophthalic acid copolymerized polyethylene terephthalate (amorphous PET) in which 6 mol% of isophthalic acid is copolymerized is prepared.
- the glass transition temperature of amorphous PET is 75 ° C.
- a laminate comprising a continuous web of amorphous PET substrate and a polyvinyl alcohol (PVA) layer is prepared as follows. Incidentally, the glass transition temperature of PVA is 80 ° C.
- a 200 ⁇ m-thick amorphous PET base material and a 4-5% PVA aqueous solution in which PVA powder having a polymerization degree of 1000 or more and a saponification degree of 99% or more are dissolved in water are prepared.
- an aqueous PVA solution is applied to a 200 ⁇ m thick amorphous PET substrate and dried at a temperature of 50 to 60 ° C. to obtain a laminate in which a 7 ⁇ m thick PVA layer is formed on the amorphous PET substrate. .
- a thin and highly functional polarizing film having a thickness of 3 ⁇ m is manufactured from the laminate including the PVA layer having a thickness of 7 ⁇ m through the following steps including a two-stage stretching process of air-assisted stretching and boric acid water stretching.
- the laminate including the 7 ⁇ m-thick PVA layer is integrally stretched with the amorphous PET substrate to produce a stretched laminate including the 5 ⁇ m-thick PVA layer.
- a laminate including a 7 ⁇ m-thick PVA layer is subjected to a stretching apparatus disposed in an oven set to a stretching temperature environment of 130 ° C. so that the stretching ratio is 1.8 times. Are stretched uniaxially at the free end.
- the PVA layer contained in the stretched laminate is changed to a 5 ⁇ m thick PVA layer in which PVA molecules are oriented.
- this colored laminate has a single layer transmittance of the PVA layer constituting the high-performance polarizing film that is finally produced by using the stretched laminate in a staining solution containing iodine and potassium iodide at a liquid temperature of 30 ° C.
- Iodine is adsorbed to the PVA layer contained in the stretched laminate by dipping for an arbitrary period of time so as to be 40 to 44%.
- the staining solution uses water as a solvent, and an iodine concentration within the range of 0.12 to 0.30% by weight and a potassium iodide concentration within the range of 0.7 to 2.1% by weight.
- concentration ratio of iodine and potassium iodide is 1 to 7.
- potassium iodide is required to dissolve iodine in water. More specifically, by immersing the stretched laminate in a dyeing solution having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight for 60 seconds, iodine is applied to a 5 ⁇ m-thick PVA layer in which PVA molecules are oriented. A colored laminate is adsorbed on the substrate.
- the colored laminated body is further stretched integrally with the amorphous PET base material by the second stage boric acid underwater stretching step to produce an optical film laminate including a PVA layer constituting a highly functional polarizing film having a thickness of 3 ⁇ m.
- the optical film laminate is subjected to stretching by applying the colored laminate to a stretching apparatus provided in a treatment apparatus set to a boric acid aqueous solution having a liquid temperature range of 60 to 85 ° C. containing boric acid and potassium iodide. It is stretched uniaxially at the free end so that the magnification is 3.3 times. More specifically, the liquid temperature of the boric acid aqueous solution is 65 ° C.
- the colored laminate having an adjusted iodine adsorption amount is first immersed in an aqueous boric acid solution for 5 to 10 seconds. After that, the colored laminate is passed as it is between a plurality of sets of rolls with different peripheral speeds, which is a stretching apparatus installed in the processing apparatus, and the stretching ratio can be freely increased to 3.3 times over 30 to 90 seconds. Stretch uniaxially.
- the PVA layer contained in the colored laminate is changed into a PVA layer having a thickness of 3 ⁇ m in which the adsorbed iodine is oriented higher in one direction as a polyiodine ion complex.
- This PVA layer constitutes a highly functional polarizing film of the optical film laminate.
- the optical film laminate was removed from the boric acid aqueous solution and adhered to the surface of the 3 ⁇ m-thick PVA layer formed on the amorphous PET substrate by the washing step. It is preferable to wash boric acid with an aqueous potassium iodide solution. Thereafter, the washed optical film laminate is dried by a drying process using hot air at 60 ° C.
- the cleaning process is a process for eliminating appearance defects such as boric acid precipitation.
- an adhesive is applied to the surface of a 3 ⁇ m-thick PVA layer formed on an amorphous PET substrate by a bonding and / or transfer process.
- the amorphous PET substrate can be peeled off, and the 3 ⁇ m thick PVA layer can be transferred to the 80 ⁇ m thick triacetyl cellulose film.
- the manufacturing method of said thin-shaped polarizing film may include another process other than the said process.
- Examples of other steps include an insolubilization step, a crosslinking step, and a drying (adjustment of moisture content) step.
- the other steps can be performed at any appropriate timing.
- the insolubilization step is typically performed by immersing the PVA resin layer in a boric acid aqueous solution. By performing the insolubilization treatment, water resistance can be imparted to the PVA resin layer.
- the concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water.
- the liquid temperature of the insolubilizing bath (boric acid aqueous solution) is preferably 20 ° C.
- the insolubilization step is performed after the laminate is manufactured and before the dyeing step and the underwater stretching step.
- the crosslinking step is typically performed by immersing the PVA resin layer in an aqueous boric acid solution.
- the concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water.
- blend iodide it is preferable to mix
- the blending amount of iodide is preferably 1 to 5 parts by weight with respect to 100 parts by weight of water. Specific examples of the iodide are as described above.
- the liquid temperature of the crosslinking bath is preferably 20 ° C. to 50 ° C.
- the crosslinking step is performed before the second boric acid aqueous drawing step.
- the dyeing step, the crosslinking step, and the second boric acid aqueous drawing step are performed in this order.
- the material for forming the transparent protective film provided on one or both sides of the polarizer is preferably a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like.
- polyester polymers such as polyethylene terephthalate and polyethylene naphthalate
- cellulose polymers such as diacetyl cellulose and triacetyl cellulose
- acrylic polymers such as polymethyl methacrylate
- styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin)
- AS resin acrylonitrile / styrene copolymer
- polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or the above
- the polymer that forms the transparent protective film include polymer blends. One or more kinds of arbitrary appropriate additives may be contained in the transparent protective film.
- the additive examples include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, an anti-coloring agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent.
- the content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. .
- content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
- the transparent protective film examples include a polymer film described in JP-A-2001-343529 (WO01 / 37007), for example, (A) a thermoplastic resin having a substituted and / or unsubstituted imide group in the side chain, B) Resin compositions containing a thermoplastic resin having substituted and / or unsubstituted phenyl and nitrile groups in the side chain.
- Specific examples include a film of a resin composition containing an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile / styrene copolymer.
- As the film a film made of a mixed extruded product of the resin composition or the like can be used. Since these films have a small phase difference and a small photoelastic coefficient, problems such as unevenness due to the distortion of the polarizing plate can be eliminated, and since the moisture permeability is small, the humidification durability is excellent.
- the thickness of the transparent protective film can be determined as appropriate, but is generally about 1 to 500 ⁇ m from the viewpoints of workability such as strength and handleability and thin layer properties. 1 to 300 ⁇ m is particularly preferable, and 5 to 200 ⁇ m is more preferable.
- the transparent protective film which consists of the same polymer material may be used by the front and back, and the transparent protective film which consists of a different polymer material etc. may be used.
- Functional surfaces such as a hard coat layer, an antireflection layer, an antisticking layer, a diffusion layer or an antiglare layer can be provided on the surface of the transparent protective film to which the polarizer is not adhered.
- the functional layers such as the hard coat layer, antireflection layer, antisticking layer, diffusion layer and antiglare layer can be provided on the transparent protective film itself, and separately provided separately from the transparent protective film. You can also
- the polarizing plate of the present invention can be used as an optical film laminated with another optical layer in practical use.
- the optical layer is not particularly limited.
- a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), and a viewing angle compensation film.
- One or more optical layers that may be used can be used.
- a reflective polarizing plate or a semi-transmissive polarizing plate in which a polarizing plate or a semi-transmissive reflecting plate is further laminated on the polarizing plate of the present invention an elliptical polarizing plate or a circularly polarizing plate in which a retardation plate is further laminated on the polarizing plate.
- a wide viewing angle polarizing plate obtained by further laminating a viewing angle compensation film on a plate or a polarizing plate, or a polarizing plate obtained by further laminating a brightness enhancement film on the polarizing plate is preferable.
- the optical film in which the optical layer is laminated on the polarizing plate can be formed by a method of laminating separately in the manufacturing process of a liquid crystal display device or the like. It is excellent in stability and assembly work, and has the advantage of improving the manufacturing process of a liquid crystal display device and the like.
- Appropriate bonding means such as an adhesive layer can be used for lamination.
- An adhesive layer for adhering to other members such as a liquid crystal cell may be provided on the polarizing plate described above or an optical film in which at least one polarizing plate is laminated.
- the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited.
- an acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer is appropriately selected.
- those having excellent optical transparency such as an acrylic pressure-sensitive adhesive, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and being excellent in weather resistance, heat resistance and the like can be preferably used.
- the adhesive layer can also be provided on one or both sides of a polarizing plate or an optical film as a superimposed layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as adhesive layers, such as a different composition, a kind, and thickness, in the front and back of a polarizing plate or an optical film.
- the thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is generally 1 to 500 ⁇ m, preferably 1 to 200 ⁇ m, and particularly preferably 1 to 100 ⁇ m.
- the exposed surface of the adhesive layer is temporarily covered with a separator for the purpose of preventing contamination until it is put to practical use. Thereby, it can prevent contacting an adhesion layer in the usual handling state.
- a separator for example, an appropriate thin leaf body such as a plastic film, rubber sheet, paper, cloth, non-woven fabric, net, foamed sheet, metal foil, or a laminate thereof, and a silicone-based or long sheet as necessary.
- an appropriate release agent such as a chain alkyl type, fluorine type or molybdenum sulfide, can be used.
- the polarizing plate or optical film of the present invention can be preferably used for forming various devices such as a liquid crystal display device.
- the liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, a polarizing plate or an optical film, and an illumination system as necessary, and incorporating a drive circuit. There is no limitation in particular except the point which uses the polarizing plate or optical film by invention, and it can apply according to the former.
- the liquid crystal cell any type such as a TN type, an STN type, or a ⁇ type can be used.
- liquid crystal display devices such as a liquid crystal display device in which a polarizing plate or an optical film is disposed on one side or both sides of a liquid crystal cell, or a backlight or reflector used in an illumination system can be formed.
- the polarizing plate or optical film by this invention can be installed in the one side or both sides of a liquid crystal cell.
- polarizing plate or an optical film on both sides they may be the same or different.
- liquid crystal display device for example, a single layer or a suitable layer such as a diffusion plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, a backlight, Two or more layers can be arranged.
- a suitable layer such as a diffusion plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, a backlight.
- Tg Glass transition temperature> Tg was measured under the following measurement conditions using a TA Instruments dynamic viscoelasticity measuring device RSAIII. Sample size: width 10mm, length 30mm, Clamp distance 20mm, Measurement mode: Tensile, Frequency: 1 Hz, Temperature rising rate: 5 ° C./min Dynamic viscoelasticity was measured and adopted as the temperature Tg of tan ⁇ peak top.
- TAC triacetyl cellulose film
- an ultraviolet ray (gallium encapsulated metal halide lamp) Irradiation device Fusion UV Systems, Inc.
- Light HAMMER10 bulb V bulb Peak illuminance: 1600 mW / cm 2 , integrated irradiation amount 1000 / mJ / cm 2 (wavelength 380 to 440 nm) )It was used.
- the illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell.
- Radical polymerizable compound (A) HEAA (Hydroxyethylacrylamide), SP value 29.6, homopolymer Tg 123 ° C, Kojin N-MAM-PC (N-methylolacrylamide), SP value 31.5, homopolymer Tg 150 ° C, Kasano Kosan
- radical polymerizable compound (C) ACMO acryloylmorpholine
- SP value 22.9 Tg of homopolymer 150 ° C., manufactured by Kojin Co., Ltd.
- Wasmer 2MA N-methoxymethylacrylamide
- SP value 22.9 Tg of homopolymer 99 ° C., manufactured by Kasano Kosan Co., Ltd.
- Radical polymerizable compound (D) 4HBA 4-hydroxybutyl acrylate
- SP value 23.8 homopolymer Tg-14 ° C, manufactured by Osaka Organic Chemical Industry Co., Ltd.
- Photopolymerization initiator KAYACURE DETX-S diethylthioxanthone
- IRGACURE907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one), manufactured by BASF
- the active energy ray-curable adhesive compositions according to Examples 1 to 7 and Comparative Examples 1 to 5 are coated on the transparent protective film with an MCD coater (manufactured by Fuji Machine Co., Ltd.) (cell shape: honeycomb, gravure roll).
- the number of lines was 1000 lines / inch, the rotation speed was 140% / vs line speed), and the thickness was 0.5 ⁇ m.
- the active energy rays according to Examples 1 to 7 and Comparative Examples 1 to 6 were heated to 50 ° C. using an IR heater and irradiated with the ultraviolet rays on both sides. After the curable adhesive composition was cured, it was dried with hot air at 70 ° C.
- Example 8 (Production of thin polarizing film Y and production of polarizing plate using it)
- a laminated body in which a PVA layer having a thickness of 24 ⁇ m is formed on an amorphous PET base material is produced by air-assisted stretching at a stretching temperature of 130 ° C., and then, A colored laminate is produced by dyeing the stretched laminate, and the colored laminate is stretched integrally with the amorphous PET substrate so that the total stretch ratio is 5.94 times by stretching in boric acid water at a stretching temperature of 65 degrees.
- An optical film laminate comprising a 10 ⁇ m thick PVA layer was produced.
- the PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex.
- an optical film laminate including a PVA layer having a thickness of 10 ⁇ m constituting the high-functional polarizing film Y could be produced.
- the active energy ray-curable adhesive composition according to Example 1 was applied to the surface of the thin polarizing film Y of the optical film laminate, and the transparent protective film used in Example 1 was bonded from the adhesive application surface. Then, the amorphous PET base material was peeled off, and a polarizing plate using the thin polarizing film Y (polarizing plate according to Example 8) was produced.
- the polarizing plate is cut into a size of 200 mm parallel to the stretching direction of the polarizer and 20 mm in the orthogonal direction, and between the transparent protective film (untreated TAC; SP value 23.3) and the polarizer (SP value 32.8).
- TAC transparent protective film
- SP value 32.8 the transparent protective film
- the polarizer SP value 32.8
- the protective film and the polarizer were peeled off at 90 ° direction at a peeling speed of 500 mm / min, and the peel strength was measured.
- the infrared absorption spectrum of the peeling surface after peeling was measured by ATR method, and the peeling interface was evaluated based on the following reference
- A Cohesive fracture of protective film
- B Interfacial delamination between protective film / adhesive layer
- C Interfacial delamination between adhesive layer / polarizer
- D Cohesive fracture of polarizer This means that the adhesive strength is very excellent.
- B and C mean that the adhesive force at the interface of the protective film / adhesive layer (adhesive layer / polarizer) is insufficient (adhesive strength is poor).
- the adhesive strength in the case of A or D is ⁇
- a ⁇ B (“cohesive failure of protective film” and “interfacial peeling between protective film / adhesive layer” occur simultaneously) or A ⁇ C (Adhesive strength in the case of “cohesive failure of protective film” and “interfacial peeling between adhesive layer / polarizer” occur simultaneously) is ⁇
- adhesive strength in the case of B or C is x.
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Abstract
Description
本発明において、ラジカル重合性化合物や偏光子、各種透明保護フィルムなどの溶解度パラメーター(SP値)は、Fedorsの算出法[「ポリマー・エンジニアリング・アンド・サイエンス(Polymer Eng.& Sci.)」,第14巻,第2号(1974),第148~154ページ参照]すなわち、
(式中、R1およびR2は-H、-CH2CH3、-iPrまたはClを示し、R1およびR2は同一または異なっても良い)を含有することが好ましい。
(式中、R3、R4およびR5は-H、-CH3、-CH2CH3、-iPrまたはClを示し、R3、R4およびR5は同一または異なっても良い)を含有することが好ましい。上記一般式(1)および一般式(2)の光重合開始剤を併用することで、これらの光増感反応により反応が高効率化し、接着剤層の接着性が特に向上する。
(式中、R1およびR2は-H、-CH2CH3、-iPrまたはClを示し、R1およびR2は同一または異なっても良い)を単独で使用するか、あるいは一般式(1)で表される化合物と後述する380nm以上の光に対して高感度な光重合開始剤とを併用することが好ましい。一般式(1)で表される化合物を使用した場合、380nm以上の光に対して高感度な光重合開始剤を単独で使用した場合に比べて接着性に優れる。一般式(1)で表される化合物の中でも、R1およびR2が-CH2CH3であるジエチルチオキサントンが特に好ましい。組成物中の一般式(1)で表される化合物の組成比率は、組成物全量を100重量%としたとき、0.1~5.0重量%であることが好ましく、0.5~4.0重量%であることがより好ましく、0.9~3.0重量%であることがさらに好ましい。
(式中、R3、R4およびR5は-H、-CH3、-CH2CH3、-iPrまたはClを示し、R3、R4およびR5は同一または異なっても良い)を使用することが好ましい。一般式(2)で表される化合物としては、市販品でもある2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン(商品名:IRGACURE907 メーカー:BASF)が好適に使用可能である。その他、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1(商品名:IRGACURE369 メーカー:BASF)、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン(商品名:IRGACURE379 メーカー:BASF)が感度が高いため好ましい。
薄型偏光膜は、二色性物質を配向させたPVA系樹脂からなる連続ウェブの偏光膜であって、非晶性エステル系熱可塑性樹脂基材に製膜されたPVA系樹脂層を含む積層体が空中補助延伸とホウ酸水中延伸とからなる2段延伸工程で延伸されることにより、10μm以下の厚みにされたものである。かかる薄型偏光膜は、単体透過率をT、偏光度をPとしたとき、P>-(100.929T-42.4-1)×100(ただし、T<42.3)、およびP≧99.9(ただし、T≧42.3)の条件を満足する光学特性を有するようにされたものであることが好ましい。
更に具体的には、次のような方法により、薄型偏光膜を製造することができる。
上記の薄型偏光膜の製造方法は、上記工程以外に、その他の工程を含み得る。その他の工程としては、例えば、不溶化工程、架橋工程、乾燥(水分率の調節)工程等が挙げられる。その他の工程は、任意の適切なタイミングで行い得る。
上記不溶化工程は、代表的には、ホウ酸水溶液にPVA系樹脂層を浸漬させることにより行う。不溶化処理を施すことにより、PVA系樹脂層に耐水性を付与することができる。当該ホウ酸水溶液の濃度は、水100重量部に対して、好ましくは1重量部~4重量部である。不溶化浴(ホウ酸水溶液)の液温は、好ましくは20℃~50℃である。好ましくは、不溶化工程は、積層体作製後、染色工程や水中延伸工程の前に行う。
上記架橋工程は、代表的には、ホウ酸水溶液にPVA系樹脂層を浸漬させることにより行う。架橋処理を施すことにより、PVA系樹脂層に耐水性を付与することができる。当該ホウ酸水溶液の濃度は、水100重量部に対して、好ましくは1重量部~4重量部である。また、上記染色工程後に架橋工程を行う場合、さらに、ヨウ化物を配合することが好ましい。ヨウ化物を配合することにより、PVA系樹脂層に吸着させたヨウ素の溶出を抑制することができる。ヨウ化物の配合量は、水100重量部に対して、好ましくは1重量部~5重量部である。ヨウ化物の具体例は、上述のとおりである。架橋浴(ホウ酸水溶液)の液温は、好ましくは20℃~50℃である。好ましくは、架橋工程は上記第2のホウ酸水中延伸工程の前に行う。好ましい実施形態においては、染色工程、架橋工程および第2のホウ酸水中延伸工程をこの順で行う。
Tgは、TAインスツルメンツ製動的粘弾性測定装置RSAIIIを用い以下の測定条件で測定した。
サンプルサイズ:幅10mm、長さ30mm、
クランプ距離20mm、
測定モード:引っ張り、周波数:1Hz、昇温速度:5℃/分
動的粘弾性の測定を行い、tanδのピークトップの温度Tgとして採用した。
平均重合度2400、ケン化度99.9モル%の厚み75μmのポリビニルアルコールフィルムを、30℃の温水中に60秒間浸漬し膨潤させた。次いで、ヨウ素/ヨウ化カリウム(重量比=0.5/8)の濃度0.3%の水溶液に浸漬し、3.5倍まで延伸させながらフィルムを染色した。その後、65℃のホウ酸エステル水溶液中で、トータルの延伸倍率が6倍となるように延伸を行った。延伸後に、40℃のオーブンにて3分間乾燥を行い、PVA系偏光子X(SP値32.8、厚み23μm)を得た。
透明保護フィルムとして、厚み80μmのトリアセチルセルロースフィルム(TAC)(SP値23.3)を、ケン化・コロナ処理等を行わずに用いた(以下、ケン化・コロナ処理等を行っていないTACを、「未処理TAC」ともいう)。
活性エネルギー線として、紫外線(ガリウム封入メタルハライドランプ) 照射装置:Fusion UV Systems,Inc社製Light HAMMER10 バルブ:Vバルブ ピーク照度:1600mW/cm2、積算照射量1000/mJ/cm2(波長380~440nm)を使用した。なお、紫外線の照度は、Solatell社製Sola-Checkシステムを使用して測定した。
実施例1~7、比較例1~5
表2に記載の配合表に従い、各成分を混合して50℃で1時間撹拌し、実施例1~7、比較例1~5に係る活性エネルギー線硬化型接着剤組成物を得た。使用した各成分は以下のとおりである。
HEAA(ヒドロキシエチルアクリルアミド)、SP値29.6、ホモポリマーのTg123℃、興人社製
N-MAM-PC(N-メチロールアクリルアミド)、SP値31.5、ホモポリマーのTg150℃、笠野興産社製
(2)ラジカル重合性化合物(B)
アロニックスM-220(トリプロピレングリコールジアクリレート)、SP値19.0、ホモポリマーのTg69℃、東亞合成社製
ライトアクリレートDCP-A(トリシクロデカンジメタノールジアクリレート)、SP値20.3、ホモポリマーのTg134℃、共栄社化学社製
(3)ラジカル重合性化合物(C)
ACMO(アクリロイルモルホリン)、SP値22.9、ホモポリマーのTg150℃、興人社製
ワスマー2MA(N-メトキシメチルアクリルアミド)、SP値22.9、ホモポリマーのTg99℃、笠野興産社製
(4)ラジカル重合性化合物(D)
4HBA(4-ヒドロキシブチルアクリレート)、SP値23.8、ホモポリマーのTg-14℃、大阪有機化学工業社製
(5)光重合開始剤
KAYACURE DETX-S(ジエチルチオキサントン)、日本化薬社製
IRGACURE907(2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン)、BASF社製
(薄型偏光膜Yの作製とそれを用いた偏光板の作製)
薄型偏光膜Yを作製するため、まず、非晶性PET基材に24μm厚のPVA層が製膜された積層体を延伸温度130℃の空中補助延伸によって延伸積層体を生成し、次に、延伸積層体を染色によって着色積層体を生成し、さらに着色積層体を延伸温度65度のホウ酸水中延伸によって総延伸倍率が5.94倍になるように非晶性PET基材と一体に延伸された10μm厚のPVA層を含む光学フィルム積層体を生成した。このような2段延伸によって非晶性PET基材に製膜されたPVA層のPVA分子が高次に配向され、染色によって吸着されたヨウ素がポリヨウ素イオン錯体として一方向に高次に配向された高機能偏光膜Yを構成する、厚さ10μmのPVA層を含む光学フィルム積層体を生成することができた。更に、当該光学フィルム積層体の薄型偏光膜Yの表面に実施例1に係る活性エネルギー線硬化型接着剤組成物を塗布し、実施例1で使用した透明保護フィルムを接着剤塗布面から貼り合わせた後、非晶性PET基材を剥離し、薄型偏光膜Yを用いた偏光板(実施例8に係る偏光板)を作製した。
偏光板を偏光子の延伸方向と平行に200mm、直行方向に20mmの大きさに切り出し、透明保護フィルム(未処理TAC;SP値23.3)と偏光子(SP値32.8)との間にカッターナイフで切り込みを入れ、偏光板をガラス板に貼り合わせた。テンシロンにより、90度方向に保護フィルムと偏光子とを剥離速度500mm/minで剥離し、その剥離強度を測定した。また、剥離後の剥離面の赤外吸収スペクトルをATR法によって測定し、剥離界面を下記の基準に基づき評価した。
A:保護フィルムの凝集破壊
B:保護フィルム/接着剤層間の界面剥離
C:接着剤層/偏光子間の界面剥離
D:偏光子の凝集破壊
上記基準において、AおよびDは、接着力がフィルムの凝集力以上であるため、接着力が非常に優れることを意味する。一方、BおよびCは、保護フィルム/接着剤層(接着剤層/偏光子)界面の接着力が不足している(接着力が劣る)ことを意味する。これらを勘案して、AまたはDである場合の接着力を○、A・B(「保護フィルムの凝集破壊」と「保護フィルム/接着剤層間の界面剥離」とが同時に発生)あるいはA・C(「保護フィルムの凝集破壊」と「接着剤層/偏光子間の界面剥離」とが同時に発生)である場合の接着力を△、BまたはCである場合の接着力を×とする。
偏光板を、偏光子の延伸方向に50mm、垂直方向に25mmの長方形にカットした。かかる偏光板を60℃の温水に6時間浸漬した後の偏光子/透明保護フィルム間の剥れを目視観察し、下記の基準に基づき評価した。
○:剥れは確認されない
△:端部から剥れが生じているが、中心部の剥れは確認されない
×:前面に剥れが生じた
偏光板のアクリルフィルム面に粘着剤層を積層し、偏光子の延伸方向に200mm、垂直方向に400mmの長方形にカットした。ガラス板に上記偏光板をラミネートし、-40℃⇔85℃のヒートサイクル試験を行い、50サイクル後の偏光板を目視観察し、下記の基準に基づき評価した。
○:クラックの発生は見られない
△:偏光子の延伸方向に貫通しないクラックが発生した(クラック長さ200mm以下)
×:偏光子の延伸方向に貫通するクラックが発生した(クラック長さ200mm)
Claims (13)
- 硬化性成分として、ラジカル重合性化合物(A)、(B)および(C)を含有する活性エネルギー線硬化型接着剤組成物であって、組成物全量を100重量%としたとき、
SP値が29.0(kJ/m3)1/2以上32.0以下(kJ/m3)1/2であるラジカル重合性化合物(A)を20~60重量%、
SP値が18.0(kJ/m3)1/2以上21.0(kJ/m3)1/2未満であるラジカル重合性化合物(B)を10~30重量%、および
SP値が21.0(kJ/m3)1/2以上23.0(kJ/m3)1/2以下であるラジカル重合性化合物(C)を20~60重量%含有し、
前記ラジカル重合性化合物(A)、(B)および(C)それぞれのホモポリマーのガラス転移温度(Tg)がいずれも60℃以上であることを特徴とする活性エネルギー線硬化型接着剤組成物。 - 活性エネルギー線硬化型接着剤組成物中のラジカル重合性化合物の全量を100重量部としたとき、
前記ラジカル重合性化合物(A)、(B)および(C)を合計で85~100重量部含有し、さらにSP値が23.0(kJ/m3)1/2を超えて29.0(kJ/m3)1/2未満であるラジカル重合性化合物(D)を0~15重量部含有する請求項1に記載の活性エネルギー線硬化型接着剤組成物。 - 前記ラジカル重合性化合物(A)が、ヒドロキシエチルアクリルアミドおよび/またはN-メチロールアクリルアミドである請求項1または2に記載の活性エネルギー線硬化型接着剤組成物。
- 前記ラジカル重合性化合物(B)が、トリプロピレングリコールジアクリレートである請求項1~3のいずれかに記載の活性エネルギー線硬化型接着剤組成物。
- 前記ラジカル重合性化合物(C)が、アクリロイルモルホリンおよび/またはN-メトキシメチルアクリルアミドである請求項1~4のいずれかに記載の活性エネルギー線硬化型接着剤組成物。
- 偏光子の少なくとも一方の面に、接着剤層を介して波長365nmの光線透過率が5%未満である透明保護フィルムが設けられている偏光板であって、
前記接着剤層が、請求項1~7のいずれかに記載の活性エネルギー線硬化型接着剤組成物に活性エネルギー線を照射してなる硬化物層により形成されたものであることを特徴とする偏光板。 - 前記透明保護フィルムのSP値が29.0(kJ/m3)1/2以上33.0(kJ/m3)1/2未満である請求項8に記載の偏光板。
- 前記透明保護フィルムのSP値が18.0(kJ/m3)1/2以上24.0(kJ/m3)1/2未満である請求項8または9に記載の偏光板。
- 前記接着剤層のガラス転移温度(Tg)が60℃以上である請求項8~10のいずれかに記載の偏光板。
- 請求項8~11のいずれかに記載の偏光板が、少なくとも1枚積層されていることを特徴とする光学フィルム。
- 請求項8~11のいずれかに記載の偏光板、および/または請求項12に記載の光学フィルムが用いられていることを特徴とする画像表示装置。
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CN201180062580.1A CN103298897B (zh) | 2010-12-24 | 2011-12-13 | 活性能量射线固化型粘接剂组合物、偏光板、光学薄膜及图像显示装置 |
US13/996,911 US20130293949A1 (en) | 2010-12-24 | 2011-12-13 | Adhesive composition curable with active energy ray, polarizing plate, optical film, and image display device |
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TW201231603A (en) | 2012-08-01 |
CN103298897A (zh) | 2013-09-11 |
JP5313297B2 (ja) | 2013-10-09 |
TWI601800B (zh) | 2017-10-11 |
CN103298897B (zh) | 2015-11-25 |
TW201634620A (zh) | 2016-10-01 |
US20130293949A1 (en) | 2013-11-07 |
JP2012144690A (ja) | 2012-08-02 |
TWI534234B (zh) | 2016-05-21 |
KR20130143090A (ko) | 2013-12-30 |
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