WO2022004284A1 - Polarizing plate equipped with retardation layer and adhesive layer, and image display device using polarizing plate equipped with retardation layer and adhesive layer - Google Patents
Polarizing plate equipped with retardation layer and adhesive layer, and image display device using polarizing plate equipped with retardation layer and adhesive layer Download PDFInfo
- Publication number
- WO2022004284A1 WO2022004284A1 PCT/JP2021/021557 JP2021021557W WO2022004284A1 WO 2022004284 A1 WO2022004284 A1 WO 2022004284A1 JP 2021021557 W JP2021021557 W JP 2021021557W WO 2022004284 A1 WO2022004284 A1 WO 2022004284A1
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- WIPO (PCT)
- Prior art keywords
- adhesive layer
- pressure
- layer
- sensitive adhesive
- polarizing plate
- Prior art date
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Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Definitions
- the present invention relates to a polarizing plate with a retardation layer and an adhesive layer, and an image display device using the polarizing plate with a retardation layer and an adhesive layer.
- polarizing plate and a retardation plate are typically used in an image display device.
- a polarizing plate with a retardation layer in which a polarizing plate and a retardation plate are integrated is widely used (for example, Patent Document 1).
- the polarizing plate with a retardation layer may cause retardation unevenness in a high temperature environment, and as a result, color unevenness and light leakage may occur in the image display device in a high temperature environment.
- Re (450) and Re (550) are in-plane phase differences measured with light having wavelengths of 450 nm and 550 nm at 23 ° C., respectively.
- the Re (550) of the retardation layer is 100 nm to 200 nm, and the angle between the slow axis of the retardation layer and the absorption axis of the polarizing element is 40 ° to 50 ° or 130. ° to 140 °.
- the retardation layer has a thickness of 15 ⁇ m to 60 ⁇ m.
- the amount of glue slippage of the first pressure-sensitive adhesive layer after a heating test at 85 ° C. and 500 hours is 250 ⁇ m or less.
- the retardation layer comprises at least one binding group selected from the group consisting of carbonate bonds and ester bonds, structural units represented by the following general formula (1), and the following general formula (2). ), At least one structural unit selected from the group consisting of structural units represented by), a resin having a positive refractive index anisotropy; an acrylic resin; The amount is 0.5% by mass to 2.0% by mass, the acrylic resin contains 70% by mass or more of structural units derived from methyl methacrylate, and the weight average molecular weight Mw thereof is 10,000 to 200,000.
- R 1 to R 3 are independently bonded, substituted or unsubstituted alkylene groups having 1 to 4 carbon atoms, and R 4 to R 9 are independent of each other.
- Substituted alkoxy group with 1-10 carbon atoms substituted or unsubstituted aryloxy group with 1-10 carbon atoms, substituted or unsubstituted amino group, substituted or unsubstituted vinyl group with 1-10 carbon atoms, substituted or unsubstituted. It is an unsubstituted ethynyl group having 1 to 10 carbon atoms, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group; however, R 4 to R 9 are the same as each other.
- the amount of slippage of the pressure-sensitive adhesive layer between the polarizing element and the retardation layer and the polarizing plate with the retardation layer and the pressure-sensitive adhesive layer are provided.
- Re (450) is an in-plane phase difference of a film measured with light having a wavelength of 450 nm at 23 ° C.
- Phase difference in the thickness direction (Rth) is a phase difference in the thickness direction of the film measured with light having a wavelength of ⁇ nm at 23 ° C.
- Rth (450) is a phase difference in the thickness direction of a film measured with light having a wavelength of 450 nm at 23 ° C.
- the polarizing plate 10 includes a polarizing element 11, a first protective layer 12 arranged on one side of the polarizing element 11, and a second protective layer 13 arranged on the other side of the polarizing element 11. ..
- one of the first protective layer 12 and the second protective layer 13 may be omitted.
- the retardation layer 30 can also function as a protective layer for the polarizing element 11, the second protective layer 13 may be omitted.
- the angle formed by the slow axis of the retardation layer 30 and the absorption axis of the polarizing element 11 is preferably 40 ° to 50 °, more preferably 42 ° to 48 °, and even more preferably 44 ° to 46 °. It is particularly preferably about 45 °; or preferably 130 ° to 140 °, more preferably 132 ° to 138 °, still more preferably 134 ° to 136 °, and particularly preferably about. It is 135 °.
- the retarding layer and the polarizing plate with the pressure-sensitive adhesive layer may further have a conductive layer or an isotropic base material with a conductive layer (not shown).
- a conductive layer or an isotropic substrate with a conductive layer When a conductive layer or an isotropic substrate with a conductive layer is provided, the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer have a touch sensor incorporated between the image display cell (for example, an organic EL cell) and the polarizing plate. It can be applied to a so-called inner touch panel type input display device.
- the conductive layer or the isotropic base material with the conductive layer is typically provided between the retardation layer 30 and the second pressure-sensitive adhesive layer 40.
- the other retardation layer and the conductive layer or the isotropic base material with the conductive layer are typically provided in this order from the retardation layer 30 side.
- stretching typically includes immersing the laminate in an aqueous boric acid solution for stretching. Further, stretching may further comprise, if necessary, stretching the laminate in the air at a high temperature (eg, 95 ° C. or higher) prior to stretching in boric acid aqueous solution.
- a high temperature eg, 95 ° C. or higher
- the polymer film can be, for example, an extruded product of the above resin composition.
- the retardation layer and the polarizing plate with the adhesive layer are typically arranged on the visual recognition side of the image display device as described later, and the first protective layer 12 is typically arranged on the visual recognition side thereof. Therefore, the first protective layer 12 may be subjected to surface treatment such as hard coat treatment, antireflection treatment, anti-sticking treatment, and anti-glare treatment, if necessary. Further / or, if necessary, the first protective layer 12 is provided with a process for improving visibility when visually recognizing through polarized sunglasses (typically, a (elliptical) circularly polarized light function is imparted. (Giving an ultra-high phase difference) may be applied.
- polarized sunglasses typically, a (elliptical) circularly polarized light function is imparted.
- the retarding layer and the polarizing plate with the pressure-sensitive adhesive layer can be suitably applied to an image display device that can be used outdoors.
- the thickness of the retardation layer can be set so that it can function most appropriately as a ⁇ / 4 plate. In other words, the thickness can be set to obtain the desired in-plane phase difference. Specifically, the thickness is preferably 15 ⁇ m to 60 ⁇ m, more preferably 20 ⁇ m to 55 ⁇ m, and most preferably 20 ⁇ m to 50 ⁇ m.
- oligofluorene structural unit Details of the oligofluorene structural unit are described in, for example, International Publication No. 2015/159928. The publication is incorporated herein by reference.
- Aromatic bisphenol compounds 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane, 2,2-bis (4- (2-hydroxypropoxy) phenyl) propane, 1,3-bis (2-hydroxy) Dihydroxy compound having an ether group bonded to an aromatic group such as ethoxy) benzene, 4,4'-bis (2-hydroxyethoxy) biphenyl, bis (4- (2-hydroxyethoxy) phenyl) sulfone; terephthalic acid, phthalic acid.
- the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid component mentioned above can be used as a raw material for the polyester carbonate as the dicarboxylic acid itself, but depending on the production method, a dicarboxylic acid such as a methyl ester or a phenyl ester can be used. Dicarboxylic acid derivatives such as esters and dicarboxylic acid halides can also be used as raw materials.
- the resin used in the present invention preferably contains a structural unit represented by the following formula (3) as a copolymerization component among the structural units that can be introduced by the compound having an alicyclic structure.
- Spiroglycol can be used as the dihydroxy compound into which the structural unit of the formula (3) can be introduced.
- the structural unit represented by the formula (3) is preferably contained in an amount of 5% by mass or more and 90% by mass or less.
- the upper limit is more preferably 70% by mass or less, and particularly preferably 50% by mass or less.
- the lower limit is more preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 25% by mass or more.
- the resin used in the present invention preferably further contains a structural unit represented by the following formula (4) as a copolymerization component.
- dihydroxy compound into which the structural unit represented by the above formula (4) can be introduced examples include isosorbide (ISB), isomannide, and isoidet, which are in a stereoisomer relationship. These may be used individually by 1 type and may be used in combination of 2 or more type.
- the structural unit represented by the formula (4) has a characteristic of high water absorption, if the content of the structural unit represented by the formula (4) is not more than the upper limit, the molded product by water absorption The dimensional change can be suppressed to an allowable range.
- the resin used in the present invention may contain still another structural unit.
- such a structural unit may be referred to as "another structural unit”.
- 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, and 1,4-cyclohexanedicarboxylic acid (and its derivatives) are more preferable, and 1,4-cyclohexanedimethanol is more preferable.
- Methanol and tricyclodecanedimethanol are particularly preferred.
- a resin containing a structural unit derived from these monomers has an excellent balance of optical properties, heat resistance, mechanical properties, and the like. Further, since the polymerization reactivity of the diester compound is relatively low, it is preferable not to use a diester compound other than the diester compound containing an oligofluorene structural unit from the viewpoint of increasing the reaction efficiency.
- the glass transition temperature (Tg) of the resin used in the present invention is preferably 110 ° C. or higher and 160 ° C. or lower.
- the upper limit is more preferably 155 ° C or lower, more preferably 150 ° C or lower, and particularly preferably 145 ° C or lower.
- the lower limit is more preferably 120 ° C. or higher, and particularly preferably 130 ° C. or higher. If the glass transition temperature is out of the above range, the heat resistance tends to deteriorate, which may cause a dimensional change after film molding or deteriorate the reliability of quality under the usage conditions of the retardation film. On the other hand, if the glass transition temperature is excessively high, unevenness in the film thickness may occur during film molding, the film may become brittle, the stretchability may deteriorate, and the transparency of the film may be impaired.
- compositions and manufacturing method of the polycarbonate-based resin and the like are described in, for example, International Publication No. 2015/159928 (above). This description is incorporated herein by reference.
- Acrylic resin an acrylic resin as a thermoplastic resin is used.
- the monomer as a structural unit of the acrylic resin include the following compounds: methyl methacrylate, methacrylic acid, methyl acrylate, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate.
- Cyclododecyl methacrylate cyclododecyl acrylate.
- These may be used alone or in combination of two or more.
- Examples of the form in which two or more kinds of monomers are used in combination include copolymerization of two or more kinds of monomers, two or more blends of one kind of monomer homopolymer, and combinations thereof. Further, other monomers copolymerizable with these acrylic monomers (for example, olefin monomers and vinyl monomers) may be used in combination.
- Acrylic resin contains structural units derived from methyl methacrylate.
- the content of the structural unit derived from methyl methacrylate in the acrylic resin is preferably 70% by mass or more and 100% by mass or less.
- the lower limit is more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more. Within this range, excellent compatibility with the polycarbonate resin of the present invention can be obtained.
- As the structural unit other than methyl methacrylate it is preferable to use methyl acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene. Thermal stability can be improved by copolymerizing methyl acrylate.
- the refractive index of the acrylic resin can be adjusted by using phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene
- the transparent resin composition obtained by adjusting to the refractive index of the combined resin can be adjusted. It is possible to improve the sex.
- a reverse dispersion retardation film having excellent extensibility and phase difference expression and having a small haze can be obtained.
- the weight average molecular weight Mw of the acrylic resin is 10,000 or more and 200,000 or less.
- the lower limit is preferably 30,000 or more, and particularly preferably 50,000 or more.
- the upper limit is preferably 180,000 or less, and particularly preferably 150,000 or less.
- the above weight average molecular weight is a polystyrene-equivalent molecular weight measured by GPC.
- the acrylic resin does not substantially contain a branched structure from the viewpoint of compatibility. The fact that it does not contain a branched structure can be confirmed by the fact that the GPC curve of the acrylic resin is monomodal.
- twin-screw extruder it is preferable to use a twin-screw extruder in order to obtain the transparency of the resin that can withstand the optical film application. Furthermore, the residual low molecular weight components in the resin and the low molecular weight pyrolysis components during extrusion kneading may contaminate the cooling rolls and transport rolls in the film forming process and the stretching process, so that they can be removed. , It is preferable to use an extruder equipped with a vacuum vent.
- the resin composition comprises aromatic polycarbonate, aliphatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, for the purpose of modifying properties such as mechanical properties and / or solvent resistance.
- Synthetic resins such as ABS, AS, polylactic acid, polybutylene succinate, rubber, and combinations thereof may be further blended.
- the extrusion molding method particularly the melt extrusion molding method using a T-die, is particularly preferable from the viewpoint of film productivity and ease of subsequent stretching treatment.
- the molding conditions can be appropriately set according to the composition and type of the resin used, the characteristics desired for the retardation layer, and the like. In this way, a resin film containing a polycarbonate-based resin or the like and an acrylic-based resin can be obtained.
- a retardation layer having the desired optical characteristics for example, refractive index characteristics, in-plane retardation, Nz coefficient
- the stretching temperature of the film is a temperature equal to or lower than the glass transition temperature (Tg) of a polycarbonate resin or the like.
- Tg glass transition temperature
- the film is in a glass state at a temperature of Tg or less, so that stretching is practically impossible.
- an acrylic resin typically, polymethylmethacrylate
- Tg of the polycarbonate resin or the like is not substantially changed. The following can be stretched.
- the stretching temperature is preferably Tg to Tg-10 ° C, more preferably Tg to Tg-8 ° C, and even more preferably Tg to Tg-5 ° C.
- the film can be appropriately stretched even at a temperature higher than Tg as long as it is, for example, about Tg + 5 ° C., and for example, about Tg + 2 ° C.
- the retardation film constituting the retardation layer can be obtained.
- a commercially available stretched film can be used as the retardation film.
- a commercially available stretched film may be used as it is, or may be used after secondary processing (for example, stretching treatment, surface treatment) depending on the purpose.
- Specific examples of commercially available films include the trade name "Pure Ace RM" manufactured by Teijin Limited.
- the first adhesive layer 20 preferably has a glue slippage amount of 900 ⁇ m or less after a heating test at 85 ° C. and 500 hours. Is 600 ⁇ m or less, more preferably 500 ⁇ m or less, further preferably 400 ⁇ m or less, particularly preferably 300 ⁇ m or less, particularly preferably 250 ⁇ m or less, and most preferably 180 ⁇ m or less.
- the lower limit of the amount of slippage may be, for example, 20 ⁇ m.
- the creep value can be measured, for example, by the following procedure: a test sample cut out from an adhesive sheet is attached to a support plate at a 10 mm ⁇ 10 mm joint surface. In an environment of 85 ° C., a load of 500 gf is applied vertically downward with the support plate to which the test sample is attached fixed. The amount of deviation from the support plate after 1 second and 3600 seconds after applying the load is measured and designated as Cr 1 and Cr 3600 , respectively.
- ⁇ Cr obtained from Cr 1 and Cr 3600 by the following formula be the creep value.
- the first pressure-sensitive adhesive layer and / or the second pressure-sensitive adhesive layer has a storage elastic modulus at 85 ° C., preferably 1.0 ⁇ 10 4 Pa or more, preferably 2.0 ⁇ 10 4 Pa or more. , More preferably 5.0 ⁇ 10 4 Pa or more, and even more preferably 1.0 ⁇ 10 5 Pa or more.
- the storage elastic modulus is in such a range, it becomes easy to realize the desired amount of glue slippage and / or creep value.
- the storage modulus is less for example 3.0 ⁇ 10 6 Pa.
- the thickness of the first pressure-sensitive adhesive layer is preferably 2 ⁇ m to 50 ⁇ m, and more preferably 3 ⁇ m to 40 ⁇ m.
- the thickness of the second pressure-sensitive adhesive layer is preferably 4 ⁇ m to 30 ⁇ m, and more preferably 5 ⁇ m to 20 ⁇ m.
- the first adhesive layer has the desired amount of adhesive slippage
- the second adhesive layer has a desired amount of adhesive slippage. Any suitable configuration can be employed as long as the pressure-sensitive adhesive layer of the above has the desired creep value.
- the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer may be composed of the same pressure-sensitive adhesive, or may be composed of different pressure-sensitive adhesives.
- the constituent materials will be described with the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer collectively as a pressure-sensitive adhesive layer.
- Composition of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer for example, type of base polymer (polarity, Tg, softness), molecular weight), cross-linking structure (for example, type of cross-linking agent, distance between cross-linking points (molecular weight between cross-linking points), By adjusting the cross-linking density) and the like, the amount of glue slippage and / or the creep value can be controlled.
- type of base polymer polarity, Tg, softness
- molecular weight for example, type of cross-linking agent, distance between cross-linking points (molecular weight between cross-linking points)
- the base polymer pressure-sensitive adhesive layer is typically formed from a pressure-sensitive adhesive composition containing a (meth) acrylic polymer, a urethane-based polymer, a silicone-based polymer or a rubber-based polymer as a base polymer.
- a (meth) acrylic polymer is used as the base polymer
- the pressure-sensitive adhesive layer is formed from, for example, a pressure-sensitive adhesive composition containing the (meth) acrylic polymer (A).
- the (meth) acrylic polymer (A) contains an alkyl (meth) acrylate as a main component.
- the (meth) acrylic polymer (A) contains an alkyl (meth) acrylate as a main component.
- the alkyl (meth) acrylate is preferably 50% by weight or more in all the monomer components forming the (meth) acrylic polymer (A) from the viewpoint of improving the adhesiveness of the pressure-sensitive adhesive layer, and the alkyl (meth) acrylate is said.
- It can be arbitrarily set as the rest of the monomer other than acrylate.
- (meth) acrylate means acrylate and / or methacrylate.
- Examples of the alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer (A) include linear or branched alkyl groups having 1 to 18 carbon atoms.
- Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an amyl group, a hexyl group, a cyclohexyl group, a heptyl group, a 2-ethylhexyl group, an isooctyl group, a nonyl group and a decyl group.
- Alkyl (meth) acrylates can be used alone or in combination.
- the average carbon number of the alkyl group is preferably 3 to 10.
- the (meth) acrylic polymer (A) may contain a copolymerized monomer such as a carboxyl group-containing monomer (a1) and a hydroxyl group-containing monomer (a2) as a monomer component in addition to the alkyl (meth) acrylate. good.
- the copolymerizable monomers can be used alone or in combination.
- 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable, and 4-hydroxybutyl (meth) acrylate is more preferable, from the viewpoint of improving the durability of the pressure-sensitive adhesive layer.
- the content of the hydroxyl group-containing monomer (a2) is usually 0.01% by weight in all the monomer components forming the (meth) acrylic polymer (A). It is 10% by weight or less.
- the (meth) acrylic polymer (A) preferably contains, as a monomer component, a monomer having an unsaturated carbon double bond in which the glass transition temperature of the homopolymer is 0 ° C. or higher.
- a monomer having an unsaturated carbon double bond in which the glass transition temperature of the homopolymer is 0 ° C. or higher include an alkyl (meth) acrylate monomer and (meth) acrylic acid.
- the monomer (a3) is preferably a monomer having an unsaturated carbon double bond having a homopolymer glass transition temperature of 20 ° C. or higher, and has an unsaturated carbon double bond having a homopolymer glass transition temperature of 40 ° C. or higher. Monomers are more preferred.
- the proportion of the (meth) acrylic polymer (A) containing the monomer (a3) is not particularly limited.
- the content is usually 0.1% by weight to 40% by weight, more preferably 1% by weight to 30% by weight.
- the content is the total content when two or more kinds of monomers (a3) are used in combination.
- Examples of the monomer (a3) include methyl acrylate (Tg: 8 ° C.), methyl methacrylate (Tg: 105 ° C.), ethyl methacrylate (Tg: 65 ° C.), n-propyl acrylate (Tg: 3 ° C.), and n-propyl.
- the copolymerized monomer becomes a reaction point with the cross-linking agent when the pressure-sensitive adhesive composition contains the cross-linking agent described later.
- the carboxyl group-containing monomer and the hydroxyl group-containing monomer are highly reactive with the intermolecular cross-linking agent, they are preferably used for improving the cohesiveness and heat resistance of the obtained pressure-sensitive adhesive layer. Further, the carboxyl group-containing monomer is preferable in terms of achieving both durability and reworkability, and the hydroxyl group-containing monomer is preferable in terms of improving the reworkability.
- Another copolymerization monomer (a4) may be further used as the monomer component.
- the other copolymerizable monomer (a4) has a polymerizable functional group having an unsaturated double bond such as, for example, a (meth) acryloyl group or a vinyl group.
- a (meth) acryloyl group or a vinyl group By using the other copolymerization monomer (a4), the adhesiveness and heat resistance of the pressure-sensitive adhesive layer can be improved.
- the other copolymerization monomer (a4) can be used alone or in combination.
- Polyfunctional acrylates such as acrylates, tetramethylol methanetri (meth) acrylates, allyl (meth) acrylates, vinyl (meth) acrylates, epoxy acrylates, polyester acrylates, urethane acrylates; and divinylbenzene.
- the polyfunctional acrylate is preferably 1,6-hexanediol diacrylate or dipentaerythritol hexa (meth) acrylate.
- the other copolymerization monomer (a4) may be, for example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, (meth).
- (Meta) acrylic acid alkoxyalkyl esters such as 3-methoxypropyl acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate; 2-( Cyclic-polymerizable monomer such as methyl acrylate); epoxy group-containing monomer such as (meth) glycidyl acrylate, (meth) methyl glycidyl acrylate; sulfonic acid group-containing monomer such as sodium vinyl sulfonate; phosphoric acid Group-containing monomer; (meth) acrylate having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate; phenyl (meth) acrylate, (meth).
- the pressure-sensitive adhesive composition constituting the first pressure-sensitive adhesive layer and / or the pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer is preferably used as a monomer component of the (meth) acrylic polymer (A) (base polymer). May contain a (meth) acrylic acid ester having an aromatic hydrocarbon group, more preferably benzyl (meth) acrylic acid.
- the content of the other copolymerization monomer (a4) in the (meth) acrylic polymer is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, and particularly. It is preferably 5% by mass or less.
- the weight average molecular weight Mw of the (meth) acrylic polymer (A) is, for example, 200,000 to 3 million, preferably 1 million to 2.5 million, and more preferably 1.2 million to 2.5 million.
- a pressure-sensitive adhesive layer having excellent durability (particularly heat resistance) can be obtained. If the weight average molecular weight Mw exceeds 3 million, an increase in viscosity and / or gelation during polymer polymerization may occur.
- the pressure-sensitive adhesive composition can contain a reactive functional group-containing silane coupling agent.
- the reactive functional group is typically a functional group other than the acid anhydride group.
- the functional group other than the acid anhydride group include an epoxy group, a mercapto group, an amino group, an isocyanate group, an isocyanurate group, a vinyl group, a styryl group, an acetoacetyl group, a ureido group, a thiourea group and a (meth) acrylic group.
- Reactive functional group-containing silane coupling agents can be used alone or in combination.
- the blending amount of the reactive functional group-containing silane coupling agent is usually 100 parts by weight of the (meth) acrylic polymer (A). 0.001 part by weight or more and 5 parts by weight or less.
- the pressure-sensitive adhesive composition can contain a cross-linking agent.
- a cross-linking agent an organic cross-linking agent, a polyfunctional metal chelate and the like can be used.
- the organic cross-linking agent include an isocyanate-based cross-linking agent, a peroxide-based cross-linking agent, an epoxy-based cross-linking agent, and an imine-based cross-linking agent.
- a polyfunctional metal chelate is one in which a polyvalent metal is covalently or coordinated to an organic compound.
- a polyfunctional monomer can be used as a cross-linking agent.
- Crosslinkers can be used alone or in combination.
- the blending amount of the cross-linking agent in the pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer is at least such a lower limit, a high-temperature environment is obtained due to a synergistic effect with the effect of controlling the amount of glue slippage and the creep value.
- the retardation unevenness of the retarding layer and the polarizing plate with the adhesive layer underneath can be stably suppressed, and the color unevenness of the image display device in a high temperature environment can be stably suppressed.
- the pressure-sensitive adhesive composition may contain (meth) acrylic oligomers and / or ionic compounds. Further, the pressure-sensitive adhesive composition may contain an additive. Specific examples of additives include powders such as colorants and pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, and light. Stabilizers, UV absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particulates, foils and the like. Further, a redox system to which a reducing agent is added may be adopted within a controllable range.
- the pressure-sensitive adhesive composition constituting the first pressure-sensitive adhesive layer may contain a polyether compound having a reactive group (for example, a reactive silyl group).
- a polyether compound having a reactive group for example, a reactive silyl group.
- the type, number, combination, content, etc. of additives can be appropriately set according to the purpose.
- the content of the additive is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and further preferably 1 part by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer (A). be.
- the polarizing plate with the retardation layer and the pressure-sensitive adhesive layer according to the above items A to E can be applied to an image display device. Therefore, the embodiment of the present invention also includes an image display device using such a retardation layer and a polarizing plate with an adhesive layer.
- Typical examples of the image display device include a liquid crystal display device and an organic EL display device.
- the image display device according to the embodiment of the present invention is typically provided with the retardation layer and the polarizing plate with an adhesive layer according to the above items A to E on the visible side thereof.
- the image display device includes an image display panel.
- the image display panel includes an image display cell.
- the image display device may be referred to as an optical display device, the image display panel may be referred to as an optical display panel, and the image display cell may be referred to as an optical display cell.
- the polarizing plates with the retardation layer and the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples were cut out to a size of 13 inches and used as test samples.
- the test sample was subjected to a heating test at 85 ° C. and 500 hours, and after the heating test, the amount of protrusion of the first pressure-sensitive adhesive layer protruding from the end faces of the polarizing element and the retardation layer was observed with an objective lens (20 times). It was measured.
- the length of the portion of the first pressure-sensitive adhesive layer having the largest protrusion was defined as the amount of adhesive slippage.
- the transmitted light was set to 0 (zero), and adjustment was made so that the light was reflected.
- ⁇ Cr Cr 3600- Cr 1 (3) Color unevenness
- the polarizing plate with the retardation layer and the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was cut out to a size of 13 inches and bonded to a glass plate via a second pressure-sensitive adhesive layer as a test sample.
- the test sample was subjected to a heating test at 85 ° C. for 500 hours, and after the heating test, it was placed on a reflective sheet (DMS vapor deposition film manufactured by Toray Film Processing Co., Ltd.) and a spectrophotometer (manufactured by Konica Minolta Co., Ltd., product name).
- the primary sample was then autoclaved at 50 ° C. and 5 atm for 15 minutes (the sample after autoclaving is referred to as the "initial secondary sample”).
- the initial secondary sample was then subjected to treatment at 85 ° C. for 500 hours (the heated sample is referred to as the "heated secondary sample”).
- the initial secondary sample and the heated secondary sample were placed on a backlight of 10,000 candelas, light leakage was visually observed, and evaluation was performed according to the following criteria. A: No light leakage occurs.
- test sample after the durability test was visually observed and evaluated according to the following criteria.
- (6) Dimensional change rate due to humidification (humidification TMA test) A second retardation film is bonded to the first retardation film obtained in the manufacturing example so as to form a combination of the first retardation layer and the second retardation layer shown in Table 1, and the retardation is obtained. A laminate of films was obtained.
- the obtained laminate was cut into 20 mm (slow-phase axial direction of the first retardation film) ⁇ 5 mm (phase-advancing axial direction of the first retardation film) to prepare a measurement sample.
- the second retardation film was not bonded to the first retardation film, and the first retardation film was cut to obtain a measurement sample.
- the length of the measurement sample was 60 ° C / 85% RH.
- the dimensional change rate in the direction was measured.
- the holding time at 25 ° C./50% RH was 30 minutes, the holding time at 50 ° C./60% RH was 60 minutes, and the holding time at 60 ° C./85% RH was 240 minutes.
- the heating rate between 25 ° C./50% RH and 60 ° C./50% RH was 0.4 ° C./min. The results are shown in Table 1.
- a long resin film having a thickness of 135 ⁇ m was prepared by using a film forming apparatus equipped with a chill roll (set temperature: 120 to 130 ° C.) and a winder.
- the obtained long resin film was stretched in the width direction at a stretching temperature of 133 ° C. and a stretching ratio of 2.8 times to obtain a retardation film R1 having a thickness of 48 ⁇ m.
- the Re (550) of the retardation film R1 was 141 nm, the Re (450) / Re (550) was 0.82, and the Nz coefficient was 1.12.
- the reduced viscosity of PC1 is 0.46 dL / g, Mw 48,000, refractive index n D is 1.526, a melt viscosity of 2480Pa ⁇ s, a glass transition temperature of 139 ° C., the photoelastic coefficient of 9 ⁇ 10 -12 [ m 2 / N] and the wavelength dispersion Re (450) / Re (550) were 0.85.
- the pellets of the resin composition thus obtained are vacuum-dried at 100 ° C. for 6 hours or more, and then a single-screw extruder (manufactured by Isuzu Kakohki Co., Ltd., screw diameter 25 mm, cylinder set temperature: 250 ° C.).
- a single-screw extruder manufactured by Isuzu Kakohki Co., Ltd., screw diameter 25 mm, cylinder set temperature: 250 ° C.
- a film-forming device equipped with a T-die (width 300 mm, set temperature: 220 ° C), chill roll (set temperature: 120-130 ° C), and a winder, a long length of 3 m in length, 200 mm in width, and 100 ⁇ m in thickness.
- An unstretched film was produced. This long unstretched film was stretched at a stretching temperature of Tg and a stretching ratio of 2.4 times.
- the retardation film R2 constituting the retardation layer was obtained.
- the retardation film R2 exhibited a refractive index characteristic of nx> ny> nz, Re (550) was 145 nm, and Re (450) / Re (550) was 0.85.
- the prepared liquid crystal coating liquid is applied to the surface of a norbornene-based resin film (manufactured by Zeon Corporation, trade name "Zeonex”), which is a base film, with a bar coater, and then heated at 80 ° C. for 4 minutes. And dried to orient the liquid crystal contained in the coating film.
- the coating film was cured by irradiation with ultraviolet rays to form a second retardation film, the liquid crystal solidified layer R4 (thickness 0.58 ⁇ m), on the base film.
- the weight ratio of iodine and potassium iodide was adjusted so that the simple substance transmittance of the obtained polarizing element was 45.0% and the weight ratio was 1: 7. However, it was stretched 1.4 times.
- the cross-linking treatment adopted a two-step cross-linking treatment, and the first-step cross-linking treatment was carried out 1.2 times while being treated with an aqueous solution in which boric acid and potassium iodide were dissolved at 40 ° C.
- the boric acid content of the aqueous solution of the first-step crosslinking treatment was 5.0% by weight, and the potassium iodide content was 3.0% by weight.
- the second-step cross-linking treatment was carried out by stretching 1.6 times while treating with an aqueous solution in which boric acid and potassium iodide were dissolved at 65 ° C.
- the boric acid content of the aqueous solution of the second step cross-linking treatment was 4.3% by weight, and the potassium iodide content was 5.0% by weight.
- the washing treatment was carried out with an aqueous potassium iodide solution at 20 ° C.
- the potassium iodide content of the aqueous solution of the washing treatment was set to 2.6% by weight.
- the drying process was carried out at 70 ° C. for 5 minutes to obtain a stator.
- a triacetyl cellulose film (thickness 40 ⁇ m, manufactured by Konica Minolta, trade name “KC4UYW”) is bonded to one side of the above-mentioned polarizing element via a polyvinyl alcohol-based adhesive, and a polarizing plate having a protective layer / polarizing element configuration is attached. Obtained P1.
- thermoplastic resin base material an amorphous isophthal copolymerized polyethylene terephthalate film (thickness: 100 ⁇ m) having a long shape and a Tg of about 75 ° C. was used, and one side of the resin base material was subjected to corona treatment.
- a PVA aqueous solution (coating solution) was prepared by dissolving 13 parts by weight of potassium iodide in water.
- the PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60 ° C. to form a PVA-based resin layer having a thickness of 13 ⁇ m, and a laminate was prepared.
- the obtained laminate was uniaxially stretched 2.4 times in the vertical direction (longitudinal direction) in an oven at 130 ° C. (aerial auxiliary stretching treatment). Next, the laminate was immersed in an insolubilizing bath at a liquid temperature of 40 ° C.
- polarizing plate Preparation of polarizing plate
- a cycloolefin-based film (ZF-12, 23 ⁇ m, manufactured by Nippon Zeon Corporation) as a protective layer was applied to the surface of the obtained polarizing element (the surface opposite to the resin substrate) via an ultraviolet curable adhesive. I pasted them together.
- the curable adhesive was coated so as to have a total thickness of about 1.0 ⁇ m, and bonded using a roll machine. Then, a UV ray was irradiated from the cycloolefin film side to cure the adhesive.
- the resin base material was peeled off to obtain a polarizing plate P2 having a cycloolefin-based film (protective layer) / polarizing element.
- the prepared adhesive was applied to one side of a polyethylene terephthalate film (separator film, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) treated with a silicone-based release agent so that the thickness of the adhesive layer after drying was 12 ⁇ m. After that, the coating film of the pressure-sensitive adhesive was dried to form a first pressure-sensitive adhesive layer. Further, the second pressure-sensitive adhesive layer was formed in the same manner as the formation of the first pressure-sensitive adhesive layer, except that the pressure-sensitive adhesive layer was applied so as to have a thickness of 15 ⁇ m after drying.
- Examples 1 to 9 and Comparative Examples 1 to 2 The first pressure-sensitive adhesive layer formed on the surface of the separator film was transferred to a polarizing plate to prepare a polarizing plate with a pressure-sensitive adhesive layer. Further, the second pressure-sensitive adhesive layer formed on the surface of the separator film was transferred to the retardation film to prepare a retardation film with a pressure-sensitive adhesive layer. Then, the polarizing plate with the pressure-sensitive adhesive layer and the retardation film with the pressure-sensitive adhesive layer are used as a polarizing plate, a first retardation film (phase difference layer), a second retardation film (liquid crystal solidifying layer), and a pressure-sensitive adhesive (first).
- the pressure-sensitive adhesive layer (1) and the pressure-sensitive adhesive layer (2) were combined in the order shown in Table 1 to prepare a retardation layer and a polarizing plate with a pressure-sensitive adhesive layer.
- the polarizing plate and the first retardation layer are bonded so that the absorption axis of the polarizing element and the slow axis of the retardation film form an angle of 45 °.
- the obtained retardation layer and the polarizing plate with the pressure-sensitive adhesive layer were subjected to the evaluation of the above-mentioned color unevenness, light leakage and durability. The results are shown in Table 1 together with the amount of glue slippage of the first pressure-sensitive adhesive layer and the creep value of the second pressure-sensitive adhesive layer.
- the polarizing plate with the retardation layer and the pressure-sensitive adhesive layer of the present invention can be suitably used for an image display device (typically, a liquid crystal display device or an organic EL display device).
- an image display device typically, a liquid crystal display device or an organic EL display device.
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Abstract
Provided is a polarizing plate that is equipped with a retardation layer and an adhesive layer and by which an image display device can be realized in which phase difference unevenness is suppressed in high temperature environments, and color unevenness and light leakage is suppressed in high temperature environments. The polarizing plate equipped with a retardation layer and an adhesive layer according to an embodiment of the present invention comprises: a polarizing plate including a polarizer; a retardation layer attached to the polarizing plate via a first adhesive layer; and a second adhesive layer provided as an outermost layer, on the retardation layer, on the side opposite the polarizing plate. The retardation layer is constituted of a stretched film of a resin film and satisfies the relationship Re (450) < Re (550). A paste shifting amount of the first adhesive layer after a heating test at 85℃ for 500 hours is 900 μm or less, and a creep value of the second adhesive layer at 85℃ is 40 μm or less.
Description
本発明は、位相差層および粘着剤層付偏光板、ならびに、該位相差層および粘着剤層付偏光板を用いた画像表示装置に関する。
The present invention relates to a polarizing plate with a retardation layer and an adhesive layer, and an image display device using the polarizing plate with a retardation layer and an adhesive layer.
近年、液晶表示装置およびエレクトロルミネセンス(EL)表示装置(例えば、有機EL表示装置、無機EL表示装置)に代表される画像表示装置が急速に普及している。画像表示装置には、代表的には偏光板および位相差板が用いられている。実用的には、偏光板と位相差板とを一体化した位相差層付偏光板が広く用いられている(例えば、特許文献1)。しかし、位相差層付偏光板は、高温環境下において位相差ムラが発生し、その結果、高温環境下において画像表示装置に色ムラおよび光漏れが発生する場合がある。
In recent years, image display devices represented by liquid crystal displays and electroluminescence (EL) display devices (for example, organic EL display devices and inorganic EL display devices) have rapidly become widespread. A polarizing plate and a retardation plate are typically used in an image display device. Practically, a polarizing plate with a retardation layer in which a polarizing plate and a retardation plate are integrated is widely used (for example, Patent Document 1). However, the polarizing plate with a retardation layer may cause retardation unevenness in a high temperature environment, and as a result, color unevenness and light leakage may occur in the image display device in a high temperature environment.
本発明は上記従来の課題を解決するためになされたものであり、その主たる目的は、高温環境下において位相差ムラが抑制され、高温環境下において色ムラおよび光漏れが抑制された画像表示装置を実現し得る位相差層および粘着剤層付偏光板を提供することにある。
The present invention has been made to solve the above-mentioned conventional problems, and its main purpose is to suppress phase difference unevenness in a high temperature environment, and to suppress color unevenness and light leakage in a high temperature environment. It is an object of the present invention to provide a polarizing plate with a retardation layer and a pressure-sensitive adhesive layer that can realize the above.
本発明の実施形態による位相差層および粘着剤層付偏光板は、偏光子を含む偏光板と、該偏光板に第1の粘着剤層を介して貼り合わせられた位相差層と、該位相差層の該偏光板と反対側に最外層として設けられた第2の粘着剤層と、を有する。該位相差層は、樹脂フィルムの延伸フィルムで構成され、Re(450)<Re(550)の関係を満足する。該第1の粘着剤層の85℃および500時間の加熱試験後の糊ずれ量は900μm以下であり、該第2の粘着剤層の85℃におけるクリープ値は40μm以下である。ここで、Re(450)およびRe(550)は、それぞれ、23℃における波長450nmおよび550nmの光で測定した面内位相差である。
1つの実施形態においては、上記位相差層のRe(550)は100nm~200nmであり、該位相差層の遅相軸と上記偏光子の吸収軸とのなす角度は40°~50°または130°~140°である。
1つの実施形態においては、上記位相差層の厚みは15μm~60μmである。
1つの実施形態においては、上記第1の粘着剤層の85℃および500時間の加熱試験後の糊ずれ量は250μm以下である。
1つの実施形態においては、上記第2の粘着剤層を構成する粘着剤組成物は、ベースポリマー100重量部に対して架橋剤を1.5重量部以上含む。
1つの実施形態においては、上記第2の粘着剤層を構成する粘着剤組成物は、ベースポリマー100重量部に対して架橋剤を5重量部以上含む。
1つの実施形態においては、上記位相差層および粘着剤層付偏光板は、上記位相差層と上記第2の粘着剤層との間に、屈折率特性がnz>nx=nyの関係を示す別の位相差層をさらに有する。
1つの実施形態においては、上記位相差層は、カーボネート結合およびエステル結合からなる群から選択される少なくとも1つの結合基と、下記一般式(1)で表される構造単位および下記一般式(2)で表される構造単位からなる群から選択される少なくとも1つの構造単位とを含み、正の屈折率異方性を有する樹脂と;アクリル系樹脂と;を含有し、該アクリル系樹脂の含有量が0.5質量%~2.0質量%であり、該アクリル系樹脂が、メタクリル酸メチル由来の構造単位を70質量%以上含有し、その重量平均分子量Mwが10,000~200,000である:
一般式(1)および(2)中、R1~R3は、それぞれ独立に、直接結合、置換または非置換の炭素数1~4のアルキレン基であり、R4~R9は、それぞれ独立に、水素原子、置換または非置換の炭素数1~10のアルキル基、置換または非置換の炭素数4~10のアリール基、置換または非置換の炭素数1~10のアシル基、置換または非置換の炭素数1~10のアルコキシ基、置換または非置換の炭素数1~10のアリールオキシ基、置換または非置換のアミノ基、置換または非置換の炭素数1~10のビニル基、置換または非置換の炭素数1~10のエチニル基、置換基を有する硫黄原子、置換基を有するケイ素原子、ハロゲン原子、ニトロ基、またはシアノ基であり;ただし、R4~R9は、互いに同一であっても、異なっていてもよく、 R4~R9のうち隣接する少なくとも2つの基が互いに結合して環を形成していてもよい。
1つの実施形態においては、上記位相差層は、25℃/50%RH、60℃/50%RH、60℃/85%RHの順に環境を変化させる加湿TMA試験において遅相軸方向の寸法変化率が0.28%以下である。
1つの実施形態においては、上記位相差層は、上記別の位相差層が貼り合わされた状態で、25℃/50%RH、60℃/50%RH、60℃/85%RHの順に環境を変化させる加湿TMA試験において遅相軸方向の寸法変化率が0.28%以下である。
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、上記の位相差層および粘着剤層付偏光板を備える。 The polarizing plate with the retardation layer and the pressure-sensitive adhesive layer according to the embodiment of the present invention includes a polarizing plate containing a polarizing element, and a retardation layer bonded to the polarizing plate via a first pressure-sensitive adhesive layer. It has a second pressure-sensitive adhesive layer provided as an outermost layer on the opposite side of the retardation layer from the polarizing plate. The retardation layer is composed of a stretched film of a resin film, and satisfies the relationship of Re (450) <Re (550). The amount of glue slippage of the first pressure-sensitive adhesive layer after a heating test at 85 ° C. and 500 hours is 900 μm or less, and the creep value of the second pressure-sensitive adhesive layer at 85 ° C. is 40 μm or less. Here, Re (450) and Re (550) are in-plane phase differences measured with light having wavelengths of 450 nm and 550 nm at 23 ° C., respectively.
In one embodiment, the Re (550) of the retardation layer is 100 nm to 200 nm, and the angle between the slow axis of the retardation layer and the absorption axis of the polarizing element is 40 ° to 50 ° or 130. ° to 140 °.
In one embodiment, the retardation layer has a thickness of 15 μm to 60 μm.
In one embodiment, the amount of glue slippage of the first pressure-sensitive adhesive layer after a heating test at 85 ° C. and 500 hours is 250 μm or less.
In one embodiment, the pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer contains 1.5 parts by weight or more of a cross-linking agent with respect to 100 parts by weight of the base polymer.
In one embodiment, the pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer contains 5 parts by weight or more of a cross-linking agent with respect to 100 parts by weight of the base polymer.
In one embodiment, the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer show a relationship in which the refractive index characteristic is nz> nx = ny between the retardation layer and the second pressure-sensitive adhesive layer. It further has another retardation layer.
In one embodiment, the retardation layer comprises at least one binding group selected from the group consisting of carbonate bonds and ester bonds, structural units represented by the following general formula (1), and the following general formula (2). ), At least one structural unit selected from the group consisting of structural units represented by), a resin having a positive refractive index anisotropy; an acrylic resin; The amount is 0.5% by mass to 2.0% by mass, the acrylic resin contains 70% by mass or more of structural units derived from methyl methacrylate, and the weight average molecular weight Mw thereof is 10,000 to 200,000. Is:
In the general formulas (1) and (2), R 1 to R 3 are independently bonded, substituted or unsubstituted alkylene groups having 1 to 4 carbon atoms, and R 4 to R 9 are independent of each other. A hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 4 to 10 carbon atoms, a substituted or unsubstituted acyl group having 1 to 10 carbon atoms, substituted or unsubstituted. Substituted alkoxy group with 1-10 carbon atoms, substituted or unsubstituted aryloxy group with 1-10 carbon atoms, substituted or unsubstituted amino group, substituted or unsubstituted vinyl group with 1-10 carbon atoms, substituted or unsubstituted. It is an unsubstituted ethynyl group having 1 to 10 carbon atoms, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group; however, R 4 to R 9 are the same as each other. even, different even if well, may form a ring adjacent the at least two groups are bonded to each other among the R 4 ~ R 9.
In one embodiment, the retard layer has a dimensional change in the slow axial direction in a humidified TMA test in which the environment is changed in the order of 25 ° C / 50% RH, 60 ° C / 50% RH, 60 ° C / 85% RH. The rate is 0.28% or less.
In one embodiment, the retardation layer is placed in the order of 25 ° C./50% RH, 60 ° C./50% RH, and 60 ° C./85% RH in a state where the other retardation layers are bonded to each other. In the changing humidification TMA test, the dimensional change rate in the slow axis direction is 0.28% or less.
According to another aspect of the present invention, an image display device is provided. This image display device includes the above-mentioned retardation layer and a polarizing plate with an adhesive layer.
1つの実施形態においては、上記位相差層のRe(550)は100nm~200nmであり、該位相差層の遅相軸と上記偏光子の吸収軸とのなす角度は40°~50°または130°~140°である。
1つの実施形態においては、上記位相差層の厚みは15μm~60μmである。
1つの実施形態においては、上記第1の粘着剤層の85℃および500時間の加熱試験後の糊ずれ量は250μm以下である。
1つの実施形態においては、上記第2の粘着剤層を構成する粘着剤組成物は、ベースポリマー100重量部に対して架橋剤を1.5重量部以上含む。
1つの実施形態においては、上記第2の粘着剤層を構成する粘着剤組成物は、ベースポリマー100重量部に対して架橋剤を5重量部以上含む。
1つの実施形態においては、上記位相差層および粘着剤層付偏光板は、上記位相差層と上記第2の粘着剤層との間に、屈折率特性がnz>nx=nyの関係を示す別の位相差層をさらに有する。
1つの実施形態においては、上記位相差層は、カーボネート結合およびエステル結合からなる群から選択される少なくとも1つの結合基と、下記一般式(1)で表される構造単位および下記一般式(2)で表される構造単位からなる群から選択される少なくとも1つの構造単位とを含み、正の屈折率異方性を有する樹脂と;アクリル系樹脂と;を含有し、該アクリル系樹脂の含有量が0.5質量%~2.0質量%であり、該アクリル系樹脂が、メタクリル酸メチル由来の構造単位を70質量%以上含有し、その重量平均分子量Mwが10,000~200,000である:
1つの実施形態においては、上記位相差層は、25℃/50%RH、60℃/50%RH、60℃/85%RHの順に環境を変化させる加湿TMA試験において遅相軸方向の寸法変化率が0.28%以下である。
1つの実施形態においては、上記位相差層は、上記別の位相差層が貼り合わされた状態で、25℃/50%RH、60℃/50%RH、60℃/85%RHの順に環境を変化させる加湿TMA試験において遅相軸方向の寸法変化率が0.28%以下である。
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、上記の位相差層および粘着剤層付偏光板を備える。 The polarizing plate with the retardation layer and the pressure-sensitive adhesive layer according to the embodiment of the present invention includes a polarizing plate containing a polarizing element, and a retardation layer bonded to the polarizing plate via a first pressure-sensitive adhesive layer. It has a second pressure-sensitive adhesive layer provided as an outermost layer on the opposite side of the retardation layer from the polarizing plate. The retardation layer is composed of a stretched film of a resin film, and satisfies the relationship of Re (450) <Re (550). The amount of glue slippage of the first pressure-sensitive adhesive layer after a heating test at 85 ° C. and 500 hours is 900 μm or less, and the creep value of the second pressure-sensitive adhesive layer at 85 ° C. is 40 μm or less. Here, Re (450) and Re (550) are in-plane phase differences measured with light having wavelengths of 450 nm and 550 nm at 23 ° C., respectively.
In one embodiment, the Re (550) of the retardation layer is 100 nm to 200 nm, and the angle between the slow axis of the retardation layer and the absorption axis of the polarizing element is 40 ° to 50 ° or 130. ° to 140 °.
In one embodiment, the retardation layer has a thickness of 15 μm to 60 μm.
In one embodiment, the amount of glue slippage of the first pressure-sensitive adhesive layer after a heating test at 85 ° C. and 500 hours is 250 μm or less.
In one embodiment, the pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer contains 1.5 parts by weight or more of a cross-linking agent with respect to 100 parts by weight of the base polymer.
In one embodiment, the pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer contains 5 parts by weight or more of a cross-linking agent with respect to 100 parts by weight of the base polymer.
In one embodiment, the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer show a relationship in which the refractive index characteristic is nz> nx = ny between the retardation layer and the second pressure-sensitive adhesive layer. It further has another retardation layer.
In one embodiment, the retardation layer comprises at least one binding group selected from the group consisting of carbonate bonds and ester bonds, structural units represented by the following general formula (1), and the following general formula (2). ), At least one structural unit selected from the group consisting of structural units represented by), a resin having a positive refractive index anisotropy; an acrylic resin; The amount is 0.5% by mass to 2.0% by mass, the acrylic resin contains 70% by mass or more of structural units derived from methyl methacrylate, and the weight average molecular weight Mw thereof is 10,000 to 200,000. Is:
In one embodiment, the retard layer has a dimensional change in the slow axial direction in a humidified TMA test in which the environment is changed in the order of 25 ° C / 50% RH, 60 ° C / 50% RH, 60 ° C / 85% RH. The rate is 0.28% or less.
In one embodiment, the retardation layer is placed in the order of 25 ° C./50% RH, 60 ° C./50% RH, and 60 ° C./85% RH in a state where the other retardation layers are bonded to each other. In the changing humidification TMA test, the dimensional change rate in the slow axis direction is 0.28% or less.
According to another aspect of the present invention, an image display device is provided. This image display device includes the above-mentioned retardation layer and a polarizing plate with an adhesive layer.
本発明の実施形態によれば、位相差層および粘着剤層付偏光板において、偏光子と位相差層との間の粘着剤層の糊ずれ量ならびに位相差層および粘着剤層付偏光板を画像表示セルに貼り合わせるための粘着剤層のクリープ値を組み合わせて最適化することにより、高温環境下において位相差ムラが抑制された位相差層および粘着剤層付偏光板を実現することができる。その結果、高温環境下において色ムラおよび光漏れが抑制された画像表示装置を実現することができる。
According to the embodiment of the present invention, in the polarizing plate with a retardation layer and the pressure-sensitive adhesive layer, the amount of slippage of the pressure-sensitive adhesive layer between the polarizing element and the retardation layer and the polarizing plate with the retardation layer and the pressure-sensitive adhesive layer are provided. By optimizing the combination of the creep values of the pressure-sensitive adhesive layer for bonding to the image display cell, it is possible to realize a retardation layer in which retardation unevenness is suppressed and a polarizing plate with a pressure-sensitive adhesive layer in a high-temperature environment. .. As a result, it is possible to realize an image display device in which color unevenness and light leakage are suppressed in a high temperature environment.
以下、本発明の代表的な実施形態について説明するが、本発明はこれらの実施形態には限定されない。
Hereinafter, typical embodiments of the present invention will be described, but the present invention is not limited to these embodiments.
(用語および記号の定義)
本明細書における用語および記号の定義は下記の通りである。
(1)屈折率(nx、ny、nz)
「nx」は面内の屈折率が最大になる方向(すなわち、遅相軸方向)の屈折率であり、「ny」は面内で遅相軸と直交する方向(すなわち、進相軸方向)の屈折率であり、「nz」は厚み方向の屈折率である。
(2)面内位相差(Re)
「Re(λ)」は、23℃における波長λnmの光で測定したフィルムの面内位相差である。例えば、「Re(450)」は、23℃における波長450nmの光で測定したフィルムの面内位相差である。Re(λ)は、フィルムの厚みをd(nm)としたとき、式:Re=(nx-ny)×dによって求められる。
(3)厚み方向の位相差(Rth)
「Rth(λ)」は、23℃における波長λnmの光で測定したフィルムの厚み方向の位相差である。例えば、「Rth(450)」は、23℃における波長450nmの光で測定したフィルムの厚み方向の位相差である。Rth(λ)は、フィルムの厚みをd(nm)としたとき、式:Rth=(nx-nz)×dによって求められる。
(4)Nz係数
Nz係数は、Nz=Rth/Reによって求められる。
(5)角度
本明細書において角度に言及するときは、特に明記しない限り、当該角度は時計回りおよび反時計回りの両方の方向の角度を包含する。 (Definition of terms and symbols)
Definitions of terms and symbols herein are as follows.
(1) Refractive index (nx, ny, nz)
"Nx" is the refractive index in the direction in which the refractive index in the plane is maximized (that is, the slow-phase axis direction), and "ny" is the direction orthogonal to the slow-phase axis in the plane (that is, the phase-advancing axis direction). Is the refractive index of, and "nz" is the refractive index in the thickness direction.
(2) In-plane phase difference (Re)
“Re (λ)” is the in-plane phase difference of the film measured with light having a wavelength of λ nm at 23 ° C. For example, "Re (450)" is an in-plane phase difference of a film measured with light having a wavelength of 450 nm at 23 ° C. Re (λ) is obtained by the formula: Re = (nx−ny) × d, where d (nm) is the thickness of the film.
(3) Phase difference in the thickness direction (Rth)
“Rth (λ)” is a phase difference in the thickness direction of the film measured with light having a wavelength of λ nm at 23 ° C. For example, "Rth (450)" is a phase difference in the thickness direction of a film measured with light having a wavelength of 450 nm at 23 ° C. Rth (λ) is obtained by the formula: Rth = (nx-nz) × d, where d (nm) is the thickness of the film.
(4) Nz coefficient The Nz coefficient is obtained by Nz = Rth / Re.
(5) Angle When referring to an angle herein, the angle includes angles in both clockwise and counterclockwise directions, unless otherwise stated.
本明細書における用語および記号の定義は下記の通りである。
(1)屈折率(nx、ny、nz)
「nx」は面内の屈折率が最大になる方向(すなわち、遅相軸方向)の屈折率であり、「ny」は面内で遅相軸と直交する方向(すなわち、進相軸方向)の屈折率であり、「nz」は厚み方向の屈折率である。
(2)面内位相差(Re)
「Re(λ)」は、23℃における波長λnmの光で測定したフィルムの面内位相差である。例えば、「Re(450)」は、23℃における波長450nmの光で測定したフィルムの面内位相差である。Re(λ)は、フィルムの厚みをd(nm)としたとき、式:Re=(nx-ny)×dによって求められる。
(3)厚み方向の位相差(Rth)
「Rth(λ)」は、23℃における波長λnmの光で測定したフィルムの厚み方向の位相差である。例えば、「Rth(450)」は、23℃における波長450nmの光で測定したフィルムの厚み方向の位相差である。Rth(λ)は、フィルムの厚みをd(nm)としたとき、式:Rth=(nx-nz)×dによって求められる。
(4)Nz係数
Nz係数は、Nz=Rth/Reによって求められる。
(5)角度
本明細書において角度に言及するときは、特に明記しない限り、当該角度は時計回りおよび反時計回りの両方の方向の角度を包含する。 (Definition of terms and symbols)
Definitions of terms and symbols herein are as follows.
(1) Refractive index (nx, ny, nz)
"Nx" is the refractive index in the direction in which the refractive index in the plane is maximized (that is, the slow-phase axis direction), and "ny" is the direction orthogonal to the slow-phase axis in the plane (that is, the phase-advancing axis direction). Is the refractive index of, and "nz" is the refractive index in the thickness direction.
(2) In-plane phase difference (Re)
“Re (λ)” is the in-plane phase difference of the film measured with light having a wavelength of λ nm at 23 ° C. For example, "Re (450)" is an in-plane phase difference of a film measured with light having a wavelength of 450 nm at 23 ° C. Re (λ) is obtained by the formula: Re = (nx−ny) × d, where d (nm) is the thickness of the film.
(3) Phase difference in the thickness direction (Rth)
“Rth (λ)” is a phase difference in the thickness direction of the film measured with light having a wavelength of λ nm at 23 ° C. For example, "Rth (450)" is a phase difference in the thickness direction of a film measured with light having a wavelength of 450 nm at 23 ° C. Rth (λ) is obtained by the formula: Rth = (nx-nz) × d, where d (nm) is the thickness of the film.
(4) Nz coefficient The Nz coefficient is obtained by Nz = Rth / Re.
(5) Angle When referring to an angle herein, the angle includes angles in both clockwise and counterclockwise directions, unless otherwise stated.
A.位相差層および粘着剤層付偏光板の全体構成
図1は、本発明の1つの実施形態による位相差層および粘着剤層付偏光板の概略断面図である。図示例の位相差層および粘着剤層付偏光板100は、偏光板10と、偏光板10に第1の粘着剤層20を介して貼り合わせられた位相差層30と、位相差層30の偏光板10と反対側に最外層として設けられた第2の粘着剤層40と、を有する。第2の粘着剤層40により、位相差層および粘着剤層付偏光板は、画像表示セルに貼り付け可能とされている。偏光板10は、偏光子11と、偏光子11の一方の側に配置された第1の保護層12と、偏光子11のもう一方の側に配置された第2の保護層13とを含む。目的に応じて、第1の保護層12および第2の保護層13の一方は省略されてもよい。例えば、位相差層30は偏光子11の保護層としても機能し得るので、第2の保護層13は省略されてもよい。位相差層30の遅相軸と偏光子11の吸収軸とのなす角度は、好ましくは40°~50°であり、より好ましくは42°~48°であり、さらに好ましくは44°~46°であり、特に好ましくは約45°であり;あるいは、好ましくは130°~140°であり、より好ましくは132°~138°であり、さらに好ましくは134°~136°であり、特に好ましくは約135°である。 A. Overall Configuration of Polarizing Plate with Phase Difference Layer and Adhesive Layer FIG. 1 is a schematic cross-sectional view of a polarizing plate with a retardation layer and a pressure-sensitive adhesive layer according to one embodiment of the present invention. The polarizingplate 100 with the retardation layer and the pressure-sensitive adhesive layer in the illustrated example includes the polarizing plate 10, the retardation layer 30 bonded to the polarizing plate 10 via the first pressure-sensitive adhesive layer 20, and the retardation layer 30. It has a second pressure-sensitive adhesive layer 40 provided as an outermost layer on the side opposite to the polarizing plate 10. The second pressure-sensitive adhesive layer 40 makes it possible to attach the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer to the image display cell. The polarizing plate 10 includes a polarizing element 11, a first protective layer 12 arranged on one side of the polarizing element 11, and a second protective layer 13 arranged on the other side of the polarizing element 11. .. Depending on the purpose, one of the first protective layer 12 and the second protective layer 13 may be omitted. For example, since the retardation layer 30 can also function as a protective layer for the polarizing element 11, the second protective layer 13 may be omitted. The angle formed by the slow axis of the retardation layer 30 and the absorption axis of the polarizing element 11 is preferably 40 ° to 50 °, more preferably 42 ° to 48 °, and even more preferably 44 ° to 46 °. It is particularly preferably about 45 °; or preferably 130 ° to 140 °, more preferably 132 ° to 138 °, still more preferably 134 ° to 136 °, and particularly preferably about. It is 135 °.
図1は、本発明の1つの実施形態による位相差層および粘着剤層付偏光板の概略断面図である。図示例の位相差層および粘着剤層付偏光板100は、偏光板10と、偏光板10に第1の粘着剤層20を介して貼り合わせられた位相差層30と、位相差層30の偏光板10と反対側に最外層として設けられた第2の粘着剤層40と、を有する。第2の粘着剤層40により、位相差層および粘着剤層付偏光板は、画像表示セルに貼り付け可能とされている。偏光板10は、偏光子11と、偏光子11の一方の側に配置された第1の保護層12と、偏光子11のもう一方の側に配置された第2の保護層13とを含む。目的に応じて、第1の保護層12および第2の保護層13の一方は省略されてもよい。例えば、位相差層30は偏光子11の保護層としても機能し得るので、第2の保護層13は省略されてもよい。位相差層30の遅相軸と偏光子11の吸収軸とのなす角度は、好ましくは40°~50°であり、より好ましくは42°~48°であり、さらに好ましくは44°~46°であり、特に好ましくは約45°であり;あるいは、好ましくは130°~140°であり、より好ましくは132°~138°であり、さらに好ましくは134°~136°であり、特に好ましくは約135°である。 A. Overall Configuration of Polarizing Plate with Phase Difference Layer and Adhesive Layer FIG. 1 is a schematic cross-sectional view of a polarizing plate with a retardation layer and a pressure-sensitive adhesive layer according to one embodiment of the present invention. The polarizing
位相差層30は、樹脂フィルムの延伸フィルムで構成され、Re(450)<Re(550)の関係を満足する。位相差層30のRe(550)は、代表的には100nm~200nmである。第1の粘着剤層20の85℃および500時間の加熱試験後の糊ずれ量は900μm以下であり、第2の粘着剤層40の85℃におけるクリープ値は40μm以下である。位相差層および粘着剤層付偏光板を構成する各層の詳細については後述する。
The retardation layer 30 is made of a stretched film of a resin film and satisfies the relationship of Re (450) <Re (550). The Re (550) of the retardation layer 30 is typically 100 nm to 200 nm. The amount of glue slippage of the first pressure-sensitive adhesive layer 20 after the heating test at 85 ° C. and 500 hours is 900 μm or less, and the creep value of the second pressure-sensitive adhesive layer 40 at 85 ° C. is 40 μm or less. Details of each layer constituting the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer will be described later.
1つの実施形態においては、位相差層および粘着剤層付偏光板は、位相差層30と第2の粘着剤層40との間に別の位相差層(図示せず)をさらに有していてもよい。別の位相差層は、代表的には、屈折率特性がnz>nx=nyの関係を示す。このような別の位相差層を設けることにより、斜め方向の反射を良好に防止することができ、反射防止機能の広視野角化が可能となる。
In one embodiment, the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer further have another retardation layer (not shown) between the retardation layer 30 and the second pressure-sensitive adhesive layer 40. You may. The other retardation layer typically shows a relationship in which the refractive index characteristics are nz> nx = ny. By providing such another retardation layer, it is possible to satisfactorily prevent reflection in the oblique direction, and it is possible to widen the viewing angle of the antireflection function.
1つの実施形態においては、位相差層および粘着剤層付偏光板は、導電層または導電層付等方性基材(図示せず)をさらに有していてもよい。導電層または導電層付等方性基材が設けられる場合、位相差層および粘着剤層付偏光板は、画像表示セル(例えば、有機ELセル)と偏光板との間にタッチセンサが組み込まれた、いわゆるインナータッチパネル型入力表示装置に適用され得る。導電層または導電層付等方性基材は、代表的には、位相差層30と第2の粘着剤層40との間に設けられる。別の位相差層が設けられる場合、別の位相差層ならびに導電層または導電層付等方性基材は、代表的には、位相差層30側からこの順に設けられる。
In one embodiment, the retarding layer and the polarizing plate with the pressure-sensitive adhesive layer may further have a conductive layer or an isotropic base material with a conductive layer (not shown). When a conductive layer or an isotropic substrate with a conductive layer is provided, the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer have a touch sensor incorporated between the image display cell (for example, an organic EL cell) and the polarizing plate. It can be applied to a so-called inner touch panel type input display device. The conductive layer or the isotropic base material with the conductive layer is typically provided between the retardation layer 30 and the second pressure-sensitive adhesive layer 40. When another retardation layer is provided, the other retardation layer and the conductive layer or the isotropic base material with the conductive layer are typically provided in this order from the retardation layer 30 side.
位相差層および粘着剤層付偏光板は、さらなる位相差層(図示せず)を有していてもよい。さらなる位相差層は、別の位相差層と組み合わせて設けられてもよく、単独で(すなわち、別の位相差層を設けることなく)設けられてもよい。さらなる位相差層の光学的特性(例えば、屈折率特性、面内位相差、Nz係数、光弾性係数)、厚み、配置位置等は、目的に応じて適切に設定され得る。
The retardation layer and the polarizing plate with the pressure-sensitive adhesive layer may have a further retardation layer (not shown). The additional retardation layer may be provided in combination with another retardation layer, or may be provided alone (that is, without providing another retardation layer). The optical characteristics (for example, refractive index characteristics, in-plane retardation, Nz coefficient, photoelastic coefficient), thickness, arrangement position, and the like of the further retardation layer can be appropriately set according to the purpose.
位相差層および粘着剤層付偏光板は、枚葉状であってもよく長尺状であってもよい。本明細書において「長尺状」とは、幅に対して長さが十分に長い細長形状を意味し、例えば、幅に対して長さが10倍以上、好ましくは20倍以上の細長形状を含む。長尺状の位相差層および粘着剤層付偏光板は、ロール状に巻回可能である。
The retardation layer and the polarizing plate with the pressure-sensitive adhesive layer may be single-wafer-shaped or long-shaped. As used herein, the term "long" means an elongated shape having a length sufficiently long with respect to the width, and for example, an elongated shape having a length of 10 times or more, preferably 20 times or more with respect to the width. include. The elongated retardation layer and the polarizing plate with the pressure-sensitive adhesive layer can be wound in a roll shape.
実用的には、第2の粘着剤層40の表面には、位相差層および粘着剤層付偏光板が使用に供されるまで、剥離フィルムが仮着されていることが好ましい。剥離フィルムを仮着することにより、第2の粘着剤層を保護するとともに、位相差層および粘着剤層付偏光板のロール形成が可能となる。
Practically, it is preferable that a release film is temporarily attached to the surface of the second pressure-sensitive adhesive layer 40 until the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer are used. Temporarily attaching the release film protects the second pressure-sensitive adhesive layer and enables roll formation of the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer.
以下、位相差層および粘着剤層付偏光板の構成要素について説明する。
Hereinafter, the components of the polarizing plate with the retardation layer and the pressure-sensitive adhesive layer will be described.
B.偏光子
偏光子11としては、任意の適切な偏光子が採用され得る。例えば、偏光子を形成する樹脂フィルムは、単層の樹脂フィルムであってもよく、二層以上の積層体であってもよい。 B. Polarizer As thepolarizing element 11, any suitable polarizing element may be adopted. For example, the resin film forming the polarizing element may be a single-layer resin film or a laminated body having two or more layers.
偏光子11としては、任意の適切な偏光子が採用され得る。例えば、偏光子を形成する樹脂フィルムは、単層の樹脂フィルムであってもよく、二層以上の積層体であってもよい。 B. Polarizer As the
単層の樹脂フィルムから構成される偏光子の具体例としては、ポリビニルアルコール(PVA)系フィルム、部分ホルマール化PVA系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料等の二色性物質による染色処理および延伸処理が施されたもの、PVAの脱水処理物やポリ塩化ビニルの脱塩酸処理物等ポリエン系配向フィルム等が挙げられる。好ましくは、光学特性に優れることから、PVA系フィルムをヨウ素で染色し一軸延伸して得られた偏光子が用いられる。
Specific examples of the polarizing element composed of a single-layer resin film include a hydrophilic polymer film such as a polyvinyl alcohol (PVA) -based film, a partially formalized PVA-based film, and an ethylene / vinyl acetate copolymer-based partially saponified film. Examples thereof include those which have been dyed and stretched with a bicolor substance such as iodine and a bicolor dye, and polyene-based oriented films such as a dehydrated product of PVA and a dehydrogenated product of polyvinyl chloride. Preferably, since the PVA-based film is excellent in optical properties, a polarizing element obtained by dyeing a PVA-based film with iodine and uniaxially stretching the film is used.
上記ヨウ素による染色は、例えば、PVA系フィルムをヨウ素水溶液に浸漬することにより行われる。上記一軸延伸の延伸倍率は、好ましくは3~7倍である。延伸は、染色処理後に行ってもよいし、染色しながら行ってもよい。また、延伸してから染色してもよい。必要に応じて、PVA系フィルムに、膨潤処理、架橋処理、洗浄処理、乾燥処理等が施される。例えば、染色の前にPVA系フィルムを水に浸漬して水洗することで、PVA系フィルム表面の汚れやブロッキング防止剤を洗浄することができるだけでなく、PVA系フィルムを膨潤させて染色ムラなどを防止することができる。
The dyeing with iodine is performed, for example, by immersing a PVA-based film in an aqueous iodine solution. The draw ratio of the uniaxial stretching is preferably 3 to 7 times. The stretching may be performed after the dyeing treatment or may be performed while dyeing. Further, it may be dyed after being stretched. If necessary, the PVA-based film is subjected to a swelling treatment, a crosslinking treatment, a cleaning treatment, a drying treatment and the like. For example, by immersing the PVA-based film in water and washing it with water before dyeing, it is possible not only to clean the dirt and blocking inhibitor on the surface of the PVA-based film, but also to swell the PVA-based film to prevent uneven dyeing. Can be prevented.
積層体を用いて得られる偏光子の具体例としては、樹脂基材と当該樹脂基材に積層されたPVA系樹脂層(PVA系樹脂フィルム)との積層体、あるいは、樹脂基材と当該樹脂基材に塗布形成されたPVA系樹脂層との積層体を用いて得られる偏光子が挙げられる。樹脂基材と当該樹脂基材に塗布形成されたPVA系樹脂層との積層体を用いて得られる偏光子は、例えば、PVA系樹脂溶液を樹脂基材に塗布し、乾燥させて樹脂基材上にPVA系樹脂層を形成して、樹脂基材とPVA系樹脂層との積層体を得ること;当該積層体を延伸および染色してPVA系樹脂層を偏光子とすること;により作製され得る。本実施形態においては、延伸は、代表的には積層体をホウ酸水溶液中に浸漬させて延伸することを含む。さらに、延伸は、必要に応じて、ホウ酸水溶液中での延伸の前に積層体を高温(例えば、95℃以上)で空中延伸することをさらに含み得る。得られた樹脂基材/偏光子の積層体はそのまま用いてもよく(すなわち、樹脂基材を偏光子の保護層としてもよく)、樹脂基材/偏光子の積層体から樹脂基材を剥離し、当該剥離面に目的に応じた任意の適切な保護層を積層して用いてもよい。このような偏光子の製造方法の詳細は、例えば特開2012-73580号公報、特許第6470455号に記載されている。これらの特許文献の記載は、本明細書に参考として援用される。
Specific examples of the polarizing element obtained by using the laminate include a laminate of a resin base material and a PVA-based resin layer (PVA-based resin film) laminated on the resin base material, or a resin base material and the resin. Examples thereof include a polarizing element obtained by using a laminate with a PVA-based resin layer coated and formed on a base material. The polarizing element obtained by using the laminate of the resin base material and the PVA-based resin layer coated and formed on the resin base material is, for example, a resin base material obtained by applying a PVA-based resin solution to the resin base material and drying it. It is produced by forming a PVA-based resin layer on the PVA-based resin layer to obtain a laminate of a resin base material and a PVA-based resin layer; and stretching and dyeing the laminate to make the PVA-based resin layer a stator. obtain. In the present embodiment, stretching typically includes immersing the laminate in an aqueous boric acid solution for stretching. Further, stretching may further comprise, if necessary, stretching the laminate in the air at a high temperature (eg, 95 ° C. or higher) prior to stretching in boric acid aqueous solution. The obtained resin base material / polarizing element laminate may be used as it is (that is, the resin base material may be used as a protective layer for the polarizing element), and the resin base material is peeled off from the resin base material / polarizing element laminate. Then, an arbitrary appropriate protective layer according to the purpose may be laminated on the peeled surface and used. Details of the method for producing such a polarizing element are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580 and Japanese Patent No. 6470455. The description of these patent documents is incorporated herein by reference.
偏光子は、好ましくは単層の樹脂フィルムから構成され得る。このような構成であれば、第1粘着剤層および第2の粘着剤層の最適化との相乗的な効果により、高温環境下における位相差ムラが抑制された位相差層および粘着剤層付偏光板が得られ得る。
The polarizing element may preferably be composed of a single-layer resin film. With such a configuration, with a retardation layer and a pressure-sensitive adhesive layer in which retardation unevenness is suppressed in a high temperature environment due to a synergistic effect with optimization of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer. A polarizing plate can be obtained.
偏光子の厚みは、好ましくは15μm以下であり、より好ましくは1μm~12μmであり、さらに好ましくは3μm~12μmである。偏光子の厚みがこのような範囲であれば、加熱時のカールを良好に抑制することができ、および、良好な加熱時の外観耐久性が得られる。
また、偏光子の厚みは、特に好ましくは、8μm以下である。偏光子の厚みがこのような上限以下であれば、高湿環境下において、位相差層および粘着剤層付偏光板が被着体から剥がれること、および、粘着剤層に泡が発生することを抑制できる。 The thickness of the polarizing element is preferably 15 μm or less, more preferably 1 μm to 12 μm, and even more preferably 3 μm to 12 μm. When the thickness of the polarizing element is within such a range, curling during heating can be satisfactorily suppressed, and good appearance durability during heating can be obtained.
The thickness of the polarizing element is particularly preferably 8 μm or less. If the thickness of the polarizing element is not more than such an upper limit, the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer may be peeled off from the adherend and bubbles may be generated in the pressure-sensitive adhesive layer in a high humidity environment. Can be suppressed.
また、偏光子の厚みは、特に好ましくは、8μm以下である。偏光子の厚みがこのような上限以下であれば、高湿環境下において、位相差層および粘着剤層付偏光板が被着体から剥がれること、および、粘着剤層に泡が発生することを抑制できる。 The thickness of the polarizing element is preferably 15 μm or less, more preferably 1 μm to 12 μm, and even more preferably 3 μm to 12 μm. When the thickness of the polarizing element is within such a range, curling during heating can be satisfactorily suppressed, and good appearance durability during heating can be obtained.
The thickness of the polarizing element is particularly preferably 8 μm or less. If the thickness of the polarizing element is not more than such an upper limit, the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer may be peeled off from the adherend and bubbles may be generated in the pressure-sensitive adhesive layer in a high humidity environment. Can be suppressed.
偏光子は、好ましくは、波長380nm~780nmのいずれかの波長で吸収二色性を示す。偏光子の単体透過率は、例えば41.5%~46.0%であり、好ましくは43.0%~46.0%であり、より好ましくは44.5%~46.0%である。偏光子の偏光度は、好ましくは97.0%以上であり、より好ましくは99.0%以上であり、さらに好ましくは99.9%以上である。
The polarizing element preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm. The simple substance transmittance of the polarizing element is, for example, 41.5% to 46.0%, preferably 43.0% to 46.0%, and more preferably 44.5% to 46.0%. The degree of polarization of the polarizing element is preferably 97.0% or more, more preferably 99.0% or more, and further preferably 99.9% or more.
C.保護層
第1の保護層12および第2の保護層13は、それぞれ、偏光子の保護層として使用できる任意の適切なフィルムで形成される。当該フィルムの主成分となる材料の具体例としては、トリアセチルセルロース(TAC)等のセルロース系樹脂や、ポリエステル系、ポリビニルアルコール系、ポリカーボネート系、ポリアミド系、ポリイミド系、ポリエーテルスルホン系、ポリスルホン系、ポリスチレン系、ポリノルボルネン系、ポリオレフィン系、(メタ)アクリル系、アセテート系等の透明樹脂等が挙げられる。また、(メタ)アクリル系、ウレタン系、(メタ)アクリルウレタン系、エポキシ系、シリコーン系等の熱硬化型樹脂または紫外線硬化型樹脂等も挙げられる。この他にも、例えば、シロキサン系ポリマー等のガラス質系ポリマーも挙げられる。また、特開2001-343529号公報(WO01/37007)に記載のポリマーフィルムも使用できる。このフィルムの材料としては、例えば、側鎖に置換または非置換のイミド基を有する熱可塑性樹脂と、側鎖に置換または非置換のフェニル基ならびにニトリル基を有する熱可塑性樹脂を含有する樹脂組成物が使用でき、例えば、イソブテンとN-メチルマレイミドからなる交互共重合体と、アクリロニトリル・スチレン共重合体とを有する樹脂組成物が挙げられる。当該ポリマーフィルムは、例えば、上記樹脂組成物の押出成形物であり得る。 C. Protective Layer The firstprotective layer 12 and the second protective layer 13 are each formed of any suitable film that can be used as a protective layer for the polarizing element. Specific examples of the material that is the main component of the film include cellulose-based resins such as triacetyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, polyethersulfone-based, and polysulfone-based. , Polyester-based, polycarbonate-based, polyolefin-based, (meth) acrylic-based, acetate-based transparent resins and the like. Further, thermosetting resins such as (meth) acrylic, urethane, (meth) acrylic urethane, epoxy, and silicone, or ultraviolet curable resins can also be mentioned. In addition to this, for example, glassy polymers such as siloxane-based polymers can also be mentioned. Further, the polymer film described in JP-A-2001-343529 (WO01 / 37007) can also be used. As the material of this film, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain. Can be used, and examples thereof include a resin composition having an alternating copolymer composed of isobutene and N-methylmaleimide and an acrylonitrile / styrene copolymer. The polymer film can be, for example, an extruded product of the above resin composition.
第1の保護層12および第2の保護層13は、それぞれ、偏光子の保護層として使用できる任意の適切なフィルムで形成される。当該フィルムの主成分となる材料の具体例としては、トリアセチルセルロース(TAC)等のセルロース系樹脂や、ポリエステル系、ポリビニルアルコール系、ポリカーボネート系、ポリアミド系、ポリイミド系、ポリエーテルスルホン系、ポリスルホン系、ポリスチレン系、ポリノルボルネン系、ポリオレフィン系、(メタ)アクリル系、アセテート系等の透明樹脂等が挙げられる。また、(メタ)アクリル系、ウレタン系、(メタ)アクリルウレタン系、エポキシ系、シリコーン系等の熱硬化型樹脂または紫外線硬化型樹脂等も挙げられる。この他にも、例えば、シロキサン系ポリマー等のガラス質系ポリマーも挙げられる。また、特開2001-343529号公報(WO01/37007)に記載のポリマーフィルムも使用できる。このフィルムの材料としては、例えば、側鎖に置換または非置換のイミド基を有する熱可塑性樹脂と、側鎖に置換または非置換のフェニル基ならびにニトリル基を有する熱可塑性樹脂を含有する樹脂組成物が使用でき、例えば、イソブテンとN-メチルマレイミドからなる交互共重合体と、アクリロニトリル・スチレン共重合体とを有する樹脂組成物が挙げられる。当該ポリマーフィルムは、例えば、上記樹脂組成物の押出成形物であり得る。 C. Protective Layer The first
位相差層および粘着剤層付偏光板は、後述するように代表的には画像表示装置の視認側に配置され、第1の保護層12は、代表的にはその視認側に配置される。したがって、第1の保護層12には、必要に応じて、ハードコート処理、反射防止処理、スティッキング防止処理、アンチグレア処理等の表面処理が施されていてもよい。さらに/あるいは、第1の保護層12には、必要に応じて、偏光サングラスを介して視認する場合の視認性を改善する処理(代表的には、(楕)円偏光機能を付与すること、超高位相差を付与すること)が施されていてもよい。このような処理を施すことにより、偏光サングラス等の偏光レンズを介して表示画面を視認した場合でも、優れた視認性を実現することができる。したがって、位相差層および粘着剤層付偏光板は、屋外で用いられ得る画像表示装置にも好適に適用され得る。
The retardation layer and the polarizing plate with the adhesive layer are typically arranged on the visual recognition side of the image display device as described later, and the first protective layer 12 is typically arranged on the visual recognition side thereof. Therefore, the first protective layer 12 may be subjected to surface treatment such as hard coat treatment, antireflection treatment, anti-sticking treatment, and anti-glare treatment, if necessary. Further / or, if necessary, the first protective layer 12 is provided with a process for improving visibility when visually recognizing through polarized sunglasses (typically, a (elliptical) circularly polarized light function is imparted. (Giving an ultra-high phase difference) may be applied. By performing such processing, excellent visibility can be realized even when the display screen is visually recognized through a polarizing lens such as polarized sunglasses. Therefore, the retarding layer and the polarizing plate with the pressure-sensitive adhesive layer can be suitably applied to an image display device that can be used outdoors.
第1の保護層の厚みは、代表的には300μm以下であり、好ましくは100μm以下、より好ましくは5μm~80μm、さらに好ましくは10μm~60μmである。なお、表面処理が施されている場合、外側保護層の厚みは、表面処理層の厚みを含めた厚みである。
The thickness of the first protective layer is typically 300 μm or less, preferably 100 μm or less, more preferably 5 μm to 80 μm, and even more preferably 10 μm to 60 μm. When the surface treatment is applied, the thickness of the outer protective layer is the thickness including the thickness of the surface treatment layer.
第2の保護層13は、1つの実施形態においては、光学的に等方性であることが好ましい。本明細書において「光学的に等方性である」とは、面内位相差Re(550)が0nm~10nmであり、厚み方向の位相差Rth(550)が-10nm~+10nmであることをいう。
The second protective layer 13 is preferably optically isotropic in one embodiment. As used herein, "optically isotropic" means that the in-plane retardation Re (550) is 0 nm to 10 nm and the thickness direction retardation Rth (550) is -10 nm to +10 nm. Say.
D.位相差層
D-1.位相差層の特性
位相差層の面内位相差Re(550)は、上記のとおり100nm~200nmであり、好ましくは110nm~180nmであり、より好ましくは120nm~160nmであり、さらに好ましくは130nm~150nmである。すなわち、位相差層は、いわゆるλ/4板として機能し得る。 D. Phase difference layer D-1. Characteristics of the retardation layer The in-plane retardation Re (550) of the retardation layer is 100 nm to 200 nm, preferably 110 nm to 180 nm, more preferably 120 nm to 160 nm, and further preferably 130 nm to 130 nm as described above. It is 150 nm. That is, the retardation layer can function as a so-called λ / 4 plate.
D-1.位相差層の特性
位相差層の面内位相差Re(550)は、上記のとおり100nm~200nmであり、好ましくは110nm~180nmであり、より好ましくは120nm~160nmであり、さらに好ましくは130nm~150nmである。すなわち、位相差層は、いわゆるλ/4板として機能し得る。 D. Phase difference layer D-1. Characteristics of the retardation layer The in-plane retardation Re (550) of the retardation layer is 100 nm to 200 nm, preferably 110 nm to 180 nm, more preferably 120 nm to 160 nm, and further preferably 130 nm to 130 nm as described above. It is 150 nm. That is, the retardation layer can function as a so-called λ / 4 plate.
位相差層は、上記のとおりRe(450)<Re(550)の関係を満たし、好ましくはRe(550)<Re(650)の関係をさらに満たす。すなわち、位相差層は、位相差値が測定光の波長に応じて大きくなる逆分散の波長依存性を示す。位相差フィルムのRe(450)/Re(550)は、例えば0.5を超えて1.0未満であり、好ましくは0.7~0.95であり、より好ましくは0.75~0.92であり、さらに好ましくは0.8~0.9である。Re(650)/Re(550)は、好ましくは1.0以上1.15未満であり、より好ましくは1.03~1.1である。
The retardation layer satisfies the relationship of Re (450) <Re (550) as described above, and preferably further satisfies the relationship of Re (550) <Re (650). That is, the retardation layer exhibits a wavelength dependence of inverse dispersion in which the retardation value increases with the wavelength of the measurement light. The Re (450) / Re (550) of the retardation film is, for example, more than 0.5 and less than 1.0, preferably 0.7 to 0.95, and more preferably 0.75 to 0. It is 92, more preferably 0.8 to 0.9. Re (650) / Re (550) is preferably 1.0 or more and less than 1.15, and more preferably 1.03 to 1.1.
位相差層は、上記のように面内位相差を有するので、nx>nyの関係を有する。位相差層は、nx>nyの関係を有する限り、任意の適切な屈折率特性を示す。位相差層の屈折率特性は、代表的にはnx>ny≧nzの関係を示す。なお、ここで「ny=nz」はnyとnzが完全に等しい場合だけではなく、実質的に等しい場合を包含する。したがって、本発明の効果を損なわない範囲で、ny<nzとなる場合があり得る。位相差層のNz係数は、好ましくは0.9~2.0であり、より好ましくは0.9~1.5であり、さらに好ましくは0.9~1.2である。このような関係を満たすことにより、位相差層および粘着剤層付偏光板を画像表示装置に用いた場合に、非常に優れた反射色相を達成し得る。
Since the retardation layer has an in-plane retardation as described above, it has a relationship of nx> ny. The retardation layer exhibits any suitable refractive index characteristics as long as it has the relationship of nx> ny. The refractive index characteristics of the retardation layer typically show a relationship of nx> ny ≧ nz. Here, "ny = nz" includes not only the case where ny and nz are completely equal, but also the case where they are substantially equal. Therefore, ny <nz may be satisfied as long as the effect of the present invention is not impaired. The Nz coefficient of the retardation layer is preferably 0.9 to 2.0, more preferably 0.9 to 1.5, and even more preferably 0.9 to 1.2. By satisfying such a relationship, a very excellent reflected hue can be achieved when a polarizing plate with a retardation layer and a pressure-sensitive adhesive layer is used in an image display device.
位相差層の厚みは、λ/4板として最も適切に機能し得るように設定され得る。言い換えれば、厚みは、所望の面内位相差が得られるように設定され得る。具体的には、厚みは、好ましくは15μm~60μmであり、さらに好ましくは20μm~55μmであり、最も好ましくは20μm~50μmである。
The thickness of the retardation layer can be set so that it can function most appropriately as a λ / 4 plate. In other words, the thickness can be set to obtain the desired in-plane phase difference. Specifically, the thickness is preferably 15 μm to 60 μm, more preferably 20 μm to 55 μm, and most preferably 20 μm to 50 μm.
位相差層は、その光弾性係数の絶対値が好ましくは20×10-12(m2/N)以下であり、より好ましくは1.0×10-12(m2/N)~15×10-12(m2/N)であり、さらに好ましくは2.0×10-12(m2/N)~12×10-12(m2/N)である。光弾性係数の絶対値がこのような範囲であれば、位相差層および粘着剤層付偏光板を画像表示装置に適用した場合に表示ムラを抑制することができる。
The absolute value of the photoelastic coefficient of the retardation layer is preferably 20 × 10 -12 (m 2 / N) or less, and more preferably 1.0 × 10 -12 (m 2 / N) to 15 × 10. It is -12 (m 2 / N), more preferably 2.0 × 10 -12 (m 2 / N) to 12 × 10 -12 (m 2 / N). When the absolute value of the photoelastic coefficient is in such a range, display unevenness can be suppressed when the retarding layer and the polarizing plate with the pressure-sensitive adhesive layer are applied to the image display device.
25℃/50%RH、60℃/50%RH、60℃/85%RHの順に環境を変化させる加湿TMA試験において、位相差層の遅相軸方向の寸法変化率は、好ましくは0.45%以下であり、より好ましくは0.35%以下であり、さらに好ましくは0.28%以下であり、とりわけ好ましくは0.22%以下である。加湿TMA試験における位相差層の寸法変化率がこのような上限以下であれば、高湿環境下において、位相差層および粘着剤層付偏光板が被着体から剥がれることを抑制でき、位相差層および粘着剤層付偏光板の高湿耐久性の向上を図ることができる。なお、25℃/50%RH、60℃/50%RH、60℃/85%RHの順に環境を変化させる加湿TMA試験において、位相差層の遅相軸方向の寸法変化率は、例えば0%以上である。また、位相差層および粘着剤層付偏光板が別の位相差層(図示せず)をさらに有する場合、上記加湿TMA試験における位相差層の遅相軸方向の寸法変化率は、位相差層に別の位相差層が貼り合わされた状態で測定され、その寸法変化率の範囲は、上記と同様の範囲である。
In a humidified TMA test in which the environment is changed in the order of 25 ° C / 50% RH, 60 ° C / 50% RH, and 60 ° C / 85% RH, the dimensional change rate of the retardation layer in the slow axial direction is preferably 0.45. % Or less, more preferably 0.35% or less, still more preferably 0.28% or less, and particularly preferably 0.22% or less. When the dimensional change rate of the retardation layer in the humidifying TMA test is not more than such an upper limit, it is possible to suppress the retardation layer and the polarizing plate with the adhesive layer from peeling off from the adherend in a high humidity environment, and the retardation difference. It is possible to improve the high humidity durability of the polarizing plate with the layer and the pressure-sensitive adhesive layer. In the humidified TMA test in which the environment is changed in the order of 25 ° C./50% RH, 60 ° C./50% RH, and 60 ° C./85% RH, the dimensional change rate in the slow axial direction of the retardation layer is, for example, 0%. That is all. When the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer further have another retardation layer (not shown), the dimensional change rate of the retardation layer in the humidification TMA test in the slow axis direction is the retardation layer. It is measured in a state where another retardation layer is bonded to the surface, and the range of the dimensional change rate is the same range as described above.
D-2.位相差層の構成材料
位相差層は、代表的には、カーボネート結合およびエステル結合からなる群から選択される少なくとも1つの結合基を含む樹脂を含有する。言い換えれば、位相差層は、ポリカーボネート系樹脂、ポリエステル系樹脂またはポリエステルカーボネート系樹脂(以下、これらをまとめてポリカーボネート系樹脂等と称する場合がある)を含有する。ポリカーボネート系樹脂等は、上記一般式(1)で表される構造単位および/または上記一般式(2)で表される構造単位からなる群から選択される少なくとも1つの構造単位を含む。これらの構造単位は、2価のオリゴフルオレンに由来する構造単位であり、以下、オリゴフルオレン構造単位と称する場合がある。このようなポリカーボネート系樹脂等は、正の屈折率異方性を有する。 D-2. Constituent Material of Phase Difference Layer The phase difference layer typically contains a resin containing at least one linking group selected from the group consisting of carbonate bonds and ester bonds. In other words, the retardation layer contains a polycarbonate-based resin, a polyester-based resin, or a polyester carbonate-based resin (hereinafter, these may be collectively referred to as a polycarbonate-based resin or the like). The polycarbonate-based resin or the like contains at least one structural unit selected from the group consisting of the structural unit represented by the general formula (1) and / or the structural unit represented by the general formula (2). These structural units are structural units derived from divalent oligofluorene, and may be hereinafter referred to as oligofluorene structural units. Such polycarbonate-based resins and the like have positive refractive index anisotropy.
位相差層は、代表的には、カーボネート結合およびエステル結合からなる群から選択される少なくとも1つの結合基を含む樹脂を含有する。言い換えれば、位相差層は、ポリカーボネート系樹脂、ポリエステル系樹脂またはポリエステルカーボネート系樹脂(以下、これらをまとめてポリカーボネート系樹脂等と称する場合がある)を含有する。ポリカーボネート系樹脂等は、上記一般式(1)で表される構造単位および/または上記一般式(2)で表される構造単位からなる群から選択される少なくとも1つの構造単位を含む。これらの構造単位は、2価のオリゴフルオレンに由来する構造単位であり、以下、オリゴフルオレン構造単位と称する場合がある。このようなポリカーボネート系樹脂等は、正の屈折率異方性を有する。 D-2. Constituent Material of Phase Difference Layer The phase difference layer typically contains a resin containing at least one linking group selected from the group consisting of carbonate bonds and ester bonds. In other words, the retardation layer contains a polycarbonate-based resin, a polyester-based resin, or a polyester carbonate-based resin (hereinafter, these may be collectively referred to as a polycarbonate-based resin or the like). The polycarbonate-based resin or the like contains at least one structural unit selected from the group consisting of the structural unit represented by the general formula (1) and / or the structural unit represented by the general formula (2). These structural units are structural units derived from divalent oligofluorene, and may be hereinafter referred to as oligofluorene structural units. Such polycarbonate-based resins and the like have positive refractive index anisotropy.
位相差層は、1つの実施形態においては、アクリル系樹脂をさらに含有し得る。アクリル系樹脂の含有量は0.5質量%~1.5質量%である。なお、本明細書において「質量」単位の百分率または部は、「重量」単位の百分率または部と同義である。
The retardation layer may further contain an acrylic resin in one embodiment. The content of the acrylic resin is 0.5% by mass to 1.5% by mass. In addition, in this specification, the percentage or part of "mass" unit is synonymous with the percentage or part of "weight" unit.
D-2-1.ポリカーボネート系樹脂等
<オリゴフルオレン構造単位>
オリゴフルオレン構造単位は、上記一般式(1)または(2)で表される。一般式(1)および(2)中、R1~R3は、それぞれ独立に、直接結合、置換または非置換の炭素数1~4のアルキレン基であり、R4~R9は、それぞれ独立に、水素原子、置換または非置換の炭素数1~10のアルキル基、置換または非置換の炭素数4~10のアリール基、置換または非置換の炭素数1~10のアシル基、置換または非置換の炭素数1~10のアルコキシ基、置換または非置換の炭素数1~10のアリールオキシ基、置換または非置換のアミノ基、置換または非置換の炭素数1~10のビニル基、置換または非置換の炭素数1~10のエチニル基、置換基を有する硫黄原子、置換基を有するケイ素原子、ハロゲン原子、ニトロ基、またはシアノ基である。ただし、R4~R9は、互いに同一であっても、異なっていてもよく、 R4~R9のうち隣接する少なくとも2つの基が互いに結合して環を形成していてもよい。 D-2-1. Polycarbonate resin, etc. <Oligofluorene structural unit>
The oligofluorene structural unit is represented by the above general formula (1) or (2). In the general formulas (1) and (2), R 1 to R 3 are independently bonded, substituted or unsubstituted alkylene groups having 1 to 4 carbon atoms, and R 4 to R 9 are independent of each other. A hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 4 to 10 carbon atoms, a substituted or unsubstituted acyl group having 1 to 10 carbon atoms, substituted or unsubstituted. Substituted alkoxy group with 1-10 carbon atoms, substituted or unsubstituted aryloxy group with 1-10 carbon atoms, substituted or unsubstituted amino group, substituted or unsubstituted vinyl group with 1-10 carbon atoms, substituted or unsubstituted. It is an unsubstituted ethynyl group having 1 to 10 carbon atoms, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, R 4 to R 9 may be the same or different from each other, and at least two adjacent groups of R 4 to R 9 may be bonded to each other to form a ring.
<オリゴフルオレン構造単位>
オリゴフルオレン構造単位は、上記一般式(1)または(2)で表される。一般式(1)および(2)中、R1~R3は、それぞれ独立に、直接結合、置換または非置換の炭素数1~4のアルキレン基であり、R4~R9は、それぞれ独立に、水素原子、置換または非置換の炭素数1~10のアルキル基、置換または非置換の炭素数4~10のアリール基、置換または非置換の炭素数1~10のアシル基、置換または非置換の炭素数1~10のアルコキシ基、置換または非置換の炭素数1~10のアリールオキシ基、置換または非置換のアミノ基、置換または非置換の炭素数1~10のビニル基、置換または非置換の炭素数1~10のエチニル基、置換基を有する硫黄原子、置換基を有するケイ素原子、ハロゲン原子、ニトロ基、またはシアノ基である。ただし、R4~R9は、互いに同一であっても、異なっていてもよく、 R4~R9のうち隣接する少なくとも2つの基が互いに結合して環を形成していてもよい。 D-2-1. Polycarbonate resin, etc. <Oligofluorene structural unit>
The oligofluorene structural unit is represented by the above general formula (1) or (2). In the general formulas (1) and (2), R 1 to R 3 are independently bonded, substituted or unsubstituted alkylene groups having 1 to 4 carbon atoms, and R 4 to R 9 are independent of each other. A hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 4 to 10 carbon atoms, a substituted or unsubstituted acyl group having 1 to 10 carbon atoms, substituted or unsubstituted. Substituted alkoxy group with 1-10 carbon atoms, substituted or unsubstituted aryloxy group with 1-10 carbon atoms, substituted or unsubstituted amino group, substituted or unsubstituted vinyl group with 1-10 carbon atoms, substituted or unsubstituted. It is an unsubstituted ethynyl group having 1 to 10 carbon atoms, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, R 4 to R 9 may be the same or different from each other, and at least two adjacent groups of R 4 to R 9 may be bonded to each other to form a ring.
ポリカーボネート系樹脂等におけるオリゴフルオレン構造単位の含有量は、樹脂全体に対して、好ましくは1質量%~40質量%であり、より好ましくは10質量%~35質量%であり、さらに好ましくは15質量%~30質量%であり、特に好ましくは18質量%~25質量%である。オリゴフルオレン構造単位の含有量が多すぎる場合、光弾性係数が大きくなりすぎる、信頼性が不十分となる、位相差発現性が不十分となるといった問題が生じるおそれがある。さらに、オリゴフルオレン構造単位が樹脂中に占める割合が高くなるため、分子設計の幅が狭くなり、樹脂の改質が求められた時に改良が困難となる場合がある。一方、仮に、非常に少量のオリゴフルオレン構造単位により所望の逆分散波長依存性が得られたとしても、この場合には、オリゴフルオレン構造単位の含有量のわずかなばらつきに応じて光学特性が敏感に変化するので、諸特性が一定の範囲に収まるように製造することが困難となる場合がある。
The content of the oligofluorene structural unit in the polycarbonate-based resin or the like is preferably 1% by mass to 40% by mass, more preferably 10% by mass to 35% by mass, and further preferably 15% by mass with respect to the entire resin. It is% to 30% by mass, and particularly preferably 18% by mass to 25% by mass. If the content of the oligofluorene structural unit is too large, problems such as an excessively large photoelastic coefficient, insufficient reliability, and insufficient phase difference expression may occur. Furthermore, since the proportion of oligofluorene structural units in the resin is high, the range of molecular design is narrowed, and it may be difficult to improve when modification of the resin is required. On the other hand, even if a very small amount of oligofluorene structural unit obtains the desired inverse dispersion wavelength dependence, in this case, the optical characteristics are sensitive to a slight variation in the content of the oligofluorene structural unit. Therefore, it may be difficult to manufacture the product so that the characteristics are within a certain range.
オリゴフルオレン構造単位の詳細は、例えば、国際公開第2015/159928号パンフレットに記載されている。当該公報は、本明細書に参考として援用される。
Details of the oligofluorene structural unit are described in, for example, International Publication No. 2015/159928. The publication is incorporated herein by reference.
<他の構造単位>
ポリカーボネート系樹脂等は、代表的には、オリゴフルオレン構造単位に加えて他の構造単位を含み得る。1つの実施形態においては、他の構造単位は、好ましくはジヒドロキシ化合物またはジエステル化合物由来であり得る。目的とする逆分散波長性を発現させるためには、負の固有複屈折を有するオリゴフルオレン構造単位とともに、正の固有複屈折を有する構造単位をポリマー構造に組み込む必要があるため、共重合する他のモノマーとしては、正の複屈折を有する構造単位の原料となるジヒドロキシ化合物又はジエステル化合物がさらに好ましい。 <Other structural units>
Polycarbonate-based resins and the like may typically contain other structural units in addition to the oligofluorene structural units. In one embodiment, the other structural unit may preferably be derived from a dihydroxy compound or a diester compound. In order to achieve the desired reverse dispersion wavelength property, it is necessary to incorporate the oligofluorene structural unit having negative intrinsic birefringence and the structural unit having positive intrinsic birefringence into the polymer structure. As the monomer of, a dihydroxy compound or a diester compound which is a raw material of a structural unit having positive birefringence is more preferable.
ポリカーボネート系樹脂等は、代表的には、オリゴフルオレン構造単位に加えて他の構造単位を含み得る。1つの実施形態においては、他の構造単位は、好ましくはジヒドロキシ化合物またはジエステル化合物由来であり得る。目的とする逆分散波長性を発現させるためには、負の固有複屈折を有するオリゴフルオレン構造単位とともに、正の固有複屈折を有する構造単位をポリマー構造に組み込む必要があるため、共重合する他のモノマーとしては、正の複屈折を有する構造単位の原料となるジヒドロキシ化合物又はジエステル化合物がさらに好ましい。 <Other structural units>
Polycarbonate-based resins and the like may typically contain other structural units in addition to the oligofluorene structural units. In one embodiment, the other structural unit may preferably be derived from a dihydroxy compound or a diester compound. In order to achieve the desired reverse dispersion wavelength property, it is necessary to incorporate the oligofluorene structural unit having negative intrinsic birefringence and the structural unit having positive intrinsic birefringence into the polymer structure. As the monomer of, a dihydroxy compound or a diester compound which is a raw material of a structural unit having positive birefringence is more preferable.
共重合モノマーとしては、芳香族環を含む構造単位を導入可能な化合物と、芳香族環を含む構造単位を導入しない、即ち脂肪族構造で構成される化合物が挙げられる。
前記脂肪族構造で構成される化合物の具体例を以下に挙げる。エチレングリコール、1,3-プロパンジオール、1,2-プロパンジオール、1,4-ブタンジオール、1,3-ブタンジオール、1,2-ブタンジオール、1,5-ヘプタンジオール、1,6-ヘキサンジオール、1,9-ノナンジオール、1,10-デカンジオール、1,12-ドデカンジオール等の直鎖脂肪族炭化水素のジヒドロキシ化合物;ネオペンチルグリコール、ヘキシレングリコール等の分岐脂肪族炭化水素のジヒドロキシ化合物;1,2-シクロヘキサンジオール、1,4-シクロヘキサンジオール、1,3-アダマンタンジオール、水添ビスフェノールA、2,2,4,4-テトラメチル-1,3-シクロブタンジオール等に例示される、脂環式炭化水素の2級アルコール、及び3級アルコールであるジヒドロキシ化合物;1,2-シクロヘキサンジメタノール、1,3-シクロヘキサンジメタノール、1,4-シクロヘキサンジメタノール、トリシクロデカンジメタノール、ペンタシクロペンタデカンジメタノール、2,6-デカリンジメタノール、1,5-デカリンジメタノール、2,3-デカリンジメタノール、2,3-ノルボルナンジメタノール、2,5-ノルボルナンジメタノール、1,3-アダマンタンジメタノール、リモネン等の、テルペン化合物から誘導されるジヒドロキシ化合物等に例示される、脂環式炭化水素の1級アルコールであるジヒドロキシ化合物;ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール等のオキシアルキレングリコール類;イソソルビド等の環状エーテル構造を有するジヒドロキシ化合物;スピログリコール、ジオキサングリコール等の環状アセタール構造を有するジヒドロキシ化合物;1,2-シクロヘキサンジカルボン酸、1,3-シクロヘキサンジカルボン酸、1,4-シクロヘキサンジカルボン酸等の脂環式ジカルボン酸;、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等の脂肪族ジカルボン酸。
前記芳香族環を含む構造単位を導入可能な化合物の具体例を以下に挙げる。2,2-ビス(4-ヒドロキシフェニル)プロパン、2,2-ビス(3-メチル-4-ヒドロキシフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3,5-ジメチルフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3,5-ジエチルフェニル)プロパン、2,2-ビス(4-ヒドロキシ-(3-フェニル)フェニル)プロパン、2,2-ビス(4-ヒドロキシ-(3,5-ジフェニル)フェニル)プロパン、2,2-ビス(4-ヒドロキシ-3,5-ジブロモフェニル)プロパン、ビス(4-ヒドロキシフェニル)メタン、1,1-ビス(4-ヒドロキシフェニル)エタン、2,2-ビス(4-ヒドロキシフェニル)ブタン、2,2-ビス(4-ヒドロキシフェニル)ペンタン、1,1-ビス(4-ヒドロキシフェニル)-1-フェニルエタン、ビス(4-ヒドロキシフェニル)ジフェニルメタン、1,1-ビス(4-ヒドロキシフェニル)-2-エチルヘキサン、1,1-ビス(4-ヒドロキシフェニル)デカン、ビス(4-ヒドロキシ-3-ニトロフェニル)メタン、3,3-ビス(4-ヒドロキシフェニル)ペンタン、1,3-ビス(2-(4-ヒドロキシフェニル)-2-プロピル)ベンゼン、1,3-ビス(2-(4-ヒドロキシフェニル)-2-プロピル)ベンゼン、2,2-ビス(4-ヒドロキシフェニル)ヘキサフルオロプロパン、1,1-ビス(4-ヒドロキシフェニル)シクロヘキサン、ビス(4-ヒドロキシフェニル)スルホン、2,4’-ジヒドロキシジフェニルスルホン、ビス(4-ヒドロキシフェニル)スルフィド、ビス(4-ヒドロキシ-3-メチルフェニル)スルフィド、ビス(4-ヒドロキシフェニル)ジスルフィド、4,4’-ジヒドロキシジフェニルエーテル、4,4’-ジヒドロキシ-3,3’-ジクロロジフェニルエーテル等の芳香族ビスフェノール化合物;2,2-ビス(4-(2-ヒドロキシエトキシ)フェニル)プロパン、2,2-ビス(4-(2-ヒドロキシプロポキシ)フェニル)プロパン、1,3-ビス(2-ヒドロキシエトキシ)ベンゼン、4,4’-ビス(2-ヒドロキシエトキシ)ビフェニル、ビス(4-(2-ヒドロキシエトキシ)フェニル)スルホン等の芳香族基に結合したエーテル基を有するジヒドロキシ化合物;テレフタル酸、フタル酸、イソフタル酸、4,4’-ジフェニルジカルボン酸、4,4’-ジフェニルエーテルジカルボン酸、4,4’-ベンゾフェノンジカルボン酸、4,4’-ジフェノキシエタンジカルボン酸、4,4’-ジフェニルスルホンジカルボン酸、2,6-ナフタレンジカルボン酸等の芳香族ジカルボン酸。
尚、上記で挙げた脂肪族ジカルボン酸及び芳香族ジカルボン酸成分はジカルボン酸そのものとして前記ポリエステルカーボネートの原料とすることができるが、製造法に応じて、メチルエステル体、フェニルエステル体等のジカルボン酸エステルや、ジカルボン酸ハライド等のジカルボン酸誘導体を原料とすることもできる。 Examples of the copolymerization monomer include a compound into which a structural unit containing an aromatic ring can be introduced and a compound in which a structural unit containing an aromatic ring is not introduced, that is, a compound having an aliphatic structure.
Specific examples of the compound having the aliphatic structure are given below. Ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexane Dihydroxy compounds of linear aliphatic hydrocarbons such as diols, 1,9-nonanediols, 1,10-decanediols and 1,12-dodecanediol; dihydroxys of branched aliphatic hydrocarbons such as neopentyl glycol and hexylene glycol. Compounds; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantandiol, hydrogenated bisphenol A, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and the like are exemplified. , Secondary alcohols of alicyclic hydrocarbons, and dihydroxy compounds which are tertiary alcohols; 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, Pentacyclopentadecanedimethanol, 2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol, 2,3-norbornandimethanol, 2,5-norbornandimethanol, 1,3- Dihydroxy compounds which are primary alcohols of alicyclic hydrocarbons exemplified by dihydroxy compounds derived from terpene compounds such as adamantandimethanol and limonene; diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol and polypropylene. Oxyalkylene glycols such as glycol; dihydroxy compounds having a cyclic ether structure such as isosorbide; dihydroxy compounds having a cyclic acetal structure such as spiroglycol and dioxane glycol; 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, An alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid; an aliphatic dicarboxylic acid such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
Specific examples of the compound into which the structural unit containing the aromatic ring can be introduced are given below. 2,2-Bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2 , 2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3-phenyl) phenyl) propane, 2,2-bis (4-hydroxy- (3,3) 5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2 , 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane , 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 1,1-bis (4-hydroxyphenyl) decane, bis (4-hydroxy-3-nitrophenyl) methane, 3,3-bis ( 4-Hydroxyphenyl) pentane, 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 2 , 2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenyl sulfone, bis (4-hydroxy) Phenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4-hydroxyphenyl) disulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, etc. Aromatic bisphenol compounds; 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane, 2,2-bis (4- (2-hydroxypropoxy) phenyl) propane, 1,3-bis (2-hydroxy) Dihydroxy compound having an ether group bonded to an aromatic group such as ethoxy) benzene, 4,4'-bis (2-hydroxyethoxy) biphenyl, bis (4- (2-hydroxyethoxy) phenyl) sulfone; terephthalic acid, phthalic acid. Acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylether dicarboxylic acid Aromatic dicarboxylic acids such as acids, 4,4'-benzophenonedicarboxylic acids, 4,4'-diphenoxyetanedicarboxylic acids, 4,4'-diphenylsulfonedicarboxylic acids, and 2,6-naphthalenedicarboxylic acids.
The aliphatic dicarboxylic acid and the aromatic dicarboxylic acid component mentioned above can be used as a raw material for the polyester carbonate as the dicarboxylic acid itself, but depending on the production method, a dicarboxylic acid such as a methyl ester or a phenyl ester can be used. Dicarboxylic acid derivatives such as esters and dicarboxylic acid halides can also be used as raw materials.
前記脂肪族構造で構成される化合物の具体例を以下に挙げる。エチレングリコール、1,3-プロパンジオール、1,2-プロパンジオール、1,4-ブタンジオール、1,3-ブタンジオール、1,2-ブタンジオール、1,5-ヘプタンジオール、1,6-ヘキサンジオール、1,9-ノナンジオール、1,10-デカンジオール、1,12-ドデカンジオール等の直鎖脂肪族炭化水素のジヒドロキシ化合物;ネオペンチルグリコール、ヘキシレングリコール等の分岐脂肪族炭化水素のジヒドロキシ化合物;1,2-シクロヘキサンジオール、1,4-シクロヘキサンジオール、1,3-アダマンタンジオール、水添ビスフェノールA、2,2,4,4-テトラメチル-1,3-シクロブタンジオール等に例示される、脂環式炭化水素の2級アルコール、及び3級アルコールであるジヒドロキシ化合物;1,2-シクロヘキサンジメタノール、1,3-シクロヘキサンジメタノール、1,4-シクロヘキサンジメタノール、トリシクロデカンジメタノール、ペンタシクロペンタデカンジメタノール、2,6-デカリンジメタノール、1,5-デカリンジメタノール、2,3-デカリンジメタノール、2,3-ノルボルナンジメタノール、2,5-ノルボルナンジメタノール、1,3-アダマンタンジメタノール、リモネン等の、テルペン化合物から誘導されるジヒドロキシ化合物等に例示される、脂環式炭化水素の1級アルコールであるジヒドロキシ化合物;ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール等のオキシアルキレングリコール類;イソソルビド等の環状エーテル構造を有するジヒドロキシ化合物;スピログリコール、ジオキサングリコール等の環状アセタール構造を有するジヒドロキシ化合物;1,2-シクロヘキサンジカルボン酸、1,3-シクロヘキサンジカルボン酸、1,4-シクロヘキサンジカルボン酸等の脂環式ジカルボン酸;、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等の脂肪族ジカルボン酸。
前記芳香族環を含む構造単位を導入可能な化合物の具体例を以下に挙げる。2,2-ビス(4-ヒドロキシフェニル)プロパン、2,2-ビス(3-メチル-4-ヒドロキシフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3,5-ジメチルフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3,5-ジエチルフェニル)プロパン、2,2-ビス(4-ヒドロキシ-(3-フェニル)フェニル)プロパン、2,2-ビス(4-ヒドロキシ-(3,5-ジフェニル)フェニル)プロパン、2,2-ビス(4-ヒドロキシ-3,5-ジブロモフェニル)プロパン、ビス(4-ヒドロキシフェニル)メタン、1,1-ビス(4-ヒドロキシフェニル)エタン、2,2-ビス(4-ヒドロキシフェニル)ブタン、2,2-ビス(4-ヒドロキシフェニル)ペンタン、1,1-ビス(4-ヒドロキシフェニル)-1-フェニルエタン、ビス(4-ヒドロキシフェニル)ジフェニルメタン、1,1-ビス(4-ヒドロキシフェニル)-2-エチルヘキサン、1,1-ビス(4-ヒドロキシフェニル)デカン、ビス(4-ヒドロキシ-3-ニトロフェニル)メタン、3,3-ビス(4-ヒドロキシフェニル)ペンタン、1,3-ビス(2-(4-ヒドロキシフェニル)-2-プロピル)ベンゼン、1,3-ビス(2-(4-ヒドロキシフェニル)-2-プロピル)ベンゼン、2,2-ビス(4-ヒドロキシフェニル)ヘキサフルオロプロパン、1,1-ビス(4-ヒドロキシフェニル)シクロヘキサン、ビス(4-ヒドロキシフェニル)スルホン、2,4’-ジヒドロキシジフェニルスルホン、ビス(4-ヒドロキシフェニル)スルフィド、ビス(4-ヒドロキシ-3-メチルフェニル)スルフィド、ビス(4-ヒドロキシフェニル)ジスルフィド、4,4’-ジヒドロキシジフェニルエーテル、4,4’-ジヒドロキシ-3,3’-ジクロロジフェニルエーテル等の芳香族ビスフェノール化合物;2,2-ビス(4-(2-ヒドロキシエトキシ)フェニル)プロパン、2,2-ビス(4-(2-ヒドロキシプロポキシ)フェニル)プロパン、1,3-ビス(2-ヒドロキシエトキシ)ベンゼン、4,4’-ビス(2-ヒドロキシエトキシ)ビフェニル、ビス(4-(2-ヒドロキシエトキシ)フェニル)スルホン等の芳香族基に結合したエーテル基を有するジヒドロキシ化合物;テレフタル酸、フタル酸、イソフタル酸、4,4’-ジフェニルジカルボン酸、4,4’-ジフェニルエーテルジカルボン酸、4,4’-ベンゾフェノンジカルボン酸、4,4’-ジフェノキシエタンジカルボン酸、4,4’-ジフェニルスルホンジカルボン酸、2,6-ナフタレンジカルボン酸等の芳香族ジカルボン酸。
尚、上記で挙げた脂肪族ジカルボン酸及び芳香族ジカルボン酸成分はジカルボン酸そのものとして前記ポリエステルカーボネートの原料とすることができるが、製造法に応じて、メチルエステル体、フェニルエステル体等のジカルボン酸エステルや、ジカルボン酸ハライド等のジカルボン酸誘導体を原料とすることもできる。 Examples of the copolymerization monomer include a compound into which a structural unit containing an aromatic ring can be introduced and a compound in which a structural unit containing an aromatic ring is not introduced, that is, a compound having an aliphatic structure.
Specific examples of the compound having the aliphatic structure are given below. Ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexane Dihydroxy compounds of linear aliphatic hydrocarbons such as diols, 1,9-nonanediols, 1,10-decanediols and 1,12-dodecanediol; dihydroxys of branched aliphatic hydrocarbons such as neopentyl glycol and hexylene glycol. Compounds; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantandiol, hydrogenated bisphenol A, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and the like are exemplified. , Secondary alcohols of alicyclic hydrocarbons, and dihydroxy compounds which are tertiary alcohols; 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, Pentacyclopentadecanedimethanol, 2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol, 2,3-norbornandimethanol, 2,5-norbornandimethanol, 1,3- Dihydroxy compounds which are primary alcohols of alicyclic hydrocarbons exemplified by dihydroxy compounds derived from terpene compounds such as adamantandimethanol and limonene; diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol and polypropylene. Oxyalkylene glycols such as glycol; dihydroxy compounds having a cyclic ether structure such as isosorbide; dihydroxy compounds having a cyclic acetal structure such as spiroglycol and dioxane glycol; 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, An alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid; an aliphatic dicarboxylic acid such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
Specific examples of the compound into which the structural unit containing the aromatic ring can be introduced are given below. 2,2-Bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2 , 2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3-phenyl) phenyl) propane, 2,2-bis (4-hydroxy- (3,3) 5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2 , 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane , 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 1,1-bis (4-hydroxyphenyl) decane, bis (4-hydroxy-3-nitrophenyl) methane, 3,3-bis ( 4-Hydroxyphenyl) pentane, 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 2 , 2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenyl sulfone, bis (4-hydroxy) Phenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4-hydroxyphenyl) disulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, etc. Aromatic bisphenol compounds; 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane, 2,2-bis (4- (2-hydroxypropoxy) phenyl) propane, 1,3-bis (2-hydroxy) Dihydroxy compound having an ether group bonded to an aromatic group such as ethoxy) benzene, 4,4'-bis (2-hydroxyethoxy) biphenyl, bis (4- (2-hydroxyethoxy) phenyl) sulfone; terephthalic acid, phthalic acid. Acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylether dicarboxylic acid Aromatic dicarboxylic acids such as acids, 4,4'-benzophenonedicarboxylic acids, 4,4'-diphenoxyetanedicarboxylic acids, 4,4'-diphenylsulfonedicarboxylic acids, and 2,6-naphthalenedicarboxylic acids.
The aliphatic dicarboxylic acid and the aromatic dicarboxylic acid component mentioned above can be used as a raw material for the polyester carbonate as the dicarboxylic acid itself, but depending on the production method, a dicarboxylic acid such as a methyl ester or a phenyl ester can be used. Dicarboxylic acid derivatives such as esters and dicarboxylic acid halides can also be used as raw materials.
共重合モノマーとして、負の複屈折を有する構造単位を有する化合物として従来より知られている、9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレン、9,9-ビス(4-ヒドロキシフェニル)フルオレン、9,9-ビス(4-ヒドロキシ-3-メチルフェニル)フルオレン等のフルオレン環を有するジヒドロキシ化合物や、フルオレン環を有するジカルボン酸化合物もオリゴフルオレン化合物と組み合わせて用いることができる。
As a copolymerization monomer, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and 9,9-bis (4-), which are conventionally known as compounds having a structural unit having a negative compound refraction, are conventionally known. Dihydroxy compounds having a fluorene ring such as hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and dicarboxylic acid compounds having a fluorene ring can also be used in combination with oligofluorene compounds.
本発明に用いられる樹脂は、前記脂環式構造を有する化合物によって導入可能な構造単位の中でも、共重合成分として下記式(3)で表される構造単位を含有することが好ましい。
The resin used in the present invention preferably contains a structural unit represented by the following formula (3) as a copolymerization component among the structural units that can be introduced by the compound having an alicyclic structure.
前記式(3)の構造単位を導入可能なジヒドロキシ化合物としては、スピログリコールを用いることができる。
Spiroglycol can be used as the dihydroxy compound into which the structural unit of the formula (3) can be introduced.
本発明に用いられる樹脂において、前記式(3)で表される構造単位は5質量%以上、90質量%以下含有されていることが好ましい。上限は70質量%以下がさらに好ましく、50質量%以下が特に好ましい。下限は10質量%以上がさらに好ましく、20質量%以上がより好ましく、25質量%以上が特に好ましい。前記式(3)で表される構造単位の含有量が前記下限以上であれば、十分な機械物性や耐熱性、低い光弾性係数が得られる。さらに、アクリル系樹脂との相溶性が向上し、得られる樹脂組成物の透明性をさらに向上することができる。また、スピログリコールは重合反応の速度が比較的に遅いため、含有量を前記上限以下に抑えることで、重合反応を制御しやすくなる。
In the resin used in the present invention, the structural unit represented by the formula (3) is preferably contained in an amount of 5% by mass or more and 90% by mass or less. The upper limit is more preferably 70% by mass or less, and particularly preferably 50% by mass or less. The lower limit is more preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 25% by mass or more. When the content of the structural unit represented by the formula (3) is at least the lower limit, sufficient mechanical characteristics, heat resistance, and a low photoelastic coefficient can be obtained. Further, the compatibility with the acrylic resin is improved, and the transparency of the obtained resin composition can be further improved. Further, since the rate of the polymerization reaction of spiroglycol is relatively slow, it becomes easy to control the polymerization reaction by suppressing the content to the above upper limit or less.
本発明に用いられる樹脂は、共重合成分としてさらに下記式(4)で表される構造単位を含有することが好ましい。
The resin used in the present invention preferably further contains a structural unit represented by the following formula (4) as a copolymerization component.
前記式(4)で表される構造単位を導入可能なジヒドロキシ化合物としては、立体異性体の関係にある、イソソルビド(ISB)、イソマンニド、イソイデットが挙げられる。これらは1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
Examples of the dihydroxy compound into which the structural unit represented by the above formula (4) can be introduced include isosorbide (ISB), isomannide, and isoidet, which are in a stereoisomer relationship. These may be used individually by 1 type and may be used in combination of 2 or more type.
本発明に用いられる樹脂において、前記式(4)で表される構造単位は5質量%以上、90質量%以下含有されていることが好ましい。上限は70質量%以下がさらに好ましく、50質量%以下が特に好ましい。下限は10質量%以上がさらに好ましく、15質量%以上が特に好ましい。前記式(4)で表される構造単位の含有量が前記下限以上であれば、十分な機械物性や耐熱性、低い光弾性係数が得られる。また、前記式(4)で表される構造単位は吸水性が高い特性があるため、前記式(4)で表される構造単位の含有量が前記上限以下であれば、吸水による成形体の寸法変化を許容範囲に抑えることができる。
In the resin used in the present invention, the structural unit represented by the above formula (4) is preferably contained in an amount of 5% by mass or more and 90% by mass or less. The upper limit is more preferably 70% by mass or less, and particularly preferably 50% by mass or less. The lower limit is more preferably 10% by mass or more, and particularly preferably 15% by mass or more. When the content of the structural unit represented by the formula (4) is at least the above lower limit, sufficient mechanical characteristics, heat resistance, and a low photoelastic coefficient can be obtained. Further, since the structural unit represented by the formula (4) has a characteristic of high water absorption, if the content of the structural unit represented by the formula (4) is not more than the upper limit, the molded product by water absorption The dimensional change can be suppressed to an allowable range.
本発明に用いられる樹脂は、さらに別の構造単位を含んでいてもよい。尚、かかる構造単位を「その他の構造単位」と称することがある。その他の構造単位を有するモノマーとしては、1,4-シクロヘキサンジメタノール、トリシクロデカンジメタノール、1,4-シクロヘキサンジカルボン酸(及びその誘導体)を採用することがより好ましく、1,4-シクロヘキサンジメタノールとトリシクロデカンジメタノールが特に好ましい。これらのモノマーに由来する構造単位を含む樹脂は、光学特性や耐熱性、機械特性等のバランスに優れている。また、ジエステル化合物の重合反応性は比較的低いため、反応効率を高める観点から、オリゴフルオレン構造単位を含有するジエステル化合物以外のジエステル化合物は用いないことが好ましい。
The resin used in the present invention may contain still another structural unit. In addition, such a structural unit may be referred to as "another structural unit". As the monomer having other structural units, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, and 1,4-cyclohexanedicarboxylic acid (and its derivatives) are more preferable, and 1,4-cyclohexanedimethanol is more preferable. Methanol and tricyclodecanedimethanol are particularly preferred. A resin containing a structural unit derived from these monomers has an excellent balance of optical properties, heat resistance, mechanical properties, and the like. Further, since the polymerization reactivity of the diester compound is relatively low, it is preferable not to use a diester compound other than the diester compound containing an oligofluorene structural unit from the viewpoint of increasing the reaction efficiency.
本発明に用いられる樹脂のガラス転移温度(Tg)は、110℃以上160℃以下であることが好ましい。上限は155℃以下がさらに好ましく、150℃以下がより好ましく、145℃以下が特に好ましい。下限は120℃以上がさらに好ましく、130℃以上が特に好ましい。ガラス転移温度が上記範囲外であると耐熱性が悪くなる傾向にあり、フィルム成形後に寸法変化を起こしたり、位相差フィルムの使用条件下における品質の信頼性が悪化する可能性がある。一方、ガラス転移温度が過度に高いと、フィルム成形時にフィルム厚みの斑が生じたり、フィルムが脆くなり、延伸性が悪化したりする場合があり、また、フィルムの透明性を損なう場合がある。
The glass transition temperature (Tg) of the resin used in the present invention is preferably 110 ° C. or higher and 160 ° C. or lower. The upper limit is more preferably 155 ° C or lower, more preferably 150 ° C or lower, and particularly preferably 145 ° C or lower. The lower limit is more preferably 120 ° C. or higher, and particularly preferably 130 ° C. or higher. If the glass transition temperature is out of the above range, the heat resistance tends to deteriorate, which may cause a dimensional change after film molding or deteriorate the reliability of quality under the usage conditions of the retardation film. On the other hand, if the glass transition temperature is excessively high, unevenness in the film thickness may occur during film molding, the film may become brittle, the stretchability may deteriorate, and the transparency of the film may be impaired.
ポリカーボネート系樹脂等の構成および製造方法等の詳細は、例えば、国際公開第2015/159928号パンフレット(上記)に記載されている。この記載は、本明細書に参考として援用される。
Details of the composition and manufacturing method of the polycarbonate-based resin and the like are described in, for example, International Publication No. 2015/159928 (above). This description is incorporated herein by reference.
D-2-2.アクリル系樹脂
アクリル系樹脂としては、熱可塑性樹脂としてのアクリル系樹脂が使用される。アクリル系樹脂の構造単位となる単量体としては、例えば、以下の化合物が挙げられる:メタクリル酸メチル、メタクリル酸、アクリル酸メチル、アクリル酸、ベンジル(メタ)アクリレート、n-ブチル(メタ)アクリレート、i-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、トリデシル(メタ)アクリレート、ステアリル(メタ)アクリレート、グリシジル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、2-メトキシエチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ノルボルニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、アクリル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、コハク酸2-(メタ)アクロイルオキシエチル、マレイン酸2-(メタ)アクロイルオキシエチル、フタル酸2-(メタ)アクロイルオキシエチル、ヘキサヒドロフタル酸2-(メタ)アクリオイルオキシエチル、ペンタメチルピペリジル(メタ)アクリレート、テトラメチルピペリジル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、シクロペンチルメタクリレート、シクロペンチルアクリレート、シクロヘキシルメタクリレート、シクロヘキシルアクリレート、シクロヘプチルメタクリレート、シクロヘプチルアクリレート、シクロオクチルメタクリレート、シクロオクチルアクリレート、シクロドデシルメタクリレート、シクロドデシルアクリレート。これらは、単独で用いてもよく、2種類以上を組み合わせて用いてもよい。2種以上の単量体を組み合わせて用いる形態は、2種以上の単量体の共重合、1種の単量体の単独重合体の2つ以上のブレンド、およびこれらの組み合わせが挙げられる。さらに、これらのアクリル系単量体と共重合可能な他の単量体(例えば、オレフィン系単量体、ビニル系単量体)を併用してもよい。 D-2-2. Acrylic resin As the acrylic resin, an acrylic resin as a thermoplastic resin is used. Examples of the monomer as a structural unit of the acrylic resin include the following compounds: methyl methacrylate, methacrylic acid, methyl acrylate, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate. , I-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxy Propyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acrylic (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acro succinate Iloxyethyl, 2- (meth) acroyloxyethyl maleate, 2- (meth) acroyloxyethyl phthalate, 2- (meth) aclioil oxyethyl hexahydrophthalate, pentamethylpiperidyl (meth) acrylate, Tetramethylpiperidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, cyclopentyl methacrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, cycloheptyl methacrylate, cycloheptyl acrylate, cyclooctyl methacrylate, cyclooctyl acrylate. , Cyclododecyl methacrylate, cyclododecyl acrylate. These may be used alone or in combination of two or more. Examples of the form in which two or more kinds of monomers are used in combination include copolymerization of two or more kinds of monomers, two or more blends of one kind of monomer homopolymer, and combinations thereof. Further, other monomers copolymerizable with these acrylic monomers (for example, olefin monomers and vinyl monomers) may be used in combination.
アクリル系樹脂としては、熱可塑性樹脂としてのアクリル系樹脂が使用される。アクリル系樹脂の構造単位となる単量体としては、例えば、以下の化合物が挙げられる:メタクリル酸メチル、メタクリル酸、アクリル酸メチル、アクリル酸、ベンジル(メタ)アクリレート、n-ブチル(メタ)アクリレート、i-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、トリデシル(メタ)アクリレート、ステアリル(メタ)アクリレート、グリシジル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、2-メトキシエチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ノルボルニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、アクリル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、コハク酸2-(メタ)アクロイルオキシエチル、マレイン酸2-(メタ)アクロイルオキシエチル、フタル酸2-(メタ)アクロイルオキシエチル、ヘキサヒドロフタル酸2-(メタ)アクリオイルオキシエチル、ペンタメチルピペリジル(メタ)アクリレート、テトラメチルピペリジル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、シクロペンチルメタクリレート、シクロペンチルアクリレート、シクロヘキシルメタクリレート、シクロヘキシルアクリレート、シクロヘプチルメタクリレート、シクロヘプチルアクリレート、シクロオクチルメタクリレート、シクロオクチルアクリレート、シクロドデシルメタクリレート、シクロドデシルアクリレート。これらは、単独で用いてもよく、2種類以上を組み合わせて用いてもよい。2種以上の単量体を組み合わせて用いる形態は、2種以上の単量体の共重合、1種の単量体の単独重合体の2つ以上のブレンド、およびこれらの組み合わせが挙げられる。さらに、これらのアクリル系単量体と共重合可能な他の単量体(例えば、オレフィン系単量体、ビニル系単量体)を併用してもよい。 D-2-2. Acrylic resin As the acrylic resin, an acrylic resin as a thermoplastic resin is used. Examples of the monomer as a structural unit of the acrylic resin include the following compounds: methyl methacrylate, methacrylic acid, methyl acrylate, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate. , I-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxy Propyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acrylic (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acro succinate Iloxyethyl, 2- (meth) acroyloxyethyl maleate, 2- (meth) acroyloxyethyl phthalate, 2- (meth) aclioil oxyethyl hexahydrophthalate, pentamethylpiperidyl (meth) acrylate, Tetramethylpiperidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, cyclopentyl methacrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, cycloheptyl methacrylate, cycloheptyl acrylate, cyclooctyl methacrylate, cyclooctyl acrylate. , Cyclododecyl methacrylate, cyclododecyl acrylate. These may be used alone or in combination of two or more. Examples of the form in which two or more kinds of monomers are used in combination include copolymerization of two or more kinds of monomers, two or more blends of one kind of monomer homopolymer, and combinations thereof. Further, other monomers copolymerizable with these acrylic monomers (for example, olefin monomers and vinyl monomers) may be used in combination.
アクリル系樹脂は、メタクリル酸メチル由来の構造単位を含む。アクリル系樹脂におけるメタクリル酸メチル由来の構造単位の含有量は70質量%以上、100質量%以下が好ましい。下限は80質量%以上がより好ましく、90質量%以上がさらに好ましく、95質量%以上が特に好ましい。この範囲であると、本発明のポリカーボネート系樹脂と優れた相溶性が得られる。メタクリル酸メチル以外の構造単位としては、アクリル酸メチル、フェニル(メタ)アクリレート、ベンジル(メタ)アクリレート、スチレンを用いることが好ましい。アクリル酸メチルを共重合することで熱安定性を向上させることができる。フェニル(メタ)アクリレート、ベンジル(メタ)アクリレート、スチレンを用いることで、アクリル系樹脂の屈折率を調整することができるため、組み合わせる樹脂の屈折率に合わせ込むことで、得られる樹脂組成物の透明性を向上させることができる。このようなアクリル系樹脂を用いることで、伸張性および位相差発現性に優れ、かつ、ヘイズの小さい逆分散位相差フィルムが得られ得る。
Acrylic resin contains structural units derived from methyl methacrylate. The content of the structural unit derived from methyl methacrylate in the acrylic resin is preferably 70% by mass or more and 100% by mass or less. The lower limit is more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more. Within this range, excellent compatibility with the polycarbonate resin of the present invention can be obtained. As the structural unit other than methyl methacrylate, it is preferable to use methyl acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene. Thermal stability can be improved by copolymerizing methyl acrylate. Since the refractive index of the acrylic resin can be adjusted by using phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene, the transparent resin composition obtained by adjusting to the refractive index of the combined resin can be adjusted. It is possible to improve the sex. By using such an acrylic resin, a reverse dispersion retardation film having excellent extensibility and phase difference expression and having a small haze can be obtained.
アクリル系樹脂の重量平均分子量Mwは、10,000以上、200,000以下である。下限は30,000以上が好ましく、50,000以上が特に好ましい。上限は180,000以下が好ましく、150,000以下が特に好ましい。分子量がこのような範囲であれば、ポリカーボネート系樹脂との相溶性が得られることで、最終的な位相差フィルム(位相差層)の透明性を向上させることができ、かつ、延伸時の伸張性を十分に向上させる効果が得られる。尚、上記の重量平均分子量はGPCにより測定される、ポリスチレン換算の分子量である。また、アクリル系樹脂は実質的に分岐構造を含有しないことが相溶性の観点から好ましい。分岐構造を含有しないことは、アクリル系樹脂のGPCカーブが単峰性であることなどで確認できる。
The weight average molecular weight Mw of the acrylic resin is 10,000 or more and 200,000 or less. The lower limit is preferably 30,000 or more, and particularly preferably 50,000 or more. The upper limit is preferably 180,000 or less, and particularly preferably 150,000 or less. When the molecular weight is in such a range, compatibility with the polycarbonate resin can be obtained, so that the transparency of the final retardation film (phase difference layer) can be improved, and the elongation during stretching can be improved. The effect of sufficiently improving the sex can be obtained. The above weight average molecular weight is a polystyrene-equivalent molecular weight measured by GPC. Further, it is preferable that the acrylic resin does not substantially contain a branched structure from the viewpoint of compatibility. The fact that it does not contain a branched structure can be confirmed by the fact that the GPC curve of the acrylic resin is monomodal.
D-2-3.ポリカーボネート系樹脂等とアクリル系樹脂とのブレンド
ポリカーボネート系樹脂等とアクリル系樹脂とはブレンドされ、樹脂組成物として位相差フィルム(位相差層)の製造方法に供される(製造方法はC-3項で後述する)。ポリカーボネート系樹脂等とアクリル系樹脂とは、好ましくは、溶融状態でブレンドされ得る。溶融状態でブレンドする方法としては、代表的には、押出機を用いた溶融混練が挙げられる。混練温度(溶融樹脂温度)は、好ましくは200℃~280℃であり、より好ましくは220℃~270℃であり、さらに好ましくは230℃~260℃である。混練温度がこのような範囲であれば、熱分解を抑制しながら、両樹脂が均一にブレンドされた樹脂組成物のペレットが得られ得る。押出機中の溶融樹脂温度が280℃を超えると、樹脂の着色および/または熱分解が発生する場合がある。一方、押出機中の溶融樹脂温度が200℃を下回ると、樹脂粘度が高くなり過ぎて押出機に過大な負荷が掛かったり、樹脂の溶融が不十分となる場合がある。なお、押出機の構成、スクリューの構成等としては、任意の適切な構成が採用され得る。光学フィルム用途に耐え得る樹脂の透明性を得るためには二軸押出機を用いることが好ましい。さらに、樹脂中の残存低分子成分や、押出混錬中の低分子量の熱分解成分は、製膜工程や延伸工程で冷却ロールや搬送ロールを汚染する懸念があるため、これを除去するために、真空ベントを備える押出機を用いることが好ましい。 D-2-3. Blending of Polycarbonate Resin, etc. and Acrylic Resin Polycarbonate Resin, etc. and Acrylic Resin are blended and used as a resin composition in a method for producing a retardation film (phase difference layer) (the production method is C-3). Will be described later in the section). The polycarbonate-based resin or the like and the acrylic-based resin can be preferably blended in a molten state. A typical method for blending in a molten state includes melt kneading using an extruder. The kneading temperature (molten resin temperature) is preferably 200 ° C. to 280 ° C., more preferably 220 ° C. to 270 ° C., and further preferably 230 ° C. to 260 ° C. When the kneading temperature is in such a range, pellets of a resin composition in which both resins are uniformly blended can be obtained while suppressing thermal decomposition. If the temperature of the molten resin in the extruder exceeds 280 ° C., coloration and / or thermal decomposition of the resin may occur. On the other hand, if the temperature of the molten resin in the extruder is lower than 200 ° C., the viscosity of the resin may become too high, an excessive load may be applied to the extruder, or the resin may be insufficiently melted. Any appropriate configuration can be adopted as the configuration of the extruder, the configuration of the screw, and the like. It is preferable to use a twin-screw extruder in order to obtain the transparency of the resin that can withstand the optical film application. Furthermore, the residual low molecular weight components in the resin and the low molecular weight pyrolysis components during extrusion kneading may contaminate the cooling rolls and transport rolls in the film forming process and the stretching process, so that they can be removed. , It is preferable to use an extruder equipped with a vacuum vent.
ポリカーボネート系樹脂等とアクリル系樹脂とはブレンドされ、樹脂組成物として位相差フィルム(位相差層)の製造方法に供される(製造方法はC-3項で後述する)。ポリカーボネート系樹脂等とアクリル系樹脂とは、好ましくは、溶融状態でブレンドされ得る。溶融状態でブレンドする方法としては、代表的には、押出機を用いた溶融混練が挙げられる。混練温度(溶融樹脂温度)は、好ましくは200℃~280℃であり、より好ましくは220℃~270℃であり、さらに好ましくは230℃~260℃である。混練温度がこのような範囲であれば、熱分解を抑制しながら、両樹脂が均一にブレンドされた樹脂組成物のペレットが得られ得る。押出機中の溶融樹脂温度が280℃を超えると、樹脂の着色および/または熱分解が発生する場合がある。一方、押出機中の溶融樹脂温度が200℃を下回ると、樹脂粘度が高くなり過ぎて押出機に過大な負荷が掛かったり、樹脂の溶融が不十分となる場合がある。なお、押出機の構成、スクリューの構成等としては、任意の適切な構成が採用され得る。光学フィルム用途に耐え得る樹脂の透明性を得るためには二軸押出機を用いることが好ましい。さらに、樹脂中の残存低分子成分や、押出混錬中の低分子量の熱分解成分は、製膜工程や延伸工程で冷却ロールや搬送ロールを汚染する懸念があるため、これを除去するために、真空ベントを備える押出機を用いることが好ましい。 D-2-3. Blending of Polycarbonate Resin, etc. and Acrylic Resin Polycarbonate Resin, etc. and Acrylic Resin are blended and used as a resin composition in a method for producing a retardation film (phase difference layer) (the production method is C-3). Will be described later in the section). The polycarbonate-based resin or the like and the acrylic-based resin can be preferably blended in a molten state. A typical method for blending in a molten state includes melt kneading using an extruder. The kneading temperature (molten resin temperature) is preferably 200 ° C. to 280 ° C., more preferably 220 ° C. to 270 ° C., and further preferably 230 ° C. to 260 ° C. When the kneading temperature is in such a range, pellets of a resin composition in which both resins are uniformly blended can be obtained while suppressing thermal decomposition. If the temperature of the molten resin in the extruder exceeds 280 ° C., coloration and / or thermal decomposition of the resin may occur. On the other hand, if the temperature of the molten resin in the extruder is lower than 200 ° C., the viscosity of the resin may become too high, an excessive load may be applied to the extruder, or the resin may be insufficiently melted. Any appropriate configuration can be adopted as the configuration of the extruder, the configuration of the screw, and the like. It is preferable to use a twin-screw extruder in order to obtain the transparency of the resin that can withstand the optical film application. Furthermore, the residual low molecular weight components in the resin and the low molecular weight pyrolysis components during extrusion kneading may contaminate the cooling rolls and transport rolls in the film forming process and the stretching process, so that they can be removed. , It is preferable to use an extruder equipped with a vacuum vent.
樹脂組成物(結果として、位相差層)におけるアクリル系樹脂の含有量は、例えば0.5質量%以上、2.0質量%以下である。下限は0.6質量%以上がより好ましい。上限は1.5質量%以下が好ましく、1.0重量%以下がより好ましく、0.9重量%以下がさらに好ましく、0.8質量%以下が特に好ましい。このように、ポリカーボネート系樹脂にアクリル系樹脂をごく限定的な比率で配合することにより、伸張性および位相差発現性を顕著に増大させることができる。さらに、ヘイズを抑制することができる。このような効果は理論的には明らかでなく、試行錯誤により得られた予期せぬ優れた効果である。なお、アクリル系樹脂の含有量が少なすぎると、上記の効果が得られない場合がある。一方、アクリル系樹脂の含有量が多すぎると、ヘイズが高くなってしまう場合がある。また、伸張性および位相差発現性も上記範囲内の場合に比べて不十分となったり、かえって低下してしまう場合が多い。
The content of the acrylic resin in the resin composition (as a result, the retardation layer) is, for example, 0.5% by mass or more and 2.0% by mass or less. The lower limit is more preferably 0.6% by mass or more. The upper limit is preferably 1.5% by mass or less, more preferably 1.0% by weight or less, further preferably 0.9% by weight or less, and particularly preferably 0.8% by mass or less. As described above, by blending the acrylic resin with the polycarbonate resin in a very limited ratio, the extensibility and the phase difference expression can be remarkably increased. Furthermore, haze can be suppressed. Such an effect is not clear in theory, and is an unexpectedly excellent effect obtained by trial and error. If the content of the acrylic resin is too small, the above effect may not be obtained. On the other hand, if the content of the acrylic resin is too large, the haze may increase. In addition, the extensibility and the phase difference expression are often insufficient or even lower than those within the above range.
樹脂組成物は、機械特性および/または耐溶剤性等の特性を改質する目的で、芳香族ポリカーボネート、脂肪族ポリカーボネート、芳香族ポリエステル、脂肪族ポリエステル、ポリアミド、ポリスチレン、ポリオレフィン、アクリル、アモルファスポリオレフィン、ABS、AS、ポリ乳酸、ポリブチレンスクシネート等の合成樹脂、ゴム、およびこれらの組み合わせがさらにブレンドされてもよい。
The resin composition comprises aromatic polycarbonate, aliphatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, for the purpose of modifying properties such as mechanical properties and / or solvent resistance. Synthetic resins such as ABS, AS, polylactic acid, polybutylene succinate, rubber, and combinations thereof may be further blended.
樹脂組成物は、添加剤をさらに含んでいてもよい。添加剤の具体例としては、熱安定剤、酸化防止剤、触媒失活剤、紫外線吸収剤、光安定剤、離型剤、染顔料、衝撃改良剤、帯電防止剤、滑剤、潤滑剤、可塑剤、相溶化剤、核剤、難燃剤、無機充填剤、発泡剤が挙げられる。樹脂組成物に含まれる添加剤の種類、数、組み合わせ、含有量等は、目的に応じて適切に設定され得る。
The resin composition may further contain additives. Specific examples of additives include heat stabilizers, antioxidants, catalyst deactivating agents, ultraviolet absorbers, light stabilizers, mold release agents, dye pigments, impact improvers, antistatic agents, lubricants, lubricants, and plasticizers. Examples include agents, compatibilizers, nucleating agents, flame retardants, inorganic fillers and effervescent agents. The type, number, combination, content, etc. of the additives contained in the resin composition can be appropriately set according to the purpose.
D-3.位相差層の形成方法
位相差層は、上記D-2項に記載の樹脂組成物からフィルムを形成し、さらにそのフィルムを延伸することにより得られる。樹脂組成物からフィルムを形成する方法としては、任意の適切な成形加工法が採用され得る。具体例としては、圧縮成形法、トランスファー成形法、射出成形法、押出成形法、ブロー成形法、粉末成形法、FRP成形法、キャスト塗工法(例えば、流延法)、カレンダー成形法、熱プレス法等が挙げられる。中でも得られるフィルムの平滑性を高め、良好な光学的均一性を得ることができる押出成形法、またはキャスト塗工法が好ましい。キャスト塗工法では残存溶媒による問題が生じるおそれがあるため、特に好ましくは押出成形法、中でもTダイを用いた溶融押出成形法がフィルムの生産性や、後の延伸処理のし易さの観点から好ましい。成形条件は、使用される樹脂の組成や種類、位相差層に所望される特性等に応じて適宜設定され得る。このようにして、ポリカーボネート系樹脂等とアクリル系樹脂とを含む樹脂フィルムが得られ得る。 D-3. Method for Forming a Phase Difference Layer The retardation layer is obtained by forming a film from the resin composition according to the above item D-2 and further stretching the film. As a method for forming a film from the resin composition, any suitable molding processing method can be adopted. Specific examples include a compression molding method, a transfer molding method, an injection molding method, an extrusion molding method, a blow molding method, a powder molding method, an FRP molding method, a cast coating method (for example, a casting method), a calendar molding method, and a hot press. The law etc. can be mentioned. Of these, an extrusion molding method or a cast coating method that can improve the smoothness of the obtained film and obtain good optical uniformity is preferable. Since the cast coating method may cause problems due to the residual solvent, the extrusion molding method, particularly the melt extrusion molding method using a T-die, is particularly preferable from the viewpoint of film productivity and ease of subsequent stretching treatment. preferable. The molding conditions can be appropriately set according to the composition and type of the resin used, the characteristics desired for the retardation layer, and the like. In this way, a resin film containing a polycarbonate-based resin or the like and an acrylic-based resin can be obtained.
位相差層は、上記D-2項に記載の樹脂組成物からフィルムを形成し、さらにそのフィルムを延伸することにより得られる。樹脂組成物からフィルムを形成する方法としては、任意の適切な成形加工法が採用され得る。具体例としては、圧縮成形法、トランスファー成形法、射出成形法、押出成形法、ブロー成形法、粉末成形法、FRP成形法、キャスト塗工法(例えば、流延法)、カレンダー成形法、熱プレス法等が挙げられる。中でも得られるフィルムの平滑性を高め、良好な光学的均一性を得ることができる押出成形法、またはキャスト塗工法が好ましい。キャスト塗工法では残存溶媒による問題が生じるおそれがあるため、特に好ましくは押出成形法、中でもTダイを用いた溶融押出成形法がフィルムの生産性や、後の延伸処理のし易さの観点から好ましい。成形条件は、使用される樹脂の組成や種類、位相差層に所望される特性等に応じて適宜設定され得る。このようにして、ポリカーボネート系樹脂等とアクリル系樹脂とを含む樹脂フィルムが得られ得る。 D-3. Method for Forming a Phase Difference Layer The retardation layer is obtained by forming a film from the resin composition according to the above item D-2 and further stretching the film. As a method for forming a film from the resin composition, any suitable molding processing method can be adopted. Specific examples include a compression molding method, a transfer molding method, an injection molding method, an extrusion molding method, a blow molding method, a powder molding method, an FRP molding method, a cast coating method (for example, a casting method), a calendar molding method, and a hot press. The law etc. can be mentioned. Of these, an extrusion molding method or a cast coating method that can improve the smoothness of the obtained film and obtain good optical uniformity is preferable. Since the cast coating method may cause problems due to the residual solvent, the extrusion molding method, particularly the melt extrusion molding method using a T-die, is particularly preferable from the viewpoint of film productivity and ease of subsequent stretching treatment. preferable. The molding conditions can be appropriately set according to the composition and type of the resin used, the characteristics desired for the retardation layer, and the like. In this way, a resin film containing a polycarbonate-based resin or the like and an acrylic-based resin can be obtained.
樹脂フィルム(未延伸フィルム)の厚みは、得られる位相差層の所望の厚み、所望の光学特性、後述の延伸条件などに応じて、任意の適切な値に設定され得る。好ましくは50μm~300μmである。
The thickness of the resin film (unstretched film) can be set to an arbitrary appropriate value according to the desired thickness of the obtained retardation layer, desired optical characteristics, stretching conditions described later, and the like. It is preferably 50 μm to 300 μm.
上記延伸は、任意の適切な延伸方法、延伸条件(例えば、延伸温度、延伸倍率、延伸方向)が採用され得る。具体的には、自由端延伸、固定端延伸、自由端収縮、固定端収縮などの様々な延伸方法を、単独で用いることも、同時もしくは逐次で用いることもできる。延伸方向に関しても、長さ方向、幅方向、厚さ方向、斜め方向等、様々な方向や次元に行なうことができる。
For the above stretching, any appropriate stretching method and stretching conditions (for example, stretching temperature, stretching ratio, stretching direction) can be adopted. Specifically, various stretching methods such as free-end stretching, fixed-end stretching, free-end contraction, and fixed-end contraction can be used alone or simultaneously or sequentially. As for the stretching direction, it can be performed in various directions and dimensions such as a length direction, a width direction, a thickness direction, and an oblique direction.
上記延伸方法、延伸条件を適宜選択することにより、上記所望の光学特性(例えば、屈折率特性、面内位相差、Nz係数)を有する位相差層を得ることができる。
By appropriately selecting the stretching method and stretching conditions, a retardation layer having the desired optical characteristics (for example, refractive index characteristics, in-plane retardation, Nz coefficient) can be obtained.
上記フィルムの延伸温度は、1つの実施形態においては、ポリカーボネート系樹脂等のガラス転移温度(Tg)以下の温度である。通常、ポリカーボネート系樹脂等のフィルムを延伸する場合、Tg以下の温度ではフィルムがガラス状態であるので、延伸は実質的には不可能である。本発明の実施形態に用いられる樹脂フィルムによれば、アクリル系樹脂(代表的には、ポリメチルメタクリレート)を少量配合することにより、ポリカーボネート系樹脂等のTgを実質的に変化させることなく、Tg以下での延伸が可能となる。さらに、理論的には明らかではないが、Tg以下で延伸を行うことにより、伸張性および位相差発現性に優れ、かつ、ヘイズの小さい逆分散位相差フィルム(位相差層)を実現することができる。具体的には、延伸温度は、好ましくはTg~Tg-10℃であり、より好ましくはTg~Tg-8℃であり、さらに好ましくはTg~Tg-5℃である。なお、上記フィルムは、例えばTg+5℃程度、また例えばTg+2℃程度までであれば、Tgよりも高い温度であっても適切に延伸され得る。
In one embodiment, the stretching temperature of the film is a temperature equal to or lower than the glass transition temperature (Tg) of a polycarbonate resin or the like. Usually, when a film such as a polycarbonate resin is stretched, the film is in a glass state at a temperature of Tg or less, so that stretching is practically impossible. According to the resin film used in the embodiment of the present invention, by blending a small amount of an acrylic resin (typically, polymethylmethacrylate), Tg of the polycarbonate resin or the like is not substantially changed. The following can be stretched. Further, although it is not theoretically clear, it is possible to realize a reverse dispersion retardation film (phase difference layer) having excellent extensibility and phase difference expression and having a small haze by stretching at Tg or less. can. Specifically, the stretching temperature is preferably Tg to Tg-10 ° C, more preferably Tg to Tg-8 ° C, and even more preferably Tg to Tg-5 ° C. The film can be appropriately stretched even at a temperature higher than Tg as long as it is, for example, about Tg + 5 ° C., and for example, about Tg + 2 ° C.
以上のようにして、位相差層を構成する位相差フィルムが得られ得る。
As described above, the retardation film constituting the retardation layer can be obtained.
また、位相差フィルムとして、市販の延伸フィルムを用いることもできる。市販の延伸フィルムは、そのまま用いてもよく、目的に応じて2次加工(例えば、延伸処理、表面処理)して用いてもよい。市販のフィルムの具体例としては、帝人社製の商品名「ピュアエースRM」が挙げられる。
Alternatively, a commercially available stretched film can be used as the retardation film. A commercially available stretched film may be used as it is, or may be used after secondary processing (for example, stretching treatment, surface treatment) depending on the purpose. Specific examples of commercially available films include the trade name "Pure Ace RM" manufactured by Teijin Limited.
E.第1の粘着剤層および第2の粘着剤層
E-1.第1の粘着剤層および/または第2の粘着剤層の特性
第1の粘着剤層20は、上記のとおり、85℃および500時間の加熱試験後の糊ずれ量が900μm以下であり、好ましくは600μm以下であり、より好ましくは500μm以下であり、さらに好ましくは400μm以下であり、特に好ましくは300μm以下であり、とりわけ好ましくは250μm以下であり、最も好ましくは180μm以下である。糊ずれ量の下限は、例えば20μmであり得る。このような範囲の糊ずれ量を有する(好ましくは、糊ずれ量が小さい)粘着剤を偏光子と位相差層との貼り合わせに用いることにより、後述の第2の粘着剤層のクリープ値を制御することによる効果との相乗的な効果により、高温環境下における位相差ムラが抑制された位相差層および粘着剤層付偏光板を実現することができる。なお、本明細書において「糊ずれ量」とは、位相差層および粘着剤層付偏光板において加熱試験後に偏光子および位相差層の端面からはみ出した粘着剤層の最もはみ出しが大きい部分の長さをいう。 E. First adhesive layer and second adhesive layer E-1. Characteristics of the First Adhesive Layer and / or The Second Adhesive Layer As described above, the firstadhesive layer 20 preferably has a glue slippage amount of 900 μm or less after a heating test at 85 ° C. and 500 hours. Is 600 μm or less, more preferably 500 μm or less, further preferably 400 μm or less, particularly preferably 300 μm or less, particularly preferably 250 μm or less, and most preferably 180 μm or less. The lower limit of the amount of slippage may be, for example, 20 μm. By using a pressure-sensitive adhesive having a slippage amount in such a range (preferably a small glue slippage amount) for bonding the polarizing element and the retardation layer, the creep value of the second pressure-sensitive adhesive layer described later can be determined. Due to the synergistic effect with the effect of control, it is possible to realize a polarizing plate with a retardation layer and a pressure-sensitive adhesive layer in which retardation unevenness is suppressed in a high temperature environment. In the present specification, the “glue deviation amount” is the length of the portion of the polarizing plate with the retarding layer and the pressure-sensitive adhesive layer where the adhesive layer protrudes most from the end faces of the polarizing element and the retarding layer after the heating test. Say.
E-1.第1の粘着剤層および/または第2の粘着剤層の特性
第1の粘着剤層20は、上記のとおり、85℃および500時間の加熱試験後の糊ずれ量が900μm以下であり、好ましくは600μm以下であり、より好ましくは500μm以下であり、さらに好ましくは400μm以下であり、特に好ましくは300μm以下であり、とりわけ好ましくは250μm以下であり、最も好ましくは180μm以下である。糊ずれ量の下限は、例えば20μmであり得る。このような範囲の糊ずれ量を有する(好ましくは、糊ずれ量が小さい)粘着剤を偏光子と位相差層との貼り合わせに用いることにより、後述の第2の粘着剤層のクリープ値を制御することによる効果との相乗的な効果により、高温環境下における位相差ムラが抑制された位相差層および粘着剤層付偏光板を実現することができる。なお、本明細書において「糊ずれ量」とは、位相差層および粘着剤層付偏光板において加熱試験後に偏光子および位相差層の端面からはみ出した粘着剤層の最もはみ出しが大きい部分の長さをいう。 E. First adhesive layer and second adhesive layer E-1. Characteristics of the First Adhesive Layer and / or The Second Adhesive Layer As described above, the first
第2の粘着剤層40は、上記のとおり、85℃におけるクリープ値が40μm以下であり、好ましくは30μm以下であり、より好ましくは25μm以下であり、さらに好ましくは20μm以下であり、特に好ましくは15μm以下である。クリープ値の下限は、例えば5μmであり得る。このようにクリープ値の小さい粘着剤を位相差層および粘着剤層付偏光板の画像表示セルへの貼り合わせに用いることにより、上記第1の粘着剤層の糊ずれ量を制御することによる効果との相乗的な効果により、高温環境下における色ムラが抑制された画像表示装置を実現することができる。クリープ値は、例えば以下の手順で測定され得る:粘着剤シートから切り出した試験サンプルを10mm×10mmの接合面にて支持板に貼着する。85℃の環境下において、試験サンプルを貼り付けた支持板を固定した状態で、500gfの荷重を鉛直下方に加える。荷重を加えて1秒後および3600秒後の支持板からのずれ量を測定し、それぞれCr1およびCr3600とする。Cr1およびCr3600から下記式により求められるΔCrをクリープ値とする。なお、本明細書におけるクリープ値は、粘着剤層の厚みを20μmに換算した場合の値である。
ΔCr=Cr3600-Cr1 As described above, the second pressure-sensitive adhesive layer 40 has a creep value of 40 μm or less, preferably 30 μm or less, more preferably 25 μm or less, still more preferably 20 μm or less, and particularly preferably 20 μm or less at 85 ° C. It is 15 μm or less. The lower limit of the creep value can be, for example, 5 μm. By using the pressure-sensitive adhesive having a small creep value for bonding the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer to the image display cell, the effect of controlling the amount of glue slippage of the first pressure-sensitive adhesive layer is controlled. Due to the synergistic effect with the above, it is possible to realize an image display device in which color unevenness is suppressed in a high temperature environment. The creep value can be measured, for example, by the following procedure: a test sample cut out from an adhesive sheet is attached to a support plate at a 10 mm × 10 mm joint surface. In an environment of 85 ° C., a load of 500 gf is applied vertically downward with the support plate to which the test sample is attached fixed. The amount of deviation from the support plate after 1 second and 3600 seconds after applying the load is measured and designated as Cr 1 and Cr 3600 , respectively. Let ΔCr obtained from Cr 1 and Cr 3600 by the following formula be the creep value. The creep value in the present specification is a value when the thickness of the pressure-sensitive adhesive layer is converted into 20 μm.
ΔCr = Cr 3600- Cr 1
ΔCr=Cr3600-Cr1 As described above, the second pressure-
ΔCr = Cr 3600- Cr 1
第1の粘着剤層および/または第2の粘着剤層は、85℃における貯蔵弾性率が、好ましくは1.0×104Pa以上であり、好ましくは2.0×104Pa以上であり、より好ましくは5.0×104Pa以上であり、さらに好ましくは1.0×105Pa以上である。貯蔵弾性率がこのような範囲であれば、上記所望の糊ずれ量および/またはクリープ値の実現が容易となる。一方で、貯蔵弾性率は、例えば3.0×106Pa以下である。
The first pressure-sensitive adhesive layer and / or the second pressure-sensitive adhesive layer has a storage elastic modulus at 85 ° C., preferably 1.0 × 10 4 Pa or more, preferably 2.0 × 10 4 Pa or more. , More preferably 5.0 × 10 4 Pa or more, and even more preferably 1.0 × 10 5 Pa or more. When the storage elastic modulus is in such a range, it becomes easy to realize the desired amount of glue slippage and / or creep value. On the other hand, the storage modulus is less for example 3.0 × 10 6 Pa.
第1の粘着剤層の厚みは、好ましくは2μm~50μmであり、より好ましくは3μm~40μmである。第2の粘着剤層の厚みは、好ましくは4μm~30μmであり、より好ましくは5μm~20μmである。第1の粘着剤層および第2の粘着剤層の厚みがこのような範囲であれば、上記糊ずれ量およびクリープ値を制御する効果との相乗的な効果により、高温環境下における位相差ムラが抑制された位相差層および粘着剤層付偏光板を実現することができ、かつ、高温環境下における色ムラが抑制された画像表示装置を実現することができる。
The thickness of the first pressure-sensitive adhesive layer is preferably 2 μm to 50 μm, and more preferably 3 μm to 40 μm. The thickness of the second pressure-sensitive adhesive layer is preferably 4 μm to 30 μm, and more preferably 5 μm to 20 μm. When the thickness of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is within such a range, the phase difference unevenness in a high temperature environment due to the synergistic effect with the effect of controlling the amount of glue slippage and the creep value. It is possible to realize a polarizing plate with a retardation layer and a pressure-sensitive adhesive layer in which the above is suppressed, and it is possible to realize an image display device in which color unevenness is suppressed in a high temperature environment.
E-2.第1の粘着剤層および第2の粘着剤層の構成材料
第1の粘着剤層および第2の粘着剤層は、第1の粘着剤層が上記所望の糊ずれ量を有し、第2の粘着剤層が上記所望のクリープ値を有する限りにおいて、任意の適切な構成が採用され得る。第1の粘着剤層および第2の粘着剤層は、同一の粘着剤で構成されていてもよく、それぞれ異なる粘着剤で構成されていてもよい。以下、第1の粘着剤層および第2の粘着剤層をまとめて粘着剤層として、構成材料を説明する。粘着剤層を構成する粘着剤の組成(例えば、ベースポリマーの種類(極性、Tg、柔らかさ)、分子量)、架橋構造(例えば、架橋剤の種類、架橋点間距離(架橋点間分子量)、架橋密度)等を調整することにより、糊ずれ量および/またはクリープ値を制御することができる。 E-2. Constituent Material of First Adhesive Layer and Second Adhesive Layer In the first adhesive layer and the second adhesive layer, the first adhesive layer has the desired amount of adhesive slippage, and the second adhesive layer has a desired amount of adhesive slippage. Any suitable configuration can be employed as long as the pressure-sensitive adhesive layer of the above has the desired creep value. The first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer may be composed of the same pressure-sensitive adhesive, or may be composed of different pressure-sensitive adhesives. Hereinafter, the constituent materials will be described with the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer collectively as a pressure-sensitive adhesive layer. Composition of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer (for example, type of base polymer (polarity, Tg, softness), molecular weight), cross-linking structure (for example, type of cross-linking agent, distance between cross-linking points (molecular weight between cross-linking points), By adjusting the cross-linking density) and the like, the amount of glue slippage and / or the creep value can be controlled.
第1の粘着剤層および第2の粘着剤層は、第1の粘着剤層が上記所望の糊ずれ量を有し、第2の粘着剤層が上記所望のクリープ値を有する限りにおいて、任意の適切な構成が採用され得る。第1の粘着剤層および第2の粘着剤層は、同一の粘着剤で構成されていてもよく、それぞれ異なる粘着剤で構成されていてもよい。以下、第1の粘着剤層および第2の粘着剤層をまとめて粘着剤層として、構成材料を説明する。粘着剤層を構成する粘着剤の組成(例えば、ベースポリマーの種類(極性、Tg、柔らかさ)、分子量)、架橋構造(例えば、架橋剤の種類、架橋点間距離(架橋点間分子量)、架橋密度)等を調整することにより、糊ずれ量および/またはクリープ値を制御することができる。 E-2. Constituent Material of First Adhesive Layer and Second Adhesive Layer In the first adhesive layer and the second adhesive layer, the first adhesive layer has the desired amount of adhesive slippage, and the second adhesive layer has a desired amount of adhesive slippage. Any suitable configuration can be employed as long as the pressure-sensitive adhesive layer of the above has the desired creep value. The first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer may be composed of the same pressure-sensitive adhesive, or may be composed of different pressure-sensitive adhesives. Hereinafter, the constituent materials will be described with the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer collectively as a pressure-sensitive adhesive layer. Composition of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer (for example, type of base polymer (polarity, Tg, softness), molecular weight), cross-linking structure (for example, type of cross-linking agent, distance between cross-linking points (molecular weight between cross-linking points), By adjusting the cross-linking density) and the like, the amount of glue slippage and / or the creep value can be controlled.
E-2-1.ベースポリマー
粘着剤層は、代表的には、ベースポリマーとして(メタ)アクリル系ポリマー、ウレタン系ポリマー、シリコーン系ポリマーまたはゴム系ポリマーを含有する粘着剤組成物から形成される。ベースポリマーとして(メタ)アクリル系ポリマーが用いられる場合、粘着剤層は、例えば(メタ)アクリル系ポリマー(A)を含有する粘着剤組成物から形成される。(メタ)アクリル系ポリマー(A)は、アルキル(メタ)アクリレートを主成分として含有する。 E-2-1. The base polymer pressure-sensitive adhesive layer is typically formed from a pressure-sensitive adhesive composition containing a (meth) acrylic polymer, a urethane-based polymer, a silicone-based polymer or a rubber-based polymer as a base polymer. When a (meth) acrylic polymer is used as the base polymer, the pressure-sensitive adhesive layer is formed from, for example, a pressure-sensitive adhesive composition containing the (meth) acrylic polymer (A). The (meth) acrylic polymer (A) contains an alkyl (meth) acrylate as a main component.
粘着剤層は、代表的には、ベースポリマーとして(メタ)アクリル系ポリマー、ウレタン系ポリマー、シリコーン系ポリマーまたはゴム系ポリマーを含有する粘着剤組成物から形成される。ベースポリマーとして(メタ)アクリル系ポリマーが用いられる場合、粘着剤層は、例えば(メタ)アクリル系ポリマー(A)を含有する粘着剤組成物から形成される。(メタ)アクリル系ポリマー(A)は、アルキル(メタ)アクリレートを主成分として含有する。 E-2-1. The base polymer pressure-sensitive adhesive layer is typically formed from a pressure-sensitive adhesive composition containing a (meth) acrylic polymer, a urethane-based polymer, a silicone-based polymer or a rubber-based polymer as a base polymer. When a (meth) acrylic polymer is used as the base polymer, the pressure-sensitive adhesive layer is formed from, for example, a pressure-sensitive adhesive composition containing the (meth) acrylic polymer (A). The (meth) acrylic polymer (A) contains an alkyl (meth) acrylate as a main component.
<(メタ)アクリル系ポリマー(A)>
(メタ)アクリル系ポリマー(A)は、上記のとおり、アルキル(メタ)アクリレートを主成分として含有する。アルキル(メタ)アクリレートは、(メタ)アクリル系ポリマー(A)を形成する全モノマー成分において、粘着剤層の接着性を向上させる観点から、50重量%以上であることが好ましく、当該アルキル(メタ)アクリレート以外のモノマーの残部として任意に設定できる。なお、(メタ)アクリレートは、アクリレートおよび/またはメタクリレートをいう。 <(Meta) acrylic polymer (A)>
As described above, the (meth) acrylic polymer (A) contains an alkyl (meth) acrylate as a main component. The alkyl (meth) acrylate is preferably 50% by weight or more in all the monomer components forming the (meth) acrylic polymer (A) from the viewpoint of improving the adhesiveness of the pressure-sensitive adhesive layer, and the alkyl (meth) acrylate is said. ) It can be arbitrarily set as the rest of the monomer other than acrylate. In addition, (meth) acrylate means acrylate and / or methacrylate.
(メタ)アクリル系ポリマー(A)は、上記のとおり、アルキル(メタ)アクリレートを主成分として含有する。アルキル(メタ)アクリレートは、(メタ)アクリル系ポリマー(A)を形成する全モノマー成分において、粘着剤層の接着性を向上させる観点から、50重量%以上であることが好ましく、当該アルキル(メタ)アクリレート以外のモノマーの残部として任意に設定できる。なお、(メタ)アクリレートは、アクリレートおよび/またはメタクリレートをいう。 <(Meta) acrylic polymer (A)>
As described above, the (meth) acrylic polymer (A) contains an alkyl (meth) acrylate as a main component. The alkyl (meth) acrylate is preferably 50% by weight or more in all the monomer components forming the (meth) acrylic polymer (A) from the viewpoint of improving the adhesiveness of the pressure-sensitive adhesive layer, and the alkyl (meth) acrylate is said. ) It can be arbitrarily set as the rest of the monomer other than acrylate. In addition, (meth) acrylate means acrylate and / or methacrylate.
(メタ)アクリル系ポリマー(A)の主骨格を構成するアルキル(メタ)アクリレートとしては、直鎖状または分岐鎖状のアルキル基の炭素数1~18のものが挙げられる。アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、アミル基、ヘキシル基、シクロヘキシル基、ヘプチル基、2-エチルヘキシル基、イソオクチル基、ノニル基、デシル基、イソデシル基、ドデシル基、イソミリスチル基、ラウリル基、トリデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基などが挙げられる。アルキル(メタ)アクリレートは単独でまたは組み合わせて使用できる。アルキル基の平均炭素数は3~10であることが好ましい。
Examples of the alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer (A) include linear or branched alkyl groups having 1 to 18 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an amyl group, a hexyl group, a cyclohexyl group, a heptyl group, a 2-ethylhexyl group, an isooctyl group, a nonyl group and a decyl group. , Isodecyl group, dodecyl group, isomiristyl group, lauryl group, tridecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like. Alkyl (meth) acrylates can be used alone or in combination. The average carbon number of the alkyl group is preferably 3 to 10.
(メタ)アクリル系ポリマー(A)は、モノマー成分として、アルキル(メタ)アクリレート以外にも、カルボキシル基含有モノマー(a1)、ヒドロキシル基含有モノマー(a2)等の共重合モノマーを含有していてもよい。共重合モノマーは単独でまたは組み合わせて使用できる。
The (meth) acrylic polymer (A) may contain a copolymerized monomer such as a carboxyl group-containing monomer (a1) and a hydroxyl group-containing monomer (a2) as a monomer component in addition to the alkyl (meth) acrylate. good. The copolymerizable monomers can be used alone or in combination.
カルボキシル基含有モノマー(a1)は、その構造中にカルボキシル基を含み、かつ(メタ)アクリロイル基、ビニル基などの重合性不飽和二重結合を含む化合物である。カルボキシル基含有モノマーとしては、例えば、(メタ)アクリル酸、カルボキシエチル(メタ)アクリレート、カルボキシペンチル(メタ)アクリレート、イタコン酸、マレイン酸、フマール酸、クロトン酸などが挙げられる。これらの中でも、共重合性、価格、および粘着剤層の粘着特性を向上させる観点から、アクリル酸が好ましい。第1の粘着剤層を構成する粘着剤組成物および/または第2の粘着剤層を構成する粘着剤組成物は、(メタ)アクリル系ポリマー(A)(ベースポリマー)のモノマー成分として、好ましくはカルボキシル基含有モノマー、より好ましくはアクリル酸を含み得る。
The carboxyl group-containing monomer (a1) is a compound containing a carboxyl group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group and a vinyl group. Examples of the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Among these, acrylic acid is preferable from the viewpoint of improving copolymerizability, price, and adhesive properties of the pressure-sensitive adhesive layer. The pressure-sensitive adhesive composition constituting the first pressure-sensitive adhesive layer and / or the pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer is preferably used as a monomer component of the (meth) acrylic polymer (A) (base polymer). May contain a carboxyl group-containing monomer, more preferably acrylic acid.
モノマー成分としてカルボキシル基含有モノマー(a1)を使用する場合、カルボキシル基含有モノマー(a1)の含有量は、(メタ)アクリル系ポリマー(A)を形成する全モノマー成分において、通常0.01重量%以上10重量%以下である。
When the carboxyl group-containing monomer (a1) is used as the monomer component, the content of the carboxyl group-containing monomer (a1) is usually 0.01% by weight in all the monomer components forming the (meth) acrylic polymer (A). It is 10% by weight or less.
ヒドロキシル基含有モノマー(a2)は、その構造中にヒドロキシル基を含み、かつ(メタ)アクリロイル基、ビニル基などの重合性不飽和二重結合を含む化合物である。ヒドロキシル基含有モノマーとしては、例えば、2-ヒドロキシエチル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、6-ヒドロキシヘキシル(メタ)アクリレート、8-ヒドロキシオクチル(メタ)アクリレート、10-ヒドロキシデシル(メタ)アクリレート、12-ヒドロキシラウリル(メタ)アクリレートなどのヒドロキシアルキル(メタ)アクリレート;(4-ヒドロキシメチルシクロヘキシル)-メチルアクリレートなどが挙げられる。これらの中でも、粘着剤層の耐久性を向上させる観点から、2-ヒドロキシエチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートが好ましく、4-ヒドロキシブチル(メタ)アクリレートがより好ましい。
The hydroxyl group-containing monomer (a2) is a compound containing a hydroxyl group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group and a vinyl group. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl ( Examples thereof include hydroxyalkyl (meth) acrylates such as 10-hydroxydecyl (meth) acrylates and 12-hydroxylauryl (meth) acrylates; (4-hydroxymethylcyclohexyl) -methyl acrylates and the like. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable, and 4-hydroxybutyl (meth) acrylate is more preferable, from the viewpoint of improving the durability of the pressure-sensitive adhesive layer.
モノマー成分としてヒドロキシル基含有モノマー(a2)を使用する場合、ヒドロキシル基含有モノマー(a2)の含有量は、(メタ)アクリル系ポリマー(A)を形成する全モノマー成分において、通常0.01重量%以上10重量%以下である。
When the hydroxyl group-containing monomer (a2) is used as the monomer component, the content of the hydroxyl group-containing monomer (a2) is usually 0.01% by weight in all the monomer components forming the (meth) acrylic polymer (A). It is 10% by weight or less.
(メタ)アクリル系ポリマー(A)は、モノマー成分として、ホモポリマーのガラス転移温度が0℃以上である不飽和炭素二重結合を有するモノマーを含有することが好ましい。ホモポリマーのガラス転移温度が0℃以上である不飽和炭素二重結合を有するモノマー(a3)としては、アルキル(メタ)アクリレートモノマー、(メタ)アクリル酸が挙げられる。モノマー(a3)は、ホモポリマーのガラス転移温度が20℃以上である不飽和炭素二重結合を有するモノマーが好ましく、ホモポリマーのガラス転移温度が40℃以上である不飽和炭素二重結合を有するモノマーがより好ましい。
The (meth) acrylic polymer (A) preferably contains, as a monomer component, a monomer having an unsaturated carbon double bond in which the glass transition temperature of the homopolymer is 0 ° C. or higher. Examples of the monomer (a3) having an unsaturated carbon double bond in which the glass transition temperature of the homopolymer is 0 ° C. or higher include an alkyl (meth) acrylate monomer and (meth) acrylic acid. The monomer (a3) is preferably a monomer having an unsaturated carbon double bond having a homopolymer glass transition temperature of 20 ° C. or higher, and has an unsaturated carbon double bond having a homopolymer glass transition temperature of 40 ° C. or higher. Monomers are more preferred.
(メタ)アクリル系ポリマー(A)において、モノマー(a3)を含有する割合は特に限定されない。含有量は、通常0.1重量%~40重量%であり、より好ましくは1重量%~30重量%である。なお、含有量は、モノマー(a3)を2種類以上併用する場合は合計での含有量である。
The proportion of the (meth) acrylic polymer (A) containing the monomer (a3) is not particularly limited. The content is usually 0.1% by weight to 40% by weight, more preferably 1% by weight to 30% by weight. The content is the total content when two or more kinds of monomers (a3) are used in combination.
モノマー(a3)としては、例えば、メチルアクリレート(Tg:8℃)、メチルメタクリレート(Tg:105℃)、エチルメタクリレート(Tg:65℃)、n-プロピルアクリレート(Tg:3℃)、n-プロピルメタクリレート(Tg:35℃)、n-ペンチルアクリレート(Tg:22℃)、n-テトラデシルアクリレート(Tg:24℃)、n-ヘキサデシルアクリレート(Tg:35℃)、n-ヘキサデシルメタクリレート(Tg:15℃)、n-ステアリルアクリレート(Tg:30℃)、及びn-ステアリルメタクリレート(Tg:38℃)などの直鎖アルキル(メタ)アクリレート;t-ブチルアクリレート(Tg:43℃)、t-ブチルメタクリレート(Tg:48℃)、i-プロピルメタクリレート(Tg:81℃)、及びi-ブチルメタクリレート(Tg:48℃)などの分岐鎖アルキル(メタ)アクリレート;シクロヘキシルアクリレート(Tg:19℃)、シクロヘキシルメタクリレート(Tg:65℃)、イソボルニルアクリレート(Tg:94℃)、及びイソボルニルメタクリレート(Tg:180℃)などの環状アルキル(メタ)アクリレート;アクリル酸(Tg:106℃)などが挙げられる。これらは単独または組み合わせて使用できる。
Examples of the monomer (a3) include methyl acrylate (Tg: 8 ° C.), methyl methacrylate (Tg: 105 ° C.), ethyl methacrylate (Tg: 65 ° C.), n-propyl acrylate (Tg: 3 ° C.), and n-propyl. Methacrylate (Tg: 35 ° C), n-pentyl acrylate (Tg: 22 ° C), n-tetradecyl acrylate (Tg: 24 ° C), n-hexadecyl acrylate (Tg: 35 ° C), n-hexadecyl methacrylate (Tg) : 15 ° C.), linear alkyl (meth) acrylates such as n-stearyl acrylate (Tg: 30 ° C.), and n-stearyl methacrylate (Tg: 38 ° C.); t-butyl acrylate (Tg: 43 ° C.), t- Branched chain alkyl (meth) acrylates such as butyl methacrylate (Tg: 48 ° C.), i-propyl methacrylate (Tg: 81 ° C.), and i-butyl methacrylate (Tg: 48 ° C.); cyclohexyl acrylate (Tg: 19 ° C.), Cyclic alkyl (meth) acrylates such as cyclohexyl methacrylate (Tg: 65 ° C.), isobornyl acrylate (Tg: 94 ° C.), and isobornyl methacrylate (Tg: 180 ° C.); acrylic acid (Tg: 106 ° C.) and the like. Can be mentioned. These can be used alone or in combination.
共重合モノマーは、粘着剤組成物が後述する架橋剤を含有する場合に、架橋剤との反応点になる。カルボキシル基含有モノマーおよびヒドロキシル基含有モノマーは、分子間架橋剤との反応性に富むため、得られる粘着剤層の凝集性や耐熱性の向上のために好ましく用いられる。また、カルボキシル基含有モノマーは、耐久性とリワーク性を両立させる点で好ましく、ヒドロキシル基含有モノマーは、リワーク性を向上させる点で好ましい。
The copolymerized monomer becomes a reaction point with the cross-linking agent when the pressure-sensitive adhesive composition contains the cross-linking agent described later. Since the carboxyl group-containing monomer and the hydroxyl group-containing monomer are highly reactive with the intermolecular cross-linking agent, they are preferably used for improving the cohesiveness and heat resistance of the obtained pressure-sensitive adhesive layer. Further, the carboxyl group-containing monomer is preferable in terms of achieving both durability and reworkability, and the hydroxyl group-containing monomer is preferable in terms of improving the reworkability.
モノマー成分として、その他の共重合モノマー(a4)をさらに用いてもよい。その他の共重合モノマー(a4)は、例えば、(メタ)アクリロイル基またはビニル基などの不飽和二重結合を有する重合性の官能基を有する。その他の共重合モノマー(a4)を用いることにより、粘着剤層の接着性および耐熱性が改善され得る。その他の共重合モノマー(a4)は単独でまたは組み合わせて使用できる。
Another copolymerization monomer (a4) may be further used as the monomer component. The other copolymerizable monomer (a4) has a polymerizable functional group having an unsaturated double bond such as, for example, a (meth) acryloyl group or a vinyl group. By using the other copolymerization monomer (a4), the adhesiveness and heat resistance of the pressure-sensitive adhesive layer can be improved. The other copolymerization monomer (a4) can be used alone or in combination.
その他の共重合モノマー(a4)として、アミノ基含有モノマー、アミド基含有モノマーを用いることにより、粘着剤層の密着性を向上できる。アミノ基含有モノマーは、例えば、N,N-ジメチルアミノエチル(メタ)アクリレート、N,N-ジメチルアミノプロピル(メタ)アクリレートである。アミド基含有モノマーは、例えば、(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N-イソプロピルアクリルアミド、N-メチル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-ヘキシル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-メチロール-N-プロパン(メタ)アクリルアミド、アミノメチル(メタ)アクリルアミド、アミノエチル(メタ)アクリルアミド、メルカプトメチル(メタ)アクリルアミド、メルカプトエチル(メタ)アクリルアミド等のアクリルアミド系単量体;N-(メタ)アクリロイルモルホリン、N-(メタ)アクリロイルピペリジン、N-(メタ)アクリロイルピロリジン等のN-アクリロイル複素環単量体;N-ビニルピロリドン、N-ビニル-ε-カプロラクタム等のN-ビニル基含有ラクタム系単量体である。
By using an amino group-containing monomer and an amide group-containing monomer as the other copolymerization monomer (a4), the adhesion of the pressure-sensitive adhesive layer can be improved. The amino group-containing monomer is, for example, N, N-dimethylaminoethyl (meth) acrylate or N, N-dimethylaminopropyl (meth) acrylate. The amide group-containing monomer is, for example, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropylacrylamide, N-methyl (meth) acrylamide, N-butyl ( Meta) acrylamide, N-hexyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylol-N-propane (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, mercaptomethyl (meth) ) Acrylamide-based monomers such as acrylamide and mercaptoethyl (meth) acrylamide; N-acrylloyl heterocyclic monomers such as N- (meth) acryloylmorpholine, N- (meth) acryloylpiperidin and N- (meth) acryloylpyrrolidine. It is an N-vinyl group-containing lactam-based monomer such as N-vinylpyrrolidone and N-vinyl-ε-caprolactam.
その他の共重合モノマー(a4)は、多官能性モノマーであってもよい。多官能性モノマーの使用により、粘着剤層のゲル分率の調整や凝集力の制御を実施できる。多官能性モノマーは、例えば、ヘキサンジオールジ(メタ)アクリレート(1,6-ヘキサンジオールジ(メタ)アクリレート)、ブタンジオールジ(メタ)アクリレート、(ポリ)エチレングリコールジ(メタ)アクリレート、(ポリ)プロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、テトラメチロールメタントリ(メタ)アクリレート、アリル(メタ)アクリレート、ビニル(メタ)アクリレート、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート等の多官能アクリレート;及びジビニルベンゼンである。多官能アクリレートは、好ましくは1,6-ヘキサンジオールジアクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレートである。
The other copolymerization monomer (a4) may be a polyfunctional monomer. By using the polyfunctional monomer, the gel fraction of the pressure-sensitive adhesive layer can be adjusted and the cohesive force can be controlled. Examples of the polyfunctional monomer include hexanediol di (meth) acrylate (1,6-hexanediol di (meth) acrylate), butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, and (poly). ) Propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethyl propantri (meth) Polyfunctional acrylates such as acrylates, tetramethylol methanetri (meth) acrylates, allyl (meth) acrylates, vinyl (meth) acrylates, epoxy acrylates, polyester acrylates, urethane acrylates; and divinylbenzene. The polyfunctional acrylate is preferably 1,6-hexanediol diacrylate or dipentaerythritol hexa (meth) acrylate.
その他の共重合モノマー(a4)は、上述した以外に、例えば、(メタ)アクリル酸2-メトキシエチル、(メタ)アクリル酸2-エトキシエチル、(メタ)アクリル酸メトキシトリエチレングリコール、(メタ)アクリル酸3-メトキシプロピル、(メタ)アクリル酸3-エトキシプロピル、(メタ)アクリル酸4-メトキシブチル、(メタ)アクリル酸4-エトキシブチル等の(メタ)アクリル酸アルコキシアルキルエステル;2-(アリルオキシメチル)アクリル酸メチル等の環化重合性モノマー;(メタ)アクリル酸グリシジル、(メタ)アクリル酸メチルグリシジル等のエポキシ基含有モノマー;ビニルスルホン酸ナトリウム等のスルホン酸基含有モノマー;リン酸基含有モノマー;(メタ)アクリル酸シクロペンチル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸イソボルニル等の脂環式炭化水素基を有する(メタ)アクリル酸エステル;(メタ)アクリル酸フェニル、(メタ)アクリル酸フェノキシエチル、(メタ)アクリル酸ベンジル等の芳香族炭化水素基を有する(メタ)アクリル酸エステル;酢酸ビニル、プロピオン酸ビニル等のビニルエステル類;スチレン、ビニルトルエン等の芳香族ビニル化合物;エチレン、プロピレン、ブタジエン、イソプレン、イソブチレン等のオレフィン類又はジエン類;ビニルアルキルエーテル等のビニルエーテル類;塩化ビニルを用いることができる。第1の粘着剤層を構成する粘着剤組成物および/または第2の粘着剤層を構成する粘着剤組成物は、(メタ)アクリル系ポリマー(A)(ベースポリマー)のモノマー成分として、好ましくは芳香族炭化水素基を有する(メタ)アクリル酸エステル、より好ましくは(メタ)アクリル酸ベンジルを含み得る。
In addition to the above, the other copolymerization monomer (a4) may be, for example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, (meth). (Meta) acrylic acid alkoxyalkyl esters such as 3-methoxypropyl acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate; 2-( Cyclic-polymerizable monomer such as methyl acrylate); epoxy group-containing monomer such as (meth) glycidyl acrylate, (meth) methyl glycidyl acrylate; sulfonic acid group-containing monomer such as sodium vinyl sulfonate; phosphoric acid Group-containing monomer; (meth) acrylate having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate; phenyl (meth) acrylate, (meth). ) (Meta) acrylic acid esters having aromatic hydrocarbon groups such as phenoxyethyl acrylate and benzyl (meth) acrylic acid; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyl toluene. Olefins or dienes such as ethylene, propylene, butadiene, isoprene, isobutylene; vinyl ethers such as vinylalkyl ethers; vinyl chloride can be used. The pressure-sensitive adhesive composition constituting the first pressure-sensitive adhesive layer and / or the pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer is preferably used as a monomer component of the (meth) acrylic polymer (A) (base polymer). May contain a (meth) acrylic acid ester having an aromatic hydrocarbon group, more preferably benzyl (meth) acrylic acid.
(メタ)アクリル系ポリマーにおけるその他の共重合モノマー(a4)の含有量は、好ましくは20質量%以下であり、より好ましくは10質量%以下であり、さらに好ましくは8質量%以下であり、特に好ましくは5質量%以下である。
The content of the other copolymerization monomer (a4) in the (meth) acrylic polymer is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, and particularly. It is preferably 5% by mass or less.
(メタ)アクリル系ポリマー(A)の重量平均分子量Mwは、例えば20万~300万であり、好ましくは100万~250万であり、より好ましくは120万~250万である。重量平均分子量Mwがこのような範囲であれば、耐久性(特に、耐熱性)に優れた粘着剤層が得られ得る。重量平均分子量Mwが300万を超えると、粘度の上昇および/またはポリマー重合中におけるゲル化が生じる場合がある。
The weight average molecular weight Mw of the (meth) acrylic polymer (A) is, for example, 200,000 to 3 million, preferably 1 million to 2.5 million, and more preferably 1.2 million to 2.5 million. When the weight average molecular weight Mw is in such a range, a pressure-sensitive adhesive layer having excellent durability (particularly heat resistance) can be obtained. If the weight average molecular weight Mw exceeds 3 million, an increase in viscosity and / or gelation during polymer polymerization may occur.
E-2-2.反応性官能基含有シランカップリング剤
粘着剤組成物は、反応性官能基含有シランカップリング剤を含有することができる。反応性官能基含有シランカップリング剤は、反応性官能基が代表的には酸無水物基以外の官能基である。酸無水物基以外の官能基としては、例えば、エポキシ基、メルカプト基、アミノ基、イソシアネート基、イソシアヌレート基、ビニル基、スチリル基、アセトアセチル基、ウレイド基、チオウレア基、(メタ)アクリル基、複素環基、およびこれらの組み合わせが挙げられる。反応性官能基含有シランカップリング剤は単独でまたは組み合わせて使用できる。 E-2-2. Reactive functional group-containing silane coupling agent The pressure-sensitive adhesive composition can contain a reactive functional group-containing silane coupling agent. In the reactive functional group-containing silane coupling agent, the reactive functional group is typically a functional group other than the acid anhydride group. Examples of the functional group other than the acid anhydride group include an epoxy group, a mercapto group, an amino group, an isocyanate group, an isocyanurate group, a vinyl group, a styryl group, an acetoacetyl group, a ureido group, a thiourea group and a (meth) acrylic group. , A heterocyclic group, and combinations thereof. Reactive functional group-containing silane coupling agents can be used alone or in combination.
粘着剤組成物は、反応性官能基含有シランカップリング剤を含有することができる。反応性官能基含有シランカップリング剤は、反応性官能基が代表的には酸無水物基以外の官能基である。酸無水物基以外の官能基としては、例えば、エポキシ基、メルカプト基、アミノ基、イソシアネート基、イソシアヌレート基、ビニル基、スチリル基、アセトアセチル基、ウレイド基、チオウレア基、(メタ)アクリル基、複素環基、およびこれらの組み合わせが挙げられる。反応性官能基含有シランカップリング剤は単独でまたは組み合わせて使用できる。 E-2-2. Reactive functional group-containing silane coupling agent The pressure-sensitive adhesive composition can contain a reactive functional group-containing silane coupling agent. In the reactive functional group-containing silane coupling agent, the reactive functional group is typically a functional group other than the acid anhydride group. Examples of the functional group other than the acid anhydride group include an epoxy group, a mercapto group, an amino group, an isocyanate group, an isocyanurate group, a vinyl group, a styryl group, an acetoacetyl group, a ureido group, a thiourea group and a (meth) acrylic group. , A heterocyclic group, and combinations thereof. Reactive functional group-containing silane coupling agents can be used alone or in combination.
粘着剤組成物に反応性官能基含有シランカップリング剤を配合する場合、反応性官能基含有シランカップリング剤の配合量は、(メタ)アクリル系ポリマー(A)100重量部に対して、通常0.001重量部以上5重量部以下である。
When the reactive functional group-containing silane coupling agent is blended in the pressure-sensitive adhesive composition, the blending amount of the reactive functional group-containing silane coupling agent is usually 100 parts by weight of the (meth) acrylic polymer (A). 0.001 part by weight or more and 5 parts by weight or less.
E-2-3.架橋剤
粘着剤組成物は、架橋剤を含有することができる。架橋剤としては、有機系架橋剤、多官能性金属キレートなどを用いることができる。有機系架橋剤としては、例えば、イソシアネート系架橋剤、過酸化物系架橋剤、エポキシ系架橋剤、イミン系架橋剤が挙げられる。多官能性金属キレートは、多価金属が有機化合物と共有結合または配位結合しているものである。粘着剤組成物が放射線硬化型である場合、架橋剤として多官能性モノマーを用いることができる。架橋剤は単独でまたは組み合わせて使用できる。 E-2-3. Cross-linking agent The pressure-sensitive adhesive composition can contain a cross-linking agent. As the cross-linking agent, an organic cross-linking agent, a polyfunctional metal chelate and the like can be used. Examples of the organic cross-linking agent include an isocyanate-based cross-linking agent, a peroxide-based cross-linking agent, an epoxy-based cross-linking agent, and an imine-based cross-linking agent. A polyfunctional metal chelate is one in which a polyvalent metal is covalently or coordinated to an organic compound. When the pressure-sensitive adhesive composition is a radiation-curable type, a polyfunctional monomer can be used as a cross-linking agent. Crosslinkers can be used alone or in combination.
粘着剤組成物は、架橋剤を含有することができる。架橋剤としては、有機系架橋剤、多官能性金属キレートなどを用いることができる。有機系架橋剤としては、例えば、イソシアネート系架橋剤、過酸化物系架橋剤、エポキシ系架橋剤、イミン系架橋剤が挙げられる。多官能性金属キレートは、多価金属が有機化合物と共有結合または配位結合しているものである。粘着剤組成物が放射線硬化型である場合、架橋剤として多官能性モノマーを用いることができる。架橋剤は単独でまたは組み合わせて使用できる。 E-2-3. Cross-linking agent The pressure-sensitive adhesive composition can contain a cross-linking agent. As the cross-linking agent, an organic cross-linking agent, a polyfunctional metal chelate and the like can be used. Examples of the organic cross-linking agent include an isocyanate-based cross-linking agent, a peroxide-based cross-linking agent, an epoxy-based cross-linking agent, and an imine-based cross-linking agent. A polyfunctional metal chelate is one in which a polyvalent metal is covalently or coordinated to an organic compound. When the pressure-sensitive adhesive composition is a radiation-curable type, a polyfunctional monomer can be used as a cross-linking agent. Crosslinkers can be used alone or in combination.
粘着剤組成物に架橋剤を配合する場合、架橋剤の配合量は、(メタ)アクリル系ポリマー(A)(ベースポリマー)100重量部に対して、通常0.01重量部以上15重量部以下である。第2の粘着剤層を構成する粘着剤組成物は、(メタ)アクリル系ポリマー(A)100重量部に対して、架橋剤を好ましくは1.5重量部以上、より好ましくは2.0重量部以上、さらに好ましくは2.2重量部以上、特に好ましくは5重量部以上含む。第2の粘着剤層を構成する粘着剤組成物における架橋剤の配合量がこのような下限以上であれば、上記糊ずれ量およびクリープ値を制御する効果との相乗的な効果により、高温環境下における位相差層および粘着剤層付偏光板の位相差ムラを安定して抑制でき、かつ、高温環境下における画像表示装置の色ムラを安定して抑制できる。
When the cross-linking agent is blended in the pressure-sensitive adhesive composition, the blending amount of the cross-linking agent is usually 0.01 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer (A) (base polymer). Is. In the pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer, the cross-linking agent is preferably 1.5 parts by weight or more, more preferably 2.0 parts by weight, based on 100 parts by weight of the (meth) acrylic polymer (A). It contains more than 2 parts by weight, more preferably 2.2 parts by weight or more, and particularly preferably 5 parts by weight or more. When the blending amount of the cross-linking agent in the pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer is at least such a lower limit, a high-temperature environment is obtained due to a synergistic effect with the effect of controlling the amount of glue slippage and the creep value. The retardation unevenness of the retarding layer and the polarizing plate with the adhesive layer underneath can be stably suppressed, and the color unevenness of the image display device in a high temperature environment can be stably suppressed.
粘着剤組成物にイソシアネート系架橋剤を配合する場合、イソシアネート系架橋剤の配合量は、(メタ)アクリル系ポリマー100重量部に対して、通常0.01重量部以上15重量部以下である。
When the isocyanate-based cross-linking agent is blended in the pressure-sensitive adhesive composition, the blending amount of the isocyanate-based cross-linking agent is usually 0.01 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer.
粘着剤組成物に過酸化物を配合する場合、過酸化物の配合量は、(メタ)アクリル系ポリマー100重量部に対して、通常0.01重量部以上2重量部以下である。このような範囲であれば、加工性および架橋安定性などの調整が容易である。
When a peroxide is blended in the pressure-sensitive adhesive composition, the blending amount of the peroxide is usually 0.01 parts by weight or more and 2 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer. Within such a range, it is easy to adjust workability, cross-linking stability and the like.
E-2-4.添加剤
粘着剤組成物は、(メタ)アクリル系オリゴマーおよび/またはイオン性化合物を含有していてもよい。また、粘着剤組成物は、添加剤を含有していてもよい。添加剤の具体例としては、着色剤、顔料などの粉体、染料、界面活性剤、可塑剤、粘着性付与剤、表面潤滑剤、レベリング剤、軟化剤、酸化防止剤、老化防止剤、光安定剤、紫外線吸収剤、重合禁止剤、無機または有機の充填剤、金属粉、粒子状、箔状物が挙げられる。また、制御できる範囲内で、還元剤を加えてのレドックス系を採用してもよい。1つの実施形態においては、第1の粘着剤層を構成する粘着剤組成物は、反応性基(例えば、反応性シリル基)を有するポリエーテル化合物を含んでいてもよい。添加剤の種類、数、組み合わせ、含有量等は、目的に応じて適切に設定され得る。添加剤の含有量は、(メタ)アクリル系ポリマー(A)100重量部に対して、好ましくは5重量部以下であり、より好ましくは3重量部以下であり、さらに好ましくは1重量部以下である。 E-2-4. Additives The pressure-sensitive adhesive composition may contain (meth) acrylic oligomers and / or ionic compounds. Further, the pressure-sensitive adhesive composition may contain an additive. Specific examples of additives include powders such as colorants and pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, and light. Stabilizers, UV absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particulates, foils and the like. Further, a redox system to which a reducing agent is added may be adopted within a controllable range. In one embodiment, the pressure-sensitive adhesive composition constituting the first pressure-sensitive adhesive layer may contain a polyether compound having a reactive group (for example, a reactive silyl group). The type, number, combination, content, etc. of additives can be appropriately set according to the purpose. The content of the additive is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and further preferably 1 part by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer (A). be.
粘着剤組成物は、(メタ)アクリル系オリゴマーおよび/またはイオン性化合物を含有していてもよい。また、粘着剤組成物は、添加剤を含有していてもよい。添加剤の具体例としては、着色剤、顔料などの粉体、染料、界面活性剤、可塑剤、粘着性付与剤、表面潤滑剤、レベリング剤、軟化剤、酸化防止剤、老化防止剤、光安定剤、紫外線吸収剤、重合禁止剤、無機または有機の充填剤、金属粉、粒子状、箔状物が挙げられる。また、制御できる範囲内で、還元剤を加えてのレドックス系を採用してもよい。1つの実施形態においては、第1の粘着剤層を構成する粘着剤組成物は、反応性基(例えば、反応性シリル基)を有するポリエーテル化合物を含んでいてもよい。添加剤の種類、数、組み合わせ、含有量等は、目的に応じて適切に設定され得る。添加剤の含有量は、(メタ)アクリル系ポリマー(A)100重量部に対して、好ましくは5重量部以下であり、より好ましくは3重量部以下であり、さらに好ましくは1重量部以下である。 E-2-4. Additives The pressure-sensitive adhesive composition may contain (meth) acrylic oligomers and / or ionic compounds. Further, the pressure-sensitive adhesive composition may contain an additive. Specific examples of additives include powders such as colorants and pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, and light. Stabilizers, UV absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particulates, foils and the like. Further, a redox system to which a reducing agent is added may be adopted within a controllable range. In one embodiment, the pressure-sensitive adhesive composition constituting the first pressure-sensitive adhesive layer may contain a polyether compound having a reactive group (for example, a reactive silyl group). The type, number, combination, content, etc. of additives can be appropriately set according to the purpose. The content of the additive is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and further preferably 1 part by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer (A). be.
F.画像表示装置
上記A項~E項に記載の位相差層および粘着剤層付偏光板は、画像表示装置に適用され得る。したがって、本発明の実施形態は、そのような位相差層および粘着剤層付偏光板を用いた画像表示装置も包含する。画像表示装置の代表例としては、液晶表示装置、有機EL表示装置が挙げられる。本発明の実施形態による画像表示装置は、代表的には、その視認側に上記A項~E項に記載の位相差層および粘着剤層付偏光板を備える。画像表示装置は、画像表示パネルを含む。画像表示パネルは、画像表示セルを含む。なお、画像表示装置を光学表示装置と称する場合があり、画像表示パネルを光学表示パネルと称する場合があり、画像表示セルを光学表示セルと称する場合がある。 F. Image display device The polarizing plate with the retardation layer and the pressure-sensitive adhesive layer according to the above items A to E can be applied to an image display device. Therefore, the embodiment of the present invention also includes an image display device using such a retardation layer and a polarizing plate with an adhesive layer. Typical examples of the image display device include a liquid crystal display device and an organic EL display device. The image display device according to the embodiment of the present invention is typically provided with the retardation layer and the polarizing plate with an adhesive layer according to the above items A to E on the visible side thereof. The image display device includes an image display panel. The image display panel includes an image display cell. The image display device may be referred to as an optical display device, the image display panel may be referred to as an optical display panel, and the image display cell may be referred to as an optical display cell.
上記A項~E項に記載の位相差層および粘着剤層付偏光板は、画像表示装置に適用され得る。したがって、本発明の実施形態は、そのような位相差層および粘着剤層付偏光板を用いた画像表示装置も包含する。画像表示装置の代表例としては、液晶表示装置、有機EL表示装置が挙げられる。本発明の実施形態による画像表示装置は、代表的には、その視認側に上記A項~E項に記載の位相差層および粘着剤層付偏光板を備える。画像表示装置は、画像表示パネルを含む。画像表示パネルは、画像表示セルを含む。なお、画像表示装置を光学表示装置と称する場合があり、画像表示パネルを光学表示パネルと称する場合があり、画像表示セルを光学表示セルと称する場合がある。 F. Image display device The polarizing plate with the retardation layer and the pressure-sensitive adhesive layer according to the above items A to E can be applied to an image display device. Therefore, the embodiment of the present invention also includes an image display device using such a retardation layer and a polarizing plate with an adhesive layer. Typical examples of the image display device include a liquid crystal display device and an organic EL display device. The image display device according to the embodiment of the present invention is typically provided with the retardation layer and the polarizing plate with an adhesive layer according to the above items A to E on the visible side thereof. The image display device includes an image display panel. The image display panel includes an image display cell. The image display device may be referred to as an optical display device, the image display panel may be referred to as an optical display panel, and the image display cell may be referred to as an optical display cell.
以下、実施例によって本発明を具体的に説明するが、本発明はこれら実施例によって限定されるものではない。なお、各特性の測定方法は以下の通りである。
Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The measurement method for each characteristic is as follows.
(1)糊ずれ量
実施例および比較例で得られた位相差層および粘着剤層付偏光板を13インチサイズに切り出し、試験サンプルとした。当該試験サンプルを85℃および500時間の加熱試験に供し、当該加熱試験後に偏光子および位相差層の端面からはみ出した第1の粘着剤層のはみ出し量を、対物レンズ(20倍)で観察および測定した。第1の粘着剤層の最もはみ出しが大きい部分の長さを糊ずれ量とした。観察の際には透過光を0(ゼロ)とし、反射光で観察するよう調整した。
(2)クリープ値
実施例および比較例で得られた位相差層および粘着剤層付偏光板を10mm×30mmサイズに切り出し試験サンプルとした。当該試験サンプルの上端部10mm×10mmを、SUS板に第2の粘着剤層を介して貼着し、試験サンプルの下端部に500gfの荷重を鉛直下方に負荷した。85℃の環境下において、荷重を加えて1秒後および3600秒後における試験サンプルとSUS板とのずれ量を測定し、それぞれCr1およびCr3600とした。Cr1およびCr3600から下記式により求められるΔCrをクリープ値とした。
ΔCr=Cr3600-Cr1
(3)色ムラ
実施例および比較例で得られた位相差層および粘着剤層付偏光板を13インチサイズに切り出し、第2の粘着剤層を介してガラス板に貼り合わせ試験サンプルとした。当該試験サンプルを85℃および500時間の加熱試験に供し、当該加熱試験後に反射シート(東レフィルム加工社製、DMS蒸着フィルム)上に載置し、分光測色計(コニカミノルタ社製、製品名「CM-2600d」)を用いて、サンプル中央部の反射色相a* Cおよびb* C、ならびに、サンプル端部の反射色相a* Eおよびb* Eを測定した。下記式で求められるΔabを色ムラの指標とした。Δabが小さいほど色ムラが良好であることを示す。
Δab={(a* E-a* C)2+(b* E-b* C)2}1/2
(4)光漏れ
実施例および比較例で得られた位相差層および粘着剤層付偏光板を縦300mm×横185mmのサイズに切り出したものを2枚用意した。これらを、厚さ0.07mmの無アルカリガラス板の両面にクロスニコルになるようにラミネーターにて貼り合せ、一次サンプルとした。次いで、一次サンプルに、50℃、5atmで15分間のオートクレーブ処理を行った(オートクレーブ処理後のサンプルを「初期の二次サンプル」と称する)。次いで、初期の二次サンプルを、85℃の条件下で500時間の処理に供した(加熱後のサンプルを「加熱後の二次サンプル」と称する)。初期の二次サンプルおよび加熱後の二次サンプルを、1万カンデラのバックライト上に置き、光漏れを目視で観察し、下記の基準で評価した。
A:光漏れの発生がない。
B:光漏れがわずかに発生しているが、表示領域には発生せず、実用上問題ない。
C:光漏れが表示領域にわずかに発生しているが、実用上問題ない。
D:光漏れが表示領域に顕著に発生しており、実用上問題がある。
(5)耐久性
実施例および比較例で得られた位相差層および粘着剤層付偏光板を、縦300mm×横220mmのサイズに切り出し、第2の粘着剤層を介して無アルカリガラス板に貼り合わせ試験サンプルとした。当該試験サンプルを60℃、相対湿度95%の条件下で240時間の耐久性試験に供した。耐久性試験後の試験サンプルを目視で観察し、下記の基準で評価した。
A:粘着剤層に発泡、剥がれなどの外観上の変化がない。
B:粘着剤層の端部にわずかに発泡が発生しているが、実用上問題ない。
C:粘着剤層の端部に著しい剥がれが発生しており、実用上問題がある。
(6)加湿による寸法変化率(加湿TMA試験)
表1に示す第1の位相差層および第2の位相差層の組み合わせとなるように、製造例で得られた第1の位相差フィルムに第2の位相差フィルムを貼り合わせて、位相差フィルムの積層体を得た。得られた積層体を、20mm(第1の位相差フィルムの遅相軸方向)×5mm(第1の位相差フィルムの進相軸方向)にカットして測定サンプルとした。なお、実施例9では、第1の位相差フィルムに第2の位相差フィルムを貼り合わせず、第1の位相差フィルムをカットして、測定サンプルとした。熱機械分析装置を用いて、25℃/50%RH、60℃/50%RH、60℃/85%RHの順に環境を変化させた後、60℃/85%RHにおいて、測定サンプルの長さ方向(第1の位相差フィルムの遅相軸方向)における寸法変化率を測定した。なお、25℃/50%RHでの保持時間は30分とし、50℃/60%RHでの保持時間は60分とし、60℃/85%RHでの保持時間は240分とした。25℃/50%RH、60℃/50%RH間での昇温速度は0.4℃/分とした。その結果を表1に示す。 (1) Amount of slippage The polarizing plates with the retardation layer and the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples were cut out to a size of 13 inches and used as test samples. The test sample was subjected to a heating test at 85 ° C. and 500 hours, and after the heating test, the amount of protrusion of the first pressure-sensitive adhesive layer protruding from the end faces of the polarizing element and the retardation layer was observed with an objective lens (20 times). It was measured. The length of the portion of the first pressure-sensitive adhesive layer having the largest protrusion was defined as the amount of adhesive slippage. At the time of observation, the transmitted light was set to 0 (zero), and adjustment was made so that the light was reflected.
(2) Creep value The polarizing plate with the retardation layer and the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was cut into a size of 10 mm × 30 mm and used as a test sample. Theupper end portion 10 mm × 10 mm of the test sample was attached to the SUS plate via the second pressure-sensitive adhesive layer, and a load of 500 gf was applied vertically downward to the lower end portion of the test sample. In an environment of 85 ° C., the amount of deviation between the test sample and the SUS plate 1 second and 3600 seconds after the load was applied was measured and used as Cr 1 and Cr 3600 , respectively. The creep value was ΔCr obtained from Cr 1 and Cr 3600 by the following formula.
ΔCr = Cr 3600- Cr 1
(3) Color unevenness The polarizing plate with the retardation layer and the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was cut out to a size of 13 inches and bonded to a glass plate via a second pressure-sensitive adhesive layer as a test sample. The test sample was subjected to a heating test at 85 ° C. for 500 hours, and after the heating test, it was placed on a reflective sheet (DMS vapor deposition film manufactured by Toray Film Processing Co., Ltd.) and a spectrophotometer (manufactured by Konica Minolta Co., Ltd., product name). “CM-2600d”) was used to measure the reflected hues a * C and b * C at the center of the sample and the reflected hues a * E and b * E at the edges of the sample. Δab obtained by the following formula was used as an index of color unevenness. The smaller Δab, the better the color unevenness.
Δab = {(a * E- a * C ) 2 + (b * E- b * C ) 2 } 1/2
(4) Light Leakage Two polarizing plates with a retardation layer and an adhesive layer obtained in Examples and Comparative Examples were cut out to a size of 300 mm in length × 185 mm in width and prepared. These were laminated on both sides of a non-alkali glass plate having a thickness of 0.07 mm with a laminator so as to form a cross Nicol, and used as a primary sample. The primary sample was then autoclaved at 50 ° C. and 5 atm for 15 minutes (the sample after autoclaving is referred to as the "initial secondary sample"). The initial secondary sample was then subjected to treatment at 85 ° C. for 500 hours (the heated sample is referred to as the "heated secondary sample"). The initial secondary sample and the heated secondary sample were placed on a backlight of 10,000 candelas, light leakage was visually observed, and evaluation was performed according to the following criteria.
A: No light leakage occurs.
B: Light leakage is slightly generated, but it does not occur in the display area, and there is no problem in practical use.
C: Light leakage is slightly generated in the display area, but there is no problem in practical use.
D: Light leakage is remarkably generated in the display area, which is a problem in practical use.
(5) Durability The polarizing plate with the retardation layer and the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was cut into a size of 300 mm in length × 220 mm in width, and formed into a non-alkali glass plate via a second pressure-sensitive adhesive layer. It was used as a bonding test sample. The test sample was subjected to a durability test for 240 hours under the conditions of 60 ° C. and 95% relative humidity. The test sample after the durability test was visually observed and evaluated according to the following criteria.
A: There is no change in appearance such as foaming or peeling of the adhesive layer.
B: Slight foaming is generated at the end of the adhesive layer, but there is no problem in practical use.
C: Significant peeling has occurred at the end of the adhesive layer, which poses a practical problem.
(6) Dimensional change rate due to humidification (humidification TMA test)
A second retardation film is bonded to the first retardation film obtained in the manufacturing example so as to form a combination of the first retardation layer and the second retardation layer shown in Table 1, and the retardation is obtained. A laminate of films was obtained. The obtained laminate was cut into 20 mm (slow-phase axial direction of the first retardation film) × 5 mm (phase-advancing axial direction of the first retardation film) to prepare a measurement sample. In Example 9, the second retardation film was not bonded to the first retardation film, and the first retardation film was cut to obtain a measurement sample. After changing the environment in the order of 25 ° C / 50% RH, 60 ° C / 50% RH, 60 ° C / 85% RH using a thermomechanical analyzer, the length of the measurement sample at 60 ° C / 85% RH. The dimensional change rate in the direction (the slow axis direction of the first retardation film) was measured. The holding time at 25 ° C./50% RH was 30 minutes, the holding time at 50 ° C./60% RH was 60 minutes, and the holding time at 60 ° C./85% RH was 240 minutes. The heating rate between 25 ° C./50% RH and 60 ° C./50% RH was 0.4 ° C./min. The results are shown in Table 1.
実施例および比較例で得られた位相差層および粘着剤層付偏光板を13インチサイズに切り出し、試験サンプルとした。当該試験サンプルを85℃および500時間の加熱試験に供し、当該加熱試験後に偏光子および位相差層の端面からはみ出した第1の粘着剤層のはみ出し量を、対物レンズ(20倍)で観察および測定した。第1の粘着剤層の最もはみ出しが大きい部分の長さを糊ずれ量とした。観察の際には透過光を0(ゼロ)とし、反射光で観察するよう調整した。
(2)クリープ値
実施例および比較例で得られた位相差層および粘着剤層付偏光板を10mm×30mmサイズに切り出し試験サンプルとした。当該試験サンプルの上端部10mm×10mmを、SUS板に第2の粘着剤層を介して貼着し、試験サンプルの下端部に500gfの荷重を鉛直下方に負荷した。85℃の環境下において、荷重を加えて1秒後および3600秒後における試験サンプルとSUS板とのずれ量を測定し、それぞれCr1およびCr3600とした。Cr1およびCr3600から下記式により求められるΔCrをクリープ値とした。
ΔCr=Cr3600-Cr1
(3)色ムラ
実施例および比較例で得られた位相差層および粘着剤層付偏光板を13インチサイズに切り出し、第2の粘着剤層を介してガラス板に貼り合わせ試験サンプルとした。当該試験サンプルを85℃および500時間の加熱試験に供し、当該加熱試験後に反射シート(東レフィルム加工社製、DMS蒸着フィルム)上に載置し、分光測色計(コニカミノルタ社製、製品名「CM-2600d」)を用いて、サンプル中央部の反射色相a* Cおよびb* C、ならびに、サンプル端部の反射色相a* Eおよびb* Eを測定した。下記式で求められるΔabを色ムラの指標とした。Δabが小さいほど色ムラが良好であることを示す。
Δab={(a* E-a* C)2+(b* E-b* C)2}1/2
(4)光漏れ
実施例および比較例で得られた位相差層および粘着剤層付偏光板を縦300mm×横185mmのサイズに切り出したものを2枚用意した。これらを、厚さ0.07mmの無アルカリガラス板の両面にクロスニコルになるようにラミネーターにて貼り合せ、一次サンプルとした。次いで、一次サンプルに、50℃、5atmで15分間のオートクレーブ処理を行った(オートクレーブ処理後のサンプルを「初期の二次サンプル」と称する)。次いで、初期の二次サンプルを、85℃の条件下で500時間の処理に供した(加熱後のサンプルを「加熱後の二次サンプル」と称する)。初期の二次サンプルおよび加熱後の二次サンプルを、1万カンデラのバックライト上に置き、光漏れを目視で観察し、下記の基準で評価した。
A:光漏れの発生がない。
B:光漏れがわずかに発生しているが、表示領域には発生せず、実用上問題ない。
C:光漏れが表示領域にわずかに発生しているが、実用上問題ない。
D:光漏れが表示領域に顕著に発生しており、実用上問題がある。
(5)耐久性
実施例および比較例で得られた位相差層および粘着剤層付偏光板を、縦300mm×横220mmのサイズに切り出し、第2の粘着剤層を介して無アルカリガラス板に貼り合わせ試験サンプルとした。当該試験サンプルを60℃、相対湿度95%の条件下で240時間の耐久性試験に供した。耐久性試験後の試験サンプルを目視で観察し、下記の基準で評価した。
A:粘着剤層に発泡、剥がれなどの外観上の変化がない。
B:粘着剤層の端部にわずかに発泡が発生しているが、実用上問題ない。
C:粘着剤層の端部に著しい剥がれが発生しており、実用上問題がある。
(6)加湿による寸法変化率(加湿TMA試験)
表1に示す第1の位相差層および第2の位相差層の組み合わせとなるように、製造例で得られた第1の位相差フィルムに第2の位相差フィルムを貼り合わせて、位相差フィルムの積層体を得た。得られた積層体を、20mm(第1の位相差フィルムの遅相軸方向)×5mm(第1の位相差フィルムの進相軸方向)にカットして測定サンプルとした。なお、実施例9では、第1の位相差フィルムに第2の位相差フィルムを貼り合わせず、第1の位相差フィルムをカットして、測定サンプルとした。熱機械分析装置を用いて、25℃/50%RH、60℃/50%RH、60℃/85%RHの順に環境を変化させた後、60℃/85%RHにおいて、測定サンプルの長さ方向(第1の位相差フィルムの遅相軸方向)における寸法変化率を測定した。なお、25℃/50%RHでの保持時間は30分とし、50℃/60%RHでの保持時間は60分とし、60℃/85%RHでの保持時間は240分とした。25℃/50%RH、60℃/50%RH間での昇温速度は0.4℃/分とした。その結果を表1に示す。 (1) Amount of slippage The polarizing plates with the retardation layer and the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples were cut out to a size of 13 inches and used as test samples. The test sample was subjected to a heating test at 85 ° C. and 500 hours, and after the heating test, the amount of protrusion of the first pressure-sensitive adhesive layer protruding from the end faces of the polarizing element and the retardation layer was observed with an objective lens (20 times). It was measured. The length of the portion of the first pressure-sensitive adhesive layer having the largest protrusion was defined as the amount of adhesive slippage. At the time of observation, the transmitted light was set to 0 (zero), and adjustment was made so that the light was reflected.
(2) Creep value The polarizing plate with the retardation layer and the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was cut into a size of 10 mm × 30 mm and used as a test sample. The
ΔCr = Cr 3600- Cr 1
(3) Color unevenness The polarizing plate with the retardation layer and the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was cut out to a size of 13 inches and bonded to a glass plate via a second pressure-sensitive adhesive layer as a test sample. The test sample was subjected to a heating test at 85 ° C. for 500 hours, and after the heating test, it was placed on a reflective sheet (DMS vapor deposition film manufactured by Toray Film Processing Co., Ltd.) and a spectrophotometer (manufactured by Konica Minolta Co., Ltd., product name). “CM-2600d”) was used to measure the reflected hues a * C and b * C at the center of the sample and the reflected hues a * E and b * E at the edges of the sample. Δab obtained by the following formula was used as an index of color unevenness. The smaller Δab, the better the color unevenness.
Δab = {(a * E- a * C ) 2 + (b * E- b * C ) 2 } 1/2
(4) Light Leakage Two polarizing plates with a retardation layer and an adhesive layer obtained in Examples and Comparative Examples were cut out to a size of 300 mm in length × 185 mm in width and prepared. These were laminated on both sides of a non-alkali glass plate having a thickness of 0.07 mm with a laminator so as to form a cross Nicol, and used as a primary sample. The primary sample was then autoclaved at 50 ° C. and 5 atm for 15 minutes (the sample after autoclaving is referred to as the "initial secondary sample"). The initial secondary sample was then subjected to treatment at 85 ° C. for 500 hours (the heated sample is referred to as the "heated secondary sample"). The initial secondary sample and the heated secondary sample were placed on a backlight of 10,000 candelas, light leakage was visually observed, and evaluation was performed according to the following criteria.
A: No light leakage occurs.
B: Light leakage is slightly generated, but it does not occur in the display area, and there is no problem in practical use.
C: Light leakage is slightly generated in the display area, but there is no problem in practical use.
D: Light leakage is remarkably generated in the display area, which is a problem in practical use.
(5) Durability The polarizing plate with the retardation layer and the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was cut into a size of 300 mm in length × 220 mm in width, and formed into a non-alkali glass plate via a second pressure-sensitive adhesive layer. It was used as a bonding test sample. The test sample was subjected to a durability test for 240 hours under the conditions of 60 ° C. and 95% relative humidity. The test sample after the durability test was visually observed and evaluated according to the following criteria.
A: There is no change in appearance such as foaming or peeling of the adhesive layer.
B: Slight foaming is generated at the end of the adhesive layer, but there is no problem in practical use.
C: Significant peeling has occurred at the end of the adhesive layer, which poses a practical problem.
(6) Dimensional change rate due to humidification (humidification TMA test)
A second retardation film is bonded to the first retardation film obtained in the manufacturing example so as to form a combination of the first retardation layer and the second retardation layer shown in Table 1, and the retardation is obtained. A laminate of films was obtained. The obtained laminate was cut into 20 mm (slow-phase axial direction of the first retardation film) × 5 mm (phase-advancing axial direction of the first retardation film) to prepare a measurement sample. In Example 9, the second retardation film was not bonded to the first retardation film, and the first retardation film was cut to obtain a measurement sample. After changing the environment in the order of 25 ° C / 50% RH, 60 ° C / 50% RH, 60 ° C / 85% RH using a thermomechanical analyzer, the length of the measurement sample at 60 ° C / 85% RH. The dimensional change rate in the direction (the slow axis direction of the first retardation film) was measured. The holding time at 25 ° C./50% RH was 30 minutes, the holding time at 50 ° C./60% RH was 60 minutes, and the holding time at 60 ° C./85% RH was 240 minutes. The heating rate between 25 ° C./50% RH and 60 ° C./50% RH was 0.4 ° C./min. The results are shown in Table 1.
[化合物の略号]
以下の製造例で用いた化合物の略号は以下の通りである。
・BPFM:ビス[9-(2-フェノキシカルボニルエチル)フルオレン-9-イル]メタン
特開2015-25111号公報に記載の方法で合成した。
・ISB:イソソルビド[ロケットフルーレ社製]
・SPG:スピログリコール[三菱ガス化学(株)製]
・DPC:ジフェニルカーボネート[三菱ケミカル(株)製] [Abbreviation of compound]
The abbreviations of the compounds used in the following production examples are as follows.
BPFM: Bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane It was synthesized by the method described in JP-A-2015-25111.
・ ISB: Isosorbide [manufactured by Rocket Foil]
・ SPG: Spiroglycol [manufactured by Mitsubishi Gas Chemical Company, Inc.]
・ DPC: Diphenyl carbonate [manufactured by Mitsubishi Chemical Corporation]
以下の製造例で用いた化合物の略号は以下の通りである。
・BPFM:ビス[9-(2-フェノキシカルボニルエチル)フルオレン-9-イル]メタン
特開2015-25111号公報に記載の方法で合成した。
・SPG:スピログリコール[三菱ガス化学(株)製]
・DPC:ジフェニルカーボネート[三菱ケミカル(株)製] [Abbreviation of compound]
The abbreviations of the compounds used in the following production examples are as follows.
BPFM: Bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane It was synthesized by the method described in JP-A-2015-25111.
・ SPG: Spiroglycol [manufactured by Mitsubishi Gas Chemical Company, Inc.]
・ DPC: Diphenyl carbonate [manufactured by Mitsubishi Chemical Corporation]
[製造例1:第1の位相差層を構成する第1の位相差フィルムの作製]
撹拌翼および100℃に制御された還流冷却器を具備した縦型反応器2器からなるバッチ重合装置を用いて重合を行った。BPFMを29.60質量部(0.046mol)、ISBを29.21質量部(0.200mol)、SPGを42.28質量部(0.139mol)、DPCを63.77質量部(0.298mol)及び触媒として酢酸カルシウム1水和物1.19×10-2質量部(6.78×10-5mol)を仕込んだ。反応器内を減圧窒素置換した後、熱媒で加温を行い、内温が100℃になった時点で撹拌を開始した。昇温開始40分後に内温を220℃に到達させ、この温度を保持するように制御すると同時に減圧を開始し、220℃に到達してから90分で13.3kPaにした。重合反応とともに副生するフェノール蒸気を100℃の還流冷却器に導き、フェノール蒸気中に若干量含まれるモノマー成分を反応器に戻し、凝縮しないフェノール蒸気は45℃の凝縮器に導いて回収した。第1反応器に窒素を導入して一旦大気圧まで復圧させた後、第1反応器内のオリゴマー化された反応液を第2反応器に移した。次いで、第2反応器内の昇温および減圧を開始して、50分で内温240℃、圧力0.2kPaにした。その後、所定の攪拌動力となるまで重合を進行させた。所定動力に到達した時点で反応器に窒素を導入して復圧し、生成したポリエステルカーボネート系樹脂を水中に押し出し、ストランドをカッティングしてペレットを得た。 [Manufacturing Example 1: Fabrication of First Phase Difference Film Constituting First Phase Difference Layer]
Polymerization was carried out using a batch polymerization apparatus consisting of two vertical reactors equipped with a stirring blade and a reflux condenser controlled at 100 ° C. BPFM is 29.60 parts by mass (0.046 mol), ISB is 29.21 parts by mass (0.200 mol), SPG is 42.28 parts by mass (0.139 mol), and DPC is 63.77 parts by mass (0.298 mol). ) and were charged 1.19 × 10 -2 parts by weight of calcium acetate monohydrate (6.78 × 10 -5 mol) as catalyst. After substituting nitrogen under reduced pressure in the reactor, heating was performed with a heat medium, and stirring was started when the internal temperature reached 100 ° C. The internal temperature was brought to 220 ° C. 40 minutes after the start of the temperature rise, and the depressurization was started at the same time as controlling to maintain this temperature, and the temperature was 13.3 kPa 90 minutes after reaching 220 ° C. The phenol vapor produced by the polymerization reaction was guided to a reflux condenser at 100 ° C., the monomer component contained in a small amount in the phenol vapor was returned to the reactor, and the non-condensed phenol vapor was guided to a condenser at 45 ° C. for recovery. Nitrogen was introduced into the first reactor and the pressure was once restored to atmospheric pressure, and then the oligomerized reaction solution in the first reactor was transferred to the second reactor. Then, the temperature rise and depressurization in the second reactor were started, and the internal temperature was 240 ° C. and the pressure was 0.2 kPa in 50 minutes. Then, the polymerization was allowed to proceed until the stirring power became a predetermined value. When the predetermined power was reached, nitrogen was introduced into the reactor to repressurize, the produced polyester carbonate-based resin was extruded into water, and the strands were cut to obtain pellets.
撹拌翼および100℃に制御された還流冷却器を具備した縦型反応器2器からなるバッチ重合装置を用いて重合を行った。BPFMを29.60質量部(0.046mol)、ISBを29.21質量部(0.200mol)、SPGを42.28質量部(0.139mol)、DPCを63.77質量部(0.298mol)及び触媒として酢酸カルシウム1水和物1.19×10-2質量部(6.78×10-5mol)を仕込んだ。反応器内を減圧窒素置換した後、熱媒で加温を行い、内温が100℃になった時点で撹拌を開始した。昇温開始40分後に内温を220℃に到達させ、この温度を保持するように制御すると同時に減圧を開始し、220℃に到達してから90分で13.3kPaにした。重合反応とともに副生するフェノール蒸気を100℃の還流冷却器に導き、フェノール蒸気中に若干量含まれるモノマー成分を反応器に戻し、凝縮しないフェノール蒸気は45℃の凝縮器に導いて回収した。第1反応器に窒素を導入して一旦大気圧まで復圧させた後、第1反応器内のオリゴマー化された反応液を第2反応器に移した。次いで、第2反応器内の昇温および減圧を開始して、50分で内温240℃、圧力0.2kPaにした。その後、所定の攪拌動力となるまで重合を進行させた。所定動力に到達した時点で反応器に窒素を導入して復圧し、生成したポリエステルカーボネート系樹脂を水中に押し出し、ストランドをカッティングしてペレットを得た。 [Manufacturing Example 1: Fabrication of First Phase Difference Film Constituting First Phase Difference Layer]
Polymerization was carried out using a batch polymerization apparatus consisting of two vertical reactors equipped with a stirring blade and a reflux condenser controlled at 100 ° C. BPFM is 29.60 parts by mass (0.046 mol), ISB is 29.21 parts by mass (0.200 mol), SPG is 42.28 parts by mass (0.139 mol), and DPC is 63.77 parts by mass (0.298 mol). ) and were charged 1.19 × 10 -2 parts by weight of calcium acetate monohydrate (6.78 × 10 -5 mol) as catalyst. After substituting nitrogen under reduced pressure in the reactor, heating was performed with a heat medium, and stirring was started when the internal temperature reached 100 ° C. The internal temperature was brought to 220 ° C. 40 minutes after the start of the temperature rise, and the depressurization was started at the same time as controlling to maintain this temperature, and the temperature was 13.3 kPa 90 minutes after reaching 220 ° C. The phenol vapor produced by the polymerization reaction was guided to a reflux condenser at 100 ° C., the monomer component contained in a small amount in the phenol vapor was returned to the reactor, and the non-condensed phenol vapor was guided to a condenser at 45 ° C. for recovery. Nitrogen was introduced into the first reactor and the pressure was once restored to atmospheric pressure, and then the oligomerized reaction solution in the first reactor was transferred to the second reactor. Then, the temperature rise and depressurization in the second reactor were started, and the internal temperature was 240 ° C. and the pressure was 0.2 kPa in 50 minutes. Then, the polymerization was allowed to proceed until the stirring power became a predetermined value. When the predetermined power was reached, nitrogen was introduced into the reactor to repressurize, the produced polyester carbonate-based resin was extruded into water, and the strands were cut to obtain pellets.
得られたポリエステルカーボネート系樹脂(ペレット)を80℃で5時間真空乾燥をした後、単軸押出機(東芝機械社製、シリンダー設定温度:250℃)、Tダイ(幅200mm、設定温度:250℃)、チルロール(設定温度:120~130℃)および巻取機を備えたフィルム製膜装置を用いて、厚み135μmの長尺状の樹脂フィルムを作製した。得られた長尺状の樹脂フィルムを、幅方向に、延伸温度133℃、延伸倍率2.8倍で延伸し、厚み48μmの位相差フィルムR1を得た。位相差フィルムR1のRe(550)は141nmであり、Re(450)/Re(550)は0.82であり、Nz係数は1.12であった。
After vacuum-drying the obtained polyester carbonate-based resin (pellet) at 80 ° C. for 5 hours, a single-screw extruder (manufactured by Toshiba Machine Co., Ltd., cylinder set temperature: 250 ° C.), T-die (width 200 mm, set temperature: 250). A long resin film having a thickness of 135 μm was prepared by using a film forming apparatus equipped with a chill roll (set temperature: 120 to 130 ° C.) and a winder. The obtained long resin film was stretched in the width direction at a stretching temperature of 133 ° C. and a stretching ratio of 2.8 times to obtain a retardation film R1 having a thickness of 48 μm. The Re (550) of the retardation film R1 was 141 nm, the Re (450) / Re (550) was 0.82, and the Nz coefficient was 1.12.
[製造例2:第1の位相差層を構成する第1の位相差フィルムの作製]
撹拌翼、及び還流冷却器を具備した竪型撹拌反応器2器からなるバッチ重合装置を用いて重合を行った。BPFMを30.31質量部(0.047mol)、ISBを39.94質量部(0.273mol)、SPGを30.20質量部(0.099mol)、DPCを69.67質量部(0.325mol)、および触媒として酢酸カルシウム1水和物7.88×10-4質量部(4.47×10-6mol)を仕込んだ。反応器内を減圧窒素置換した後、熱媒で加温を行い、内温が100℃になった時点で撹拌を開始した。昇温開始40分後に内温を220℃に到達させ、この温度を保持するように制御すると同時に減圧を開始し、220℃に到達してから90分で13.3kPaにした。重合反応とともに副生するフェノール蒸気を110℃の還流冷却器に導き、フェノール蒸気中に若干量含まれるモノマー成分を反応器に戻し、凝縮しないフェノール蒸気は45℃の凝縮器に導いて回収した。第1反応器に窒素を導入して一旦大気圧まで復圧させた後、第1反応器内のオリゴマー化された反応液を第2反応器に移した。次いで、第2反応器内の昇温および減圧を開始して、40分で内温240℃、圧力20kPaにした。その後、さらに圧力を下げながら、所定の攪拌動力となるまで重合を進行させた。所定動力に到達した時点で反応器に窒素を導入して復圧し、生成したポリエステルカーボネートを水中に押し出し、ストランドをカッティングしてペレットを得た。この樹脂を「PC1」と称する。各モノマーに由来する構造単位の比率は、BPFM/ISB/SPG/DPC=21.5/39.4/30.0/9.1質量%である。PC1の還元粘度は0.46dL/g、Mwは48,000、屈折率nDは1.526、溶融粘度は2480Pa・s、ガラス転移温度は139℃、光弾性係数は9×10-12[m2/N]、波長分散Re(450)/Re(550)は0.85であった。 [Manufacturing Example 2: Fabrication of First Phase Difference Film Constituting First Phase Difference Layer]
Polymerization was carried out using a batch polymerization apparatus consisting of two vertical stirring reactors equipped with a stirring blade and a reflux condenser. BPFM is 30.31 parts by mass (0.047 mol), ISB is 39.94 parts by mass (0.273 mol), SPG is 30.20 parts by mass (0.099 mol), and DPC is 69.67 parts by mass (0.325 mol). ), And 7.88 × 10 -4 parts by mass (4.47 × 10 -6 mol) of calcium acetate monohydrate was charged as a catalyst. After substituting nitrogen under reduced pressure in the reactor, heating was performed with a heat medium, and stirring was started when the internal temperature reached 100 ° C. The internal temperature was brought to 220 ° C. 40 minutes after the start of the temperature rise, and the depressurization was started at the same time as controlling to maintain this temperature, and the temperature was 13.3 kPa 90 minutes after reaching 220 ° C. The phenol vapor produced by the polymerization reaction was guided to a reflux condenser at 110 ° C., the monomer component contained in a small amount in the phenol vapor was returned to the reactor, and the non-condensed phenol vapor was guided to a condenser at 45 ° C. for recovery. Nitrogen was introduced into the first reactor and the pressure was once restored to atmospheric pressure, and then the oligomerized reaction solution in the first reactor was transferred to the second reactor. Then, the temperature rise and depressurization in the second reactor were started, and the internal temperature was 240 ° C. and the pressure was 20 kPa in 40 minutes. Then, while further reducing the pressure, the polymerization was allowed to proceed until the predetermined stirring power was obtained. When the predetermined power was reached, nitrogen was introduced into the reactor to repressurize, the produced polyester carbonate was extruded into water, and the strands were cut to obtain pellets. This resin is referred to as "PC1". The ratio of structural units derived from each monomer is BPFM / ISB / SPG / DPC = 21.5 / 39.4 / 30.0 / 9.1% by mass. The reduced viscosity of PC1 is 0.46 dL / g, Mw 48,000, refractive index n D is 1.526, a melt viscosity of 2480Pa · s, a glass transition temperature of 139 ° C., the photoelastic coefficient of 9 × 10 -12 [ m 2 / N] and the wavelength dispersion Re (450) / Re (550) were 0.85.
撹拌翼、及び還流冷却器を具備した竪型撹拌反応器2器からなるバッチ重合装置を用いて重合を行った。BPFMを30.31質量部(0.047mol)、ISBを39.94質量部(0.273mol)、SPGを30.20質量部(0.099mol)、DPCを69.67質量部(0.325mol)、および触媒として酢酸カルシウム1水和物7.88×10-4質量部(4.47×10-6mol)を仕込んだ。反応器内を減圧窒素置換した後、熱媒で加温を行い、内温が100℃になった時点で撹拌を開始した。昇温開始40分後に内温を220℃に到達させ、この温度を保持するように制御すると同時に減圧を開始し、220℃に到達してから90分で13.3kPaにした。重合反応とともに副生するフェノール蒸気を110℃の還流冷却器に導き、フェノール蒸気中に若干量含まれるモノマー成分を反応器に戻し、凝縮しないフェノール蒸気は45℃の凝縮器に導いて回収した。第1反応器に窒素を導入して一旦大気圧まで復圧させた後、第1反応器内のオリゴマー化された反応液を第2反応器に移した。次いで、第2反応器内の昇温および減圧を開始して、40分で内温240℃、圧力20kPaにした。その後、さらに圧力を下げながら、所定の攪拌動力となるまで重合を進行させた。所定動力に到達した時点で反応器に窒素を導入して復圧し、生成したポリエステルカーボネートを水中に押し出し、ストランドをカッティングしてペレットを得た。この樹脂を「PC1」と称する。各モノマーに由来する構造単位の比率は、BPFM/ISB/SPG/DPC=21.5/39.4/30.0/9.1質量%である。PC1の還元粘度は0.46dL/g、Mwは48,000、屈折率nDは1.526、溶融粘度は2480Pa・s、ガラス転移温度は139℃、光弾性係数は9×10-12[m2/N]、波長分散Re(450)/Re(550)は0.85であった。 [Manufacturing Example 2: Fabrication of First Phase Difference Film Constituting First Phase Difference Layer]
Polymerization was carried out using a batch polymerization apparatus consisting of two vertical stirring reactors equipped with a stirring blade and a reflux condenser. BPFM is 30.31 parts by mass (0.047 mol), ISB is 39.94 parts by mass (0.273 mol), SPG is 30.20 parts by mass (0.099 mol), and DPC is 69.67 parts by mass (0.325 mol). ), And 7.88 × 10 -4 parts by mass (4.47 × 10 -6 mol) of calcium acetate monohydrate was charged as a catalyst. After substituting nitrogen under reduced pressure in the reactor, heating was performed with a heat medium, and stirring was started when the internal temperature reached 100 ° C. The internal temperature was brought to 220 ° C. 40 minutes after the start of the temperature rise, and the depressurization was started at the same time as controlling to maintain this temperature, and the temperature was 13.3 kPa 90 minutes after reaching 220 ° C. The phenol vapor produced by the polymerization reaction was guided to a reflux condenser at 110 ° C., the monomer component contained in a small amount in the phenol vapor was returned to the reactor, and the non-condensed phenol vapor was guided to a condenser at 45 ° C. for recovery. Nitrogen was introduced into the first reactor and the pressure was once restored to atmospheric pressure, and then the oligomerized reaction solution in the first reactor was transferred to the second reactor. Then, the temperature rise and depressurization in the second reactor were started, and the internal temperature was 240 ° C. and the pressure was 20 kPa in 40 minutes. Then, while further reducing the pressure, the polymerization was allowed to proceed until the predetermined stirring power was obtained. When the predetermined power was reached, nitrogen was introduced into the reactor to repressurize, the produced polyester carbonate was extruded into water, and the strands were cut to obtain pellets. This resin is referred to as "PC1". The ratio of structural units derived from each monomer is BPFM / ISB / SPG / DPC = 21.5 / 39.4 / 30.0 / 9.1% by mass. The reduced viscosity of PC1 is 0.46 dL / g, Mw 48,000, refractive index n D is 1.526, a melt viscosity of 2480Pa · s, a glass transition temperature of 139 ° C., the photoelastic coefficient of 9 × 10 -12 [ m 2 / N] and the wavelength dispersion Re (450) / Re (550) were 0.85.
アクリル系樹脂としてダイヤナールBR80(三菱ケミカル(株)製)を用いて、得られたポリエステルカーボネートとの押出混錬を行った。ポリカーボネートのペレット(99.5質量部)とBR80の粉(0.5質量部)を混ぜ合わせたものを、定量フィーダーを用いて(株)日本製鋼所製の二軸押出機TEX30HSSに投入した。押出機シリンダー温度は250℃に設定し、処理量12kg/hr、スクリュー回転数120rpmで押出を行った。また、押出機には真空ベントが具備されており、溶融樹脂を減圧脱揮しながら押出した。このようにして得られた樹脂組成物のペレットを、100℃で6時間以上、真空乾燥をした後、単軸押出機(いすず化工機社製、スクリュー径25mm、シリンダー設定温度:250℃)、Tダイ(幅300mm、設定温度:220℃)、チルロール(設定温度:120~130℃)および巻取機を備えたフィルム製膜装置を用いて、長さ3m、幅200mm、厚み100μmの長尺未延伸フィルムを作製した。この長尺未延伸フィルムを、延伸温度をTg、延伸倍率2.4倍で延伸した。
Using Dianal BR80 (manufactured by Mitsubishi Chemical Corporation) as an acrylic resin, extrusion kneading with the obtained polyester carbonate was performed. A mixture of polycarbonate pellets (99.5 parts by mass) and BR80 powder (0.5 parts by mass) was charged into a twin-screw extruder TEX30HSS manufactured by Japan Steel Works, Ltd. using a quantitative feeder. The extruder cylinder temperature was set to 250 ° C., and extrusion was performed at a processing amount of 12 kg / hr and a screw rotation speed of 120 rpm. Further, the extruder is equipped with a vacuum vent, and the molten resin is extruded while devolatile under reduced pressure. The pellets of the resin composition thus obtained are vacuum-dried at 100 ° C. for 6 hours or more, and then a single-screw extruder (manufactured by Isuzu Kakohki Co., Ltd., screw diameter 25 mm, cylinder set temperature: 250 ° C.). Using a film-forming device equipped with a T-die (width 300 mm, set temperature: 220 ° C), chill roll (set temperature: 120-130 ° C), and a winder, a long length of 3 m in length, 200 mm in width, and 100 μm in thickness. An unstretched film was produced. This long unstretched film was stretched at a stretching temperature of Tg and a stretching ratio of 2.4 times.
このようにして、位相差層を構成する位相差フィルムR2を得た。位相差フィルムR2は、nx>ny>nzの屈折率特性を示し、Re(550)は145nm、Re(450)/Re(550)は0.85であった。
In this way, the retardation film R2 constituting the retardation layer was obtained. The retardation film R2 exhibited a refractive index characteristic of nx> ny> nz, Re (550) was 145 nm, and Re (450) / Re (550) was 0.85.
[製造例3:第1の位相差層を構成する第1の位相差フィルムの作製]
市販のポリカーボネート樹脂フィルム(樹脂フィルムの延伸フィルム、帝人株式会社製、製品名「ピュアエースRM」、厚み50μm)を、位相差フィルムR3とした。位相差フィルムR3のRe(550)は147nmであり、Re(450)/Re(550)は0.90であった。 [Manufacturing Example 3: Fabrication of First Phase Difference Film Constituting First Phase Difference Layer]
A commercially available polycarbonate resin film (stretched film of resin film, manufactured by Teijin Limited, product name "Pure Ace RM", thickness 50 μm) was used as a retardation film R3. The Re (550) of the retardation film R3 was 147 nm, and the Re (450) / Re (550) was 0.90.
市販のポリカーボネート樹脂フィルム(樹脂フィルムの延伸フィルム、帝人株式会社製、製品名「ピュアエースRM」、厚み50μm)を、位相差フィルムR3とした。位相差フィルムR3のRe(550)は147nmであり、Re(450)/Re(550)は0.90であった。 [Manufacturing Example 3: Fabrication of First Phase Difference Film Constituting First Phase Difference Layer]
A commercially available polycarbonate resin film (stretched film of resin film, manufactured by Teijin Limited, product name "Pure Ace RM", thickness 50 μm) was used as a retardation film R3. The Re (550) of the retardation film R3 was 147 nm, and the Re (450) / Re (550) was 0.90.
[製造例4:第2の位相差層を構成する第2の位相差フィルムの作製]
下記化学式(I)(式中、65及び35は、各構成単位のモル%)により示される側鎖型液晶ポリマー(重量平均分子量5000)20重量部、ネマチック液晶相を示す重合性液晶(BASF社製、商品名「PaliocolorLC242」)80重量部、及び光重合開始剤(チバスペシャリティーケミカルズ社製、商品名「イルガキュア907」)5重量部をシクロペンタノン200重量部に溶解して、液晶塗工液を調製した。次に、基材フィルムであるノルボルネン系樹脂フィルム(日本ゼオン社製、商品名「ゼオネックス」)の表面に、調製した液晶塗工液をバーコーターにより塗工した後、80℃で4分間、加熱及び乾燥させて、塗布膜に含まれる液晶を配向させた。次に、紫外線の照射により塗布膜を硬化させて、第2の位相差フィルムである液晶固化層R4(厚さ0.58μm)を基材フィルム上に形成した。波長550nmの光に対する液晶固化層R4の面内位相差Reは0nm、厚さ方向の位相差Rthは-71nmであり(nx=1.5326、ny=1.5326、nz=1.6550)、液晶固化層R4は、nz>nx=nyの屈折率特性を示した。
[Manufacturing Example 4: Fabrication of a Second Phase Difference Film Constituting a Second Phase Difference Layer]
20 parts by weight of the side chain type liquid crystal polymer (weight average molecular weight 5000) represented by the following chemical formula (I) (where 65 and 35 are mol% of each constituent unit), and a polymerizable liquid crystal showing a nematic liquid crystal phase (BASF). 80 parts by weight of the product, trade name "Pariocolor LC242") and 5 parts by weight of the photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name "Irgacure 907") are dissolved in 200 parts by weight of cyclopentanone and liquid crystal coated. The liquid was prepared. Next, the prepared liquid crystal coating liquid is applied to the surface of a norbornene-based resin film (manufactured by Zeon Corporation, trade name "Zeonex"), which is a base film, with a bar coater, and then heated at 80 ° C. for 4 minutes. And dried to orient the liquid crystal contained in the coating film. Next, the coating film was cured by irradiation with ultraviolet rays to form a second retardation film, the liquid crystal solidified layer R4 (thickness 0.58 μm), on the base film. The in-plane retardation Re of the liquid crystal solidified layer R4 with respect to light having a wavelength of 550 nm is 0 nm, and the retardation Rth in the thickness direction is −71 nm (nx = 1.5326, ny = 1.5326, nz = 1.6550). The liquid crystal solidified layer R4 exhibited a refractive index characteristic of nz> nx = ny.
下記化学式(I)(式中、65及び35は、各構成単位のモル%)により示される側鎖型液晶ポリマー(重量平均分子量5000)20重量部、ネマチック液晶相を示す重合性液晶(BASF社製、商品名「PaliocolorLC242」)80重量部、及び光重合開始剤(チバスペシャリティーケミカルズ社製、商品名「イルガキュア907」)5重量部をシクロペンタノン200重量部に溶解して、液晶塗工液を調製した。次に、基材フィルムであるノルボルネン系樹脂フィルム(日本ゼオン社製、商品名「ゼオネックス」)の表面に、調製した液晶塗工液をバーコーターにより塗工した後、80℃で4分間、加熱及び乾燥させて、塗布膜に含まれる液晶を配向させた。次に、紫外線の照射により塗布膜を硬化させて、第2の位相差フィルムである液晶固化層R4(厚さ0.58μm)を基材フィルム上に形成した。波長550nmの光に対する液晶固化層R4の面内位相差Reは0nm、厚さ方向の位相差Rthは-71nmであり(nx=1.5326、ny=1.5326、nz=1.6550)、液晶固化層R4は、nz>nx=nyの屈折率特性を示した。
20 parts by weight of the side chain type liquid crystal polymer (weight average molecular weight 5000) represented by the following chemical formula (I) (where 65 and 35 are mol% of each constituent unit), and a polymerizable liquid crystal showing a nematic liquid crystal phase (BASF). 80 parts by weight of the product, trade name "Pariocolor LC242") and 5 parts by weight of the photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name "Irgacure 907") are dissolved in 200 parts by weight of cyclopentanone and liquid crystal coated. The liquid was prepared. Next, the prepared liquid crystal coating liquid is applied to the surface of a norbornene-based resin film (manufactured by Zeon Corporation, trade name "Zeonex"), which is a base film, with a bar coater, and then heated at 80 ° C. for 4 minutes. And dried to orient the liquid crystal contained in the coating film. Next, the coating film was cured by irradiation with ultraviolet rays to form a second retardation film, the liquid crystal solidified layer R4 (thickness 0.58 μm), on the base film. The in-plane retardation Re of the liquid crystal solidified layer R4 with respect to light having a wavelength of 550 nm is 0 nm, and the retardation Rth in the thickness direction is −71 nm (nx = 1.5326, ny = 1.5326, nz = 1.6550). The liquid crystal solidified layer R4 exhibited a refractive index characteristic of nz> nx = ny.
[製造例5:粘着剤の調製]
(アクリル系ポリマーA1の調製)
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82.1部、ベンジルアクリレート13部、4-ヒドロキシブチルアクリレート0.1部およびアクリル酸4.8部を含有するモノマー混合物を仕込んだ。さらに、このモノマー混合物100部に対して、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部を酢酸エチル100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時間重合反応を行って、重量平均分子量(Mw)220万、Mw/Mn=3.0のアクリル系ポリマーA1の溶液を調製した。 [Production Example 5: Preparation of Adhesive]
(Preparation of acrylic polymer A1)
82.1 parts of butyl acrylate, 13 parts of benzyl acrylate, 0.1 part of 4-hydroxybutyl acrylate and 4.8 parts of acrylic acid in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler. A monomer mixture containing the above was charged. Further, 0.1 part of 2,2'-azobisisobutyronitrile was charged to 100 parts of this monomer mixture together with 100 parts of ethyl acetate as a polymerization initiator, and nitrogen gas was introduced with gentle stirring to introduce nitrogen. After the substitution, the liquid temperature in the flask was maintained at around 55 ° C. and the polymerization reaction was carried out for 8 hours to prepare a solution of the acrylic polymer A1 having a weight average molecular weight (Mw) of 2.2 million and Mw / Mn = 3.0. ..
(アクリル系ポリマーA1の調製)
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82.1部、ベンジルアクリレート13部、4-ヒドロキシブチルアクリレート0.1部およびアクリル酸4.8部を含有するモノマー混合物を仕込んだ。さらに、このモノマー混合物100部に対して、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部を酢酸エチル100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時間重合反応を行って、重量平均分子量(Mw)220万、Mw/Mn=3.0のアクリル系ポリマーA1の溶液を調製した。 [Production Example 5: Preparation of Adhesive]
(Preparation of acrylic polymer A1)
82.1 parts of butyl acrylate, 13 parts of benzyl acrylate, 0.1 part of 4-hydroxybutyl acrylate and 4.8 parts of acrylic acid in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler. A monomer mixture containing the above was charged. Further, 0.1 part of 2,2'-azobisisobutyronitrile was charged to 100 parts of this monomer mixture together with 100 parts of ethyl acetate as a polymerization initiator, and nitrogen gas was introduced with gentle stirring to introduce nitrogen. After the substitution, the liquid temperature in the flask was maintained at around 55 ° C. and the polymerization reaction was carried out for 8 hours to prepare a solution of the acrylic polymer A1 having a weight average molecular weight (Mw) of 2.2 million and Mw / Mn = 3.0. ..
(粘着剤の調製)
アクリル系ポリマーA1溶液の固形分100部に対して、トリメチロールプロパン/トリレンジイソシアネート付加物(東ソー社製、商品名「コロネートL」)0.45部、過酸化物架橋剤(ベンゾイルパーオキサイド)0.1部、エポキシ基含有シランカップリング剤(信越化学工業社製、商品名「KBM-403」)0.2部、および反応性シリル基を有するポリエーテル化合物(カネカ社製、商品名「サイリルSAT10」)0.5部を配合して、粘着剤PSA1を得た。 (Preparation of adhesive)
0.45 parts of trimethylolpropane / tolylene diisocyanate adduct (manufactured by Toso Co., Ltd., trade name "Coronate L"), peroxide cross-linking agent (benzoyl peroxide) for 100 parts of solid content of acrylic polymer A1 solution. 0.1 part, 0.2 part of epoxy group-containing silane coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name "KBM-403"), and a polyether compound having a reactive silyl group (manufactured by Kaneka Co., Ltd., trade name " Cyril SAT10 ") 0.5 part was blended to obtain a pressure-sensitive adhesive PSA1.
アクリル系ポリマーA1溶液の固形分100部に対して、トリメチロールプロパン/トリレンジイソシアネート付加物(東ソー社製、商品名「コロネートL」)0.45部、過酸化物架橋剤(ベンゾイルパーオキサイド)0.1部、エポキシ基含有シランカップリング剤(信越化学工業社製、商品名「KBM-403」)0.2部、および反応性シリル基を有するポリエーテル化合物(カネカ社製、商品名「サイリルSAT10」)0.5部を配合して、粘着剤PSA1を得た。 (Preparation of adhesive)
0.45 parts of trimethylolpropane / tolylene diisocyanate adduct (manufactured by Toso Co., Ltd., trade name "Coronate L"), peroxide cross-linking agent (benzoyl peroxide) for 100 parts of solid content of acrylic polymer A1 solution. 0.1 part, 0.2 part of epoxy group-containing silane coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name "KBM-403"), and a polyether compound having a reactive silyl group (manufactured by Kaneka Co., Ltd., trade name " Cyril SAT10 ") 0.5 part was blended to obtain a pressure-sensitive adhesive PSA1.
[製造例6:粘着剤の調製]
(アクリル系ポリマーA2の調製)
ブチルアクリレート99部および4-ヒドロキシブチルアクリレート1部を含有するモノマー混合物を用いたこと以外は製造例5と同様にして、Mw180万、Mw/Mn=4.8のアクリル系ポリマーA2の溶液を調製した。 [Production Example 6: Preparation of Adhesive]
(Preparation of acrylic polymer A2)
A solution of acrylic polymer A2 having Mw 1.8 million and Mw / Mn = 4.8 was prepared in the same manner as in Production Example 5 except that a monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate was used. did.
(アクリル系ポリマーA2の調製)
ブチルアクリレート99部および4-ヒドロキシブチルアクリレート1部を含有するモノマー混合物を用いたこと以外は製造例5と同様にして、Mw180万、Mw/Mn=4.8のアクリル系ポリマーA2の溶液を調製した。 [Production Example 6: Preparation of Adhesive]
(Preparation of acrylic polymer A2)
A solution of acrylic polymer A2 having Mw 1.8 million and Mw / Mn = 4.8 was prepared in the same manner as in Production Example 5 except that a monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate was used. did.
(粘着剤の調製)
アクリル系ポリマーA2溶液の固形分100部に対して、トリメチロールプロパン/キシリレンジイソシアネート付加物(東ソー社製、商品名「タケネートD110N」)0.1部、過酸化物架橋剤(ベンゾイルパーオキサイド)0.3部およびエポキシ基含有シランカップリング剤(信越化学工業社製、商品名「KBM-403」)0.2部を配合して、粘着剤PSA2を得た。 (Preparation of adhesive)
To 100 parts of solid content of acrylic polymer A2 solution, 0.1 part of trimethylolpropane / xylylene diisocyanate adduct (manufactured by Tosoh Corporation, trade name "Takenate D110N"), peroxide cross-linking agent (benzoyl peroxide) A pressure-sensitive adhesive PSA2 was obtained by blending 0.3 part and 0.2 part of an epoxy group-containing silane coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name "KBM-403").
アクリル系ポリマーA2溶液の固形分100部に対して、トリメチロールプロパン/キシリレンジイソシアネート付加物(東ソー社製、商品名「タケネートD110N」)0.1部、過酸化物架橋剤(ベンゾイルパーオキサイド)0.3部およびエポキシ基含有シランカップリング剤(信越化学工業社製、商品名「KBM-403」)0.2部を配合して、粘着剤PSA2を得た。 (Preparation of adhesive)
To 100 parts of solid content of acrylic polymer A2 solution, 0.1 part of trimethylolpropane / xylylene diisocyanate adduct (manufactured by Tosoh Corporation, trade name "Takenate D110N"), peroxide cross-linking agent (benzoyl peroxide) A pressure-sensitive adhesive PSA2 was obtained by blending 0.3 part and 0.2 part of an epoxy group-containing silane coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name "KBM-403").
[製造例7:粘着剤の調製]
D110Nの配合量を0.02部に変更したこと以外は製造例6と同様にして、粘着剤PSA3を得た。 [Production Example 7: Preparation of Adhesive]
The pressure-sensitive adhesive PSA3 was obtained in the same manner as in Production Example 6 except that the blending amount of D110N was changed to 0.02 part.
D110Nの配合量を0.02部に変更したこと以外は製造例6と同様にして、粘着剤PSA3を得た。 [Production Example 7: Preparation of Adhesive]
The pressure-sensitive adhesive PSA3 was obtained in the same manner as in Production Example 6 except that the blending amount of D110N was changed to 0.02 part.
[製造例8:粘着剤の調製]
(アクリル系ポリマーA3の調製)
ブチルアクリレート76.1部、ベンジルアクリレート19部、4-ヒドロキシブチルアクリレート0.1部およびアクリル酸4.8部を含有するモノマー混合物を用いたこと以外は製造例5と同様にして、Mw220万、Mw/Mn=3.0のアクリル系ポリマーA3の溶液を調製した。 [Production Example 8: Preparation of Adhesive]
(Preparation of acrylic polymer A3)
Similar to Production Example 5, Mw 2.2 million, except that a monomer mixture containing 76.1 parts of butyl acrylate, 19 parts of benzyl acrylate, 0.1 part of 4-hydroxybutyl acrylate and 4.8 parts of acrylic acid was used. A solution of acrylic polymer A3 with Mw / Mn = 3.0 was prepared.
(アクリル系ポリマーA3の調製)
ブチルアクリレート76.1部、ベンジルアクリレート19部、4-ヒドロキシブチルアクリレート0.1部およびアクリル酸4.8部を含有するモノマー混合物を用いたこと以外は製造例5と同様にして、Mw220万、Mw/Mn=3.0のアクリル系ポリマーA3の溶液を調製した。 [Production Example 8: Preparation of Adhesive]
(Preparation of acrylic polymer A3)
Similar to Production Example 5, Mw 2.2 million, except that a monomer mixture containing 76.1 parts of butyl acrylate, 19 parts of benzyl acrylate, 0.1 part of 4-hydroxybutyl acrylate and 4.8 parts of acrylic acid was used. A solution of acrylic polymer A3 with Mw / Mn = 3.0 was prepared.
(粘着剤の調製)
アクリル系ポリマーA3溶液の固形分100部に対して、トリメチロールプロパン/トリレンジイソシアネート付加物(東ソー社製、商品名「コロネートL」)2.5部、過酸化物架橋剤(ベンゾイルパーオキサイド)0.1部、およびエポキシ基含有オリゴマー型シランカップリング剤(信越化学工業社製、商品名「X-41-1056」)0.2部を配合して、粘着剤PSA4を得た。 (Preparation of adhesive)
For 100 parts of solid content of acrylic polymer A3 solution, 2.5 parts of trimethylolpropane / tolylene diisocyanate adduct (manufactured by Toso Co., Ltd., trade name "Coronate L"), peroxide cross-linking agent (benzoyl peroxide) 0.1 part and 0.2 part of an epoxy group-containing oligomer-type silane coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "X-41-1056") were blended to obtain a pressure-sensitive adhesive PSA4.
アクリル系ポリマーA3溶液の固形分100部に対して、トリメチロールプロパン/トリレンジイソシアネート付加物(東ソー社製、商品名「コロネートL」)2.5部、過酸化物架橋剤(ベンゾイルパーオキサイド)0.1部、およびエポキシ基含有オリゴマー型シランカップリング剤(信越化学工業社製、商品名「X-41-1056」)0.2部を配合して、粘着剤PSA4を得た。 (Preparation of adhesive)
For 100 parts of solid content of acrylic polymer A3 solution, 2.5 parts of trimethylolpropane / tolylene diisocyanate adduct (manufactured by Toso Co., Ltd., trade name "Coronate L"), peroxide cross-linking agent (benzoyl peroxide) 0.1 part and 0.2 part of an epoxy group-containing oligomer-type silane coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "X-41-1056") were blended to obtain a pressure-sensitive adhesive PSA4.
[製造例9:粘着剤の調製]
(アクリル系ポリマーA4の調製)
ブチルアクリレート63.1部、ベンジルアクリレート32部、4-ヒドロキシブチルアクリレート0.1部およびアクリル酸4.8部を含有するモノマー混合物を用いたこと以外は製造例5と同様にして、Mw220万、Mw/Mn=3.2のアクリル系ポリマーA4の溶液を調製した。 [Production Example 9: Preparation of Adhesive]
(Preparation of acrylic polymer A4)
Similar to Production Example 5, Mw 2.2 million, except that a monomer mixture containing 63.1 parts of butyl acrylate, 32 parts of benzyl acrylate, 0.1 part of 4-hydroxybutyl acrylate and 4.8 parts of acrylic acid was used. A solution of acrylic polymer A4 with Mw / Mn = 3.2 was prepared.
(アクリル系ポリマーA4の調製)
ブチルアクリレート63.1部、ベンジルアクリレート32部、4-ヒドロキシブチルアクリレート0.1部およびアクリル酸4.8部を含有するモノマー混合物を用いたこと以外は製造例5と同様にして、Mw220万、Mw/Mn=3.2のアクリル系ポリマーA4の溶液を調製した。 [Production Example 9: Preparation of Adhesive]
(Preparation of acrylic polymer A4)
Similar to Production Example 5, Mw 2.2 million, except that a monomer mixture containing 63.1 parts of butyl acrylate, 32 parts of benzyl acrylate, 0.1 part of 4-hydroxybutyl acrylate and 4.8 parts of acrylic acid was used. A solution of acrylic polymer A4 with Mw / Mn = 3.2 was prepared.
(粘着剤の調製)
アクリル系ポリマーA4溶液の固形分100部に対して、トリメチロールプロパン/トリレンジイソシアネート付加物(東ソー社製、商品名「コロネートL」)2.5部、過酸化物架橋剤(ベンゾイルパーオキサイド)0.1部、およびエポキシ基含有オリゴマー型シランカップリング剤(信越化学工業社製、商品名「X-41-1056」)0.2部を配合して、粘着剤PSA5を得た。 (Preparation of adhesive)
For 100 parts of solid content of acrylic polymer A4 solution, 2.5 parts of trimethylolpropane / tolylene diisocyanate adduct (manufactured by Toso Co., Ltd., trade name "Coronate L"), peroxide cross-linking agent (benzoyl peroxide) 0.1 part and 0.2 part of an epoxy group-containing oligomer-type silane coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "X-41-1056") were blended to obtain a pressure-sensitive adhesive PSA5.
アクリル系ポリマーA4溶液の固形分100部に対して、トリメチロールプロパン/トリレンジイソシアネート付加物(東ソー社製、商品名「コロネートL」)2.5部、過酸化物架橋剤(ベンゾイルパーオキサイド)0.1部、およびエポキシ基含有オリゴマー型シランカップリング剤(信越化学工業社製、商品名「X-41-1056」)0.2部を配合して、粘着剤PSA5を得た。 (Preparation of adhesive)
For 100 parts of solid content of acrylic polymer A4 solution, 2.5 parts of trimethylolpropane / tolylene diisocyanate adduct (manufactured by Toso Co., Ltd., trade name "Coronate L"), peroxide cross-linking agent (benzoyl peroxide) 0.1 part and 0.2 part of an epoxy group-containing oligomer-type silane coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "X-41-1056") were blended to obtain a pressure-sensitive adhesive PSA5.
[製造例10:粘着剤の調製]
(アクリル系ポリマーA5の調製)
ブチルアクリレート94.9部、2-ヒドロキシエチルアクリレート0.1部およびアクリル酸5部を含有するモノマー混合物を用いたこと以外は製造例5と同様にして、Mw220万、Mw/Mn=3.9のアクリル系ポリマーA5の溶液を調製した。 [Production Example 10: Preparation of Adhesive]
(Preparation of acrylic polymer A5)
Mw 2.2 million, Mw / Mn = 3.9 in the same manner as in Production Example 5 except that a monomer mixture containing 94.9 parts of butyl acrylate, 0.1 part of 2-hydroxyethyl acrylate and 5 parts of acrylic acid was used. A solution of acrylic polymer A5 was prepared.
(アクリル系ポリマーA5の調製)
ブチルアクリレート94.9部、2-ヒドロキシエチルアクリレート0.1部およびアクリル酸5部を含有するモノマー混合物を用いたこと以外は製造例5と同様にして、Mw220万、Mw/Mn=3.9のアクリル系ポリマーA5の溶液を調製した。 [Production Example 10: Preparation of Adhesive]
(Preparation of acrylic polymer A5)
Mw 2.2 million, Mw / Mn = 3.9 in the same manner as in Production Example 5 except that a monomer mixture containing 94.9 parts of butyl acrylate, 0.1 part of 2-hydroxyethyl acrylate and 5 parts of acrylic acid was used. A solution of acrylic polymer A5 was prepared.
(粘着剤の調製)
アクリル系ポリマーA5溶液の固形分100部に対して、トリメチロールプロパン/トリレンジイソシアネート付加物(東ソー社製、商品名「コロネートL」)3.0部、過酸化物架橋剤(ベンゾイルパーオキサイド)0.2部およびエポキシ基含有シランカップリング剤(信越化学工業社製、商品名「KBM-403」)0.075部を配合して、粘着剤PSA6を得た。 (Preparation of adhesive)
For 100 parts of solid content of acrylic polymer A5 solution, 3.0 parts of trimethylolpropane / tolylene diisocyanate adduct (manufactured by Tosoh Corporation, trade name "Coronate L"), peroxide cross-linking agent (benzoyl peroxide) 0.2 parts and 0.075 parts of an epoxy group-containing silane coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name "KBM-403") were blended to obtain a pressure-sensitive adhesive PSA6.
アクリル系ポリマーA5溶液の固形分100部に対して、トリメチロールプロパン/トリレンジイソシアネート付加物(東ソー社製、商品名「コロネートL」)3.0部、過酸化物架橋剤(ベンゾイルパーオキサイド)0.2部およびエポキシ基含有シランカップリング剤(信越化学工業社製、商品名「KBM-403」)0.075部を配合して、粘着剤PSA6を得た。 (Preparation of adhesive)
For 100 parts of solid content of acrylic polymer A5 solution, 3.0 parts of trimethylolpropane / tolylene diisocyanate adduct (manufactured by Tosoh Corporation, trade name "Coronate L"), peroxide cross-linking agent (benzoyl peroxide) 0.2 parts and 0.075 parts of an epoxy group-containing silane coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name "KBM-403") were blended to obtain a pressure-sensitive adhesive PSA6.
[製造例11:粘着剤の調製]
アクリル系ポリマーA2溶液の固形分100部に対して、ブチルアクリレート94部、メチルアクリレート4部およびアクリル酸2部の共重合オリゴマー(Mw=4700)を30部加えたこと、D110Nの配合量を0.02部に変更したこと、および、シランカップリング剤の配合量を0.1部に変更したこと以外は製造例6と同様にして、粘着剤PSA7を得た。 [Production Example 11: Preparation of Adhesive]
To 100 parts of the solid content of the acrylic polymer A2 solution, 30 parts of a copolymer oligomer (Mw = 4700) of 94 parts of butyl acrylate, 4 parts of methyl acrylate and 2 parts of acrylic acid was added, and the blending amount of D110N was 0. The pressure-sensitive adhesive PSA7 was obtained in the same manner as in Production Example 6 except that the content was changed to 0.02 part and the blending amount of the silane coupling agent was changed to 0.1 part.
アクリル系ポリマーA2溶液の固形分100部に対して、ブチルアクリレート94部、メチルアクリレート4部およびアクリル酸2部の共重合オリゴマー(Mw=4700)を30部加えたこと、D110Nの配合量を0.02部に変更したこと、および、シランカップリング剤の配合量を0.1部に変更したこと以外は製造例6と同様にして、粘着剤PSA7を得た。 [Production Example 11: Preparation of Adhesive]
To 100 parts of the solid content of the acrylic polymer A2 solution, 30 parts of a copolymer oligomer (Mw = 4700) of 94 parts of butyl acrylate, 4 parts of methyl acrylate and 2 parts of acrylic acid was added, and the blending amount of D110N was 0. The pressure-sensitive adhesive PSA7 was obtained in the same manner as in Production Example 6 except that the content was changed to 0.02 part and the blending amount of the silane coupling agent was changed to 0.1 part.
[製造例12:粘着剤の調製]
アクリル系ポリマーA1溶液の固形分100部に対して、トリメチロールプロパン/トリレンジイソシアネート付加物(東ソー社製、商品名「コロネートL」)12.0部およびエポキシ基含有シランカップリング剤(信越化学工業社製、商品名「KBM-403」)0.1部を配合して、粘着剤PSA8を得た。 [Production Example 12: Preparation of Adhesive]
12.0 parts of trimethylolpropane / tolylene diisocyanate adduct (manufactured by Tosoh Corporation, trade name "Coronate L") and epoxy group-containing silane coupling agent (Shin-Etsu Chemical) with respect to 100 parts of solid content of acrylic polymer A1 solution. 0.1 part of (trade name "KBM-403") manufactured by Kogyo Co., Ltd. was blended to obtain a pressure-sensitive adhesive PSA8.
アクリル系ポリマーA1溶液の固形分100部に対して、トリメチロールプロパン/トリレンジイソシアネート付加物(東ソー社製、商品名「コロネートL」)12.0部およびエポキシ基含有シランカップリング剤(信越化学工業社製、商品名「KBM-403」)0.1部を配合して、粘着剤PSA8を得た。 [Production Example 12: Preparation of Adhesive]
12.0 parts of trimethylolpropane / tolylene diisocyanate adduct (manufactured by Tosoh Corporation, trade name "Coronate L") and epoxy group-containing silane coupling agent (Shin-Etsu Chemical) with respect to 100 parts of solid content of acrylic polymer A1 solution. 0.1 part of (trade name "KBM-403") manufactured by Kogyo Co., Ltd. was blended to obtain a pressure-sensitive adhesive PSA8.
[製造例13:粘着剤の調製]
コロネートLの配合量を2.5部に変更したこと以外は製造例12と同様にして、粘着剤PSA9を得た。 [Production Example 13: Preparation of Adhesive]
The pressure-sensitive adhesive PSA9 was obtained in the same manner as in Production Example 12 except that the blending amount of Coronate L was changed to 2.5 parts.
コロネートLの配合量を2.5部に変更したこと以外は製造例12と同様にして、粘着剤PSA9を得た。 [Production Example 13: Preparation of Adhesive]
The pressure-sensitive adhesive PSA9 was obtained in the same manner as in Production Example 12 except that the blending amount of Coronate L was changed to 2.5 parts.
[製造例14:偏光板の作製]
(偏光子の作製)
厚み30μmのポリビニルアルコール(PVA)系樹脂フィルム(クラレ製、製品名「PE3000」)の長尺ロールを、ロール延伸機により長手方向に5.9倍になるように長手方向に一軸延伸しながら同時に膨潤、染色、架橋、洗浄処理を施し、最後に乾燥処理を施すことにより厚み12μmの偏光子を作製した。
具体的には、膨潤処理は20℃の純水で処理しながら2.2倍に延伸した。次いで、染色処理は得られる偏光子の単体透過率が45.0%になるようにヨウ素濃度が調整されたヨウ素とヨウ化カリウムの重量比が1:7である30℃の水溶液中において処理しながら1.4倍に延伸した。更に、架橋処理は、2段階の架橋処理を採用し、1段階目の架橋処理は40℃のホウ酸とヨウ化カリウムを溶解した水溶液において処理しながら1.2倍に延伸した。1段階目の架橋処理の水溶液のホウ酸含有量は5.0重量%で、ヨウ化カリウム含有量は3.0重量%とした。2段階目の架橋処理は65℃のホウ酸とヨウ化カリウムを溶解した水溶液において処理しながら1.6倍に延伸した。2段階目の架橋処理の水溶液のホウ酸含有量は4.3重量%で、ヨウ化カリウム含有量は5.0重量%とした。また、洗浄処理は、20℃のヨウ化カリウム水溶液で処理した。洗浄処理の水溶液のヨウ化カリウム含有量は2.6重量%とした。最後に、乾燥処理は70℃で5分間乾燥させて偏光子を得た。 [Manufacturing Example 14: Fabrication of Polarizing Plate]
(Making a polarizing element)
At the same time, a long roll of a polyvinyl alcohol (PVA) resin film (manufactured by Kuraray, product name "PE3000") having a thickness of 30 μm is uniaxially stretched in the longitudinal direction so as to be 5.9 times in the longitudinal direction by a roll stretching machine. A polarizing element having a thickness of 12 μm was prepared by performing swelling, dyeing, cross-linking, and washing treatment, and finally drying treatment.
Specifically, the swelling treatment was carried out by stretching 2.2 times while treating with pure water at 20 ° C. Next, the dyeing treatment was carried out in an aqueous solution at 30 ° C. in which the weight ratio of iodine and potassium iodide was adjusted so that the simple substance transmittance of the obtained polarizing element was 45.0% and the weight ratio was 1: 7. However, it was stretched 1.4 times. Further, the cross-linking treatment adopted a two-step cross-linking treatment, and the first-step cross-linking treatment was carried out 1.2 times while being treated with an aqueous solution in which boric acid and potassium iodide were dissolved at 40 ° C. The boric acid content of the aqueous solution of the first-step crosslinking treatment was 5.0% by weight, and the potassium iodide content was 3.0% by weight. The second-step cross-linking treatment was carried out by stretching 1.6 times while treating with an aqueous solution in which boric acid and potassium iodide were dissolved at 65 ° C. The boric acid content of the aqueous solution of the second step cross-linking treatment was 4.3% by weight, and the potassium iodide content was 5.0% by weight. The washing treatment was carried out with an aqueous potassium iodide solution at 20 ° C. The potassium iodide content of the aqueous solution of the washing treatment was set to 2.6% by weight. Finally, the drying process was carried out at 70 ° C. for 5 minutes to obtain a stator.
(偏光子の作製)
厚み30μmのポリビニルアルコール(PVA)系樹脂フィルム(クラレ製、製品名「PE3000」)の長尺ロールを、ロール延伸機により長手方向に5.9倍になるように長手方向に一軸延伸しながら同時に膨潤、染色、架橋、洗浄処理を施し、最後に乾燥処理を施すことにより厚み12μmの偏光子を作製した。
具体的には、膨潤処理は20℃の純水で処理しながら2.2倍に延伸した。次いで、染色処理は得られる偏光子の単体透過率が45.0%になるようにヨウ素濃度が調整されたヨウ素とヨウ化カリウムの重量比が1:7である30℃の水溶液中において処理しながら1.4倍に延伸した。更に、架橋処理は、2段階の架橋処理を採用し、1段階目の架橋処理は40℃のホウ酸とヨウ化カリウムを溶解した水溶液において処理しながら1.2倍に延伸した。1段階目の架橋処理の水溶液のホウ酸含有量は5.0重量%で、ヨウ化カリウム含有量は3.0重量%とした。2段階目の架橋処理は65℃のホウ酸とヨウ化カリウムを溶解した水溶液において処理しながら1.6倍に延伸した。2段階目の架橋処理の水溶液のホウ酸含有量は4.3重量%で、ヨウ化カリウム含有量は5.0重量%とした。また、洗浄処理は、20℃のヨウ化カリウム水溶液で処理した。洗浄処理の水溶液のヨウ化カリウム含有量は2.6重量%とした。最後に、乾燥処理は70℃で5分間乾燥させて偏光子を得た。 [Manufacturing Example 14: Fabrication of Polarizing Plate]
(Making a polarizing element)
At the same time, a long roll of a polyvinyl alcohol (PVA) resin film (manufactured by Kuraray, product name "PE3000") having a thickness of 30 μm is uniaxially stretched in the longitudinal direction so as to be 5.9 times in the longitudinal direction by a roll stretching machine. A polarizing element having a thickness of 12 μm was prepared by performing swelling, dyeing, cross-linking, and washing treatment, and finally drying treatment.
Specifically, the swelling treatment was carried out by stretching 2.2 times while treating with pure water at 20 ° C. Next, the dyeing treatment was carried out in an aqueous solution at 30 ° C. in which the weight ratio of iodine and potassium iodide was adjusted so that the simple substance transmittance of the obtained polarizing element was 45.0% and the weight ratio was 1: 7. However, it was stretched 1.4 times. Further, the cross-linking treatment adopted a two-step cross-linking treatment, and the first-step cross-linking treatment was carried out 1.2 times while being treated with an aqueous solution in which boric acid and potassium iodide were dissolved at 40 ° C. The boric acid content of the aqueous solution of the first-step crosslinking treatment was 5.0% by weight, and the potassium iodide content was 3.0% by weight. The second-step cross-linking treatment was carried out by stretching 1.6 times while treating with an aqueous solution in which boric acid and potassium iodide were dissolved at 65 ° C. The boric acid content of the aqueous solution of the second step cross-linking treatment was 4.3% by weight, and the potassium iodide content was 5.0% by weight. The washing treatment was carried out with an aqueous potassium iodide solution at 20 ° C. The potassium iodide content of the aqueous solution of the washing treatment was set to 2.6% by weight. Finally, the drying process was carried out at 70 ° C. for 5 minutes to obtain a stator.
(偏光板の作製)
上記偏光子の片側に、ポリビニルアルコール系接着剤を介して、トリアセチルセルロースフィルム(厚み40μm、コニカミノルタ社製、商品名「KC4UYW」)を貼り合わせ、保護層/偏光子の構成を有する偏光板P1を得た。 (Preparation of polarizing plate)
A triacetyl cellulose film (thickness 40 μm, manufactured by Konica Minolta, trade name “KC4UYW”) is bonded to one side of the above-mentioned polarizing element via a polyvinyl alcohol-based adhesive, and a polarizing plate having a protective layer / polarizing element configuration is attached. Obtained P1.
上記偏光子の片側に、ポリビニルアルコール系接着剤を介して、トリアセチルセルロースフィルム(厚み40μm、コニカミノルタ社製、商品名「KC4UYW」)を貼り合わせ、保護層/偏光子の構成を有する偏光板P1を得た。 (Preparation of polarizing plate)
A triacetyl cellulose film (
[製造例15:偏光板の作製]
(偏光子の作製)
熱可塑性樹脂基材として、長尺状で、Tg約75℃である、非晶質のイソフタル共重合ポリエチレンテレフタレートフィルム(厚み:100μm)を用い、樹脂基材の片面に、コロナ処理を施した。
ポリビニルアルコール(重合度4200、ケン化度99.2モル%)およびアセトアセチル変性PVA(日本合成化学工業社製、商品名「ゴーセファイマー」)を9:1で混合したPVA系樹脂100重量部に、ヨウ化カリウム13重量部を添加したものを水に溶かし、PVA水溶液(塗布液)を調製した。
樹脂基材のコロナ処理面に、上記PVA水溶液を塗布して60℃で乾燥することにより、厚み13μmのPVA系樹脂層を形成し、積層体を作製した。
得られた積層体を、130℃のオーブン内で縦方向(長手方向)に2.4倍に一軸延伸した(空中補助延伸処理)。
次いで、積層体を、液温40℃の不溶化浴(水100重量部に対して、ホウ酸を4重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(不溶化処理)。
次いで、液温30℃の染色浴(水100重量部に対して、ヨウ素とヨウ化カリウムを1:7の重量比で配合して得られたヨウ素水溶液)に、最終的に得られる偏光子の単体透過率(Ts)が所望の値となるように濃度を調整しながら60秒間浸漬させた(染色処理)。
次いで、液温40℃の架橋浴(水100重量部に対して、ヨウ化カリウムを3重量部配合し、ホウ酸を5重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(架橋処理)。
その後、積層体を、液温70℃のホウ酸水溶液(ホウ酸濃度4重量%、ヨウ化カリウム濃度5重量%)に浸漬させながら、周速の異なるロール間で縦方向(長手方向)に総延伸倍率が5.5倍となるように一軸延伸を行った(水中延伸処理)。
その後、積層体を液温20℃の洗浄浴(水100重量部に対して、ヨウ化カリウムを4重量部配合して得られた水溶液)に浸漬させた(洗浄処理)。
その後、約90℃に保たれたオーブン中で乾燥しながら、表面温度が約75℃に保たれたSUS製の加熱ロールに接触させた(乾燥収縮処理)。
このようにして、樹脂基材上に厚み約5μmの偏光子を形成し、樹脂基材/偏光子の構成を有する偏光板を得た。 [Manufacturing Example 15: Fabrication of Polarizing Plate]
(Making a polarizing element)
As the thermoplastic resin base material, an amorphous isophthal copolymerized polyethylene terephthalate film (thickness: 100 μm) having a long shape and a Tg of about 75 ° C. was used, and one side of the resin base material was subjected to corona treatment.
100 parts by weight of PVA-based resin in which polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gosefimer") are mixed at a ratio of 9: 1. A PVA aqueous solution (coating solution) was prepared by dissolving 13 parts by weight of potassium iodide in water.
The PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60 ° C. to form a PVA-based resin layer having a thickness of 13 μm, and a laminate was prepared.
The obtained laminate was uniaxially stretched 2.4 times in the vertical direction (longitudinal direction) in an oven at 130 ° C. (aerial auxiliary stretching treatment).
Next, the laminate was immersed in an insolubilizing bath at a liquid temperature of 40 ° C. (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with 100 parts by weight of water) for 30 seconds (insolubilization treatment).
Next, in a dyeing bath having a liquid temperature of 30 ° C. (an aqueous iodine solution obtained by mixing iodine and potassium iodide in a weight ratio of 1: 7 with respect to 100 parts by weight of water), the polarizing element finally obtained is charged. It was immersed for 60 seconds while adjusting the concentration so that the simple substance transmittance (Ts) became a desired value (staining treatment).
Then, it was immersed in a cross-linked bath having a liquid temperature of 40 ° C. (a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds. (Crossing treatment).
Then, while immersing the laminate in a boric acid aqueous solution (boric acid concentration 4% by weight, potassium iodide concentration 5% by weight) at a liquid temperature of 70 ° C., the total in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds. Uniaxial stretching was performed so that the stretching ratio was 5.5 times (underwater stretching treatment).
Then, the laminate was immersed in a washing bath having a liquid temperature of 20 ° C. (an aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water) (cleaning treatment).
Then, while drying in an oven kept at about 90 ° C., it was brought into contact with a heating roll made of SUS whose surface temperature was kept at about 75 ° C. (dry shrinkage treatment).
In this way, a polarizing element having a thickness of about 5 μm was formed on the resin substrate, and a polarizing plate having a resin substrate / polarizing element configuration was obtained.
(偏光子の作製)
熱可塑性樹脂基材として、長尺状で、Tg約75℃である、非晶質のイソフタル共重合ポリエチレンテレフタレートフィルム(厚み:100μm)を用い、樹脂基材の片面に、コロナ処理を施した。
ポリビニルアルコール(重合度4200、ケン化度99.2モル%)およびアセトアセチル変性PVA(日本合成化学工業社製、商品名「ゴーセファイマー」)を9:1で混合したPVA系樹脂100重量部に、ヨウ化カリウム13重量部を添加したものを水に溶かし、PVA水溶液(塗布液)を調製した。
樹脂基材のコロナ処理面に、上記PVA水溶液を塗布して60℃で乾燥することにより、厚み13μmのPVA系樹脂層を形成し、積層体を作製した。
得られた積層体を、130℃のオーブン内で縦方向(長手方向)に2.4倍に一軸延伸した(空中補助延伸処理)。
次いで、積層体を、液温40℃の不溶化浴(水100重量部に対して、ホウ酸を4重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(不溶化処理)。
次いで、液温30℃の染色浴(水100重量部に対して、ヨウ素とヨウ化カリウムを1:7の重量比で配合して得られたヨウ素水溶液)に、最終的に得られる偏光子の単体透過率(Ts)が所望の値となるように濃度を調整しながら60秒間浸漬させた(染色処理)。
次いで、液温40℃の架橋浴(水100重量部に対して、ヨウ化カリウムを3重量部配合し、ホウ酸を5重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(架橋処理)。
その後、積層体を、液温70℃のホウ酸水溶液(ホウ酸濃度4重量%、ヨウ化カリウム濃度5重量%)に浸漬させながら、周速の異なるロール間で縦方向(長手方向)に総延伸倍率が5.5倍となるように一軸延伸を行った(水中延伸処理)。
その後、積層体を液温20℃の洗浄浴(水100重量部に対して、ヨウ化カリウムを4重量部配合して得られた水溶液)に浸漬させた(洗浄処理)。
その後、約90℃に保たれたオーブン中で乾燥しながら、表面温度が約75℃に保たれたSUS製の加熱ロールに接触させた(乾燥収縮処理)。
このようにして、樹脂基材上に厚み約5μmの偏光子を形成し、樹脂基材/偏光子の構成を有する偏光板を得た。 [Manufacturing Example 15: Fabrication of Polarizing Plate]
(Making a polarizing element)
As the thermoplastic resin base material, an amorphous isophthal copolymerized polyethylene terephthalate film (thickness: 100 μm) having a long shape and a Tg of about 75 ° C. was used, and one side of the resin base material was subjected to corona treatment.
100 parts by weight of PVA-based resin in which polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gosefimer") are mixed at a ratio of 9: 1. A PVA aqueous solution (coating solution) was prepared by dissolving 13 parts by weight of potassium iodide in water.
The PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60 ° C. to form a PVA-based resin layer having a thickness of 13 μm, and a laminate was prepared.
The obtained laminate was uniaxially stretched 2.4 times in the vertical direction (longitudinal direction) in an oven at 130 ° C. (aerial auxiliary stretching treatment).
Next, the laminate was immersed in an insolubilizing bath at a liquid temperature of 40 ° C. (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with 100 parts by weight of water) for 30 seconds (insolubilization treatment).
Next, in a dyeing bath having a liquid temperature of 30 ° C. (an aqueous iodine solution obtained by mixing iodine and potassium iodide in a weight ratio of 1: 7 with respect to 100 parts by weight of water), the polarizing element finally obtained is charged. It was immersed for 60 seconds while adjusting the concentration so that the simple substance transmittance (Ts) became a desired value (staining treatment).
Then, it was immersed in a cross-linked bath having a liquid temperature of 40 ° C. (a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds. (Crossing treatment).
Then, while immersing the laminate in a boric acid aqueous solution (boric acid concentration 4% by weight, potassium iodide concentration 5% by weight) at a liquid temperature of 70 ° C., the total in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds. Uniaxial stretching was performed so that the stretching ratio was 5.5 times (underwater stretching treatment).
Then, the laminate was immersed in a washing bath having a liquid temperature of 20 ° C. (an aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water) (cleaning treatment).
Then, while drying in an oven kept at about 90 ° C., it was brought into contact with a heating roll made of SUS whose surface temperature was kept at about 75 ° C. (dry shrinkage treatment).
In this way, a polarizing element having a thickness of about 5 μm was formed on the resin substrate, and a polarizing plate having a resin substrate / polarizing element configuration was obtained.
(偏光板の作製)
得られた偏光子の表面(樹脂基材とは反対側の面)に、保護層としてのシクロオレフィン系フィルム(日本ゼオン社製、ZF-12、23μm)を、紫外線硬化型接着剤を介して貼り合せた。具体的には、硬化型接着剤の総厚みが約1.0μmになるように塗工し、ロール機を使用して貼り合わせた。その後、UV光線をシクロオレフィン系フィルム側から照射して接着剤を硬化させた。次いで、樹脂基材を剥離してシクロオレフィン系フィルム(保護層)/偏光子の構成を有する偏光板P2を得た。 (Preparation of polarizing plate)
A cycloolefin-based film (ZF-12, 23 μm, manufactured by Nippon Zeon Corporation) as a protective layer was applied to the surface of the obtained polarizing element (the surface opposite to the resin substrate) via an ultraviolet curable adhesive. I pasted them together. Specifically, the curable adhesive was coated so as to have a total thickness of about 1.0 μm, and bonded using a roll machine. Then, a UV ray was irradiated from the cycloolefin film side to cure the adhesive. Next, the resin base material was peeled off to obtain a polarizing plate P2 having a cycloolefin-based film (protective layer) / polarizing element.
得られた偏光子の表面(樹脂基材とは反対側の面)に、保護層としてのシクロオレフィン系フィルム(日本ゼオン社製、ZF-12、23μm)を、紫外線硬化型接着剤を介して貼り合せた。具体的には、硬化型接着剤の総厚みが約1.0μmになるように塗工し、ロール機を使用して貼り合わせた。その後、UV光線をシクロオレフィン系フィルム側から照射して接着剤を硬化させた。次いで、樹脂基材を剥離してシクロオレフィン系フィルム(保護層)/偏光子の構成を有する偏光板P2を得た。 (Preparation of polarizing plate)
A cycloolefin-based film (ZF-12, 23 μm, manufactured by Nippon Zeon Corporation) as a protective layer was applied to the surface of the obtained polarizing element (the surface opposite to the resin substrate) via an ultraviolet curable adhesive. I pasted them together. Specifically, the curable adhesive was coated so as to have a total thickness of about 1.0 μm, and bonded using a roll machine. Then, a UV ray was irradiated from the cycloolefin film side to cure the adhesive. Next, the resin base material was peeled off to obtain a polarizing plate P2 having a cycloolefin-based film (protective layer) / polarizing element.
(粘着剤層の作製)
調製した粘着剤を、シリコーン系剥離剤で処理されたポリエチレンテレフタレートフィルム(セパレータフィルム、三菱化学ポリエステルフィルム社製、MRF38)の片面に、乾燥後の粘着剤層の厚みが12μmとなるように塗布した後、粘着剤の塗膜を乾燥させて、第1の粘着剤層を形成した。
また、乾燥後の粘着剤層の厚みが15μmとなるように塗布したこと以外は、第1の粘着剤層の形成と同様にして、第2の粘着剤層を形成した。 (Preparation of adhesive layer)
The prepared adhesive was applied to one side of a polyethylene terephthalate film (separator film, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) treated with a silicone-based release agent so that the thickness of the adhesive layer after drying was 12 μm. After that, the coating film of the pressure-sensitive adhesive was dried to form a first pressure-sensitive adhesive layer.
Further, the second pressure-sensitive adhesive layer was formed in the same manner as the formation of the first pressure-sensitive adhesive layer, except that the pressure-sensitive adhesive layer was applied so as to have a thickness of 15 μm after drying.
調製した粘着剤を、シリコーン系剥離剤で処理されたポリエチレンテレフタレートフィルム(セパレータフィルム、三菱化学ポリエステルフィルム社製、MRF38)の片面に、乾燥後の粘着剤層の厚みが12μmとなるように塗布した後、粘着剤の塗膜を乾燥させて、第1の粘着剤層を形成した。
また、乾燥後の粘着剤層の厚みが15μmとなるように塗布したこと以外は、第1の粘着剤層の形成と同様にして、第2の粘着剤層を形成した。 (Preparation of adhesive layer)
The prepared adhesive was applied to one side of a polyethylene terephthalate film (separator film, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) treated with a silicone-based release agent so that the thickness of the adhesive layer after drying was 12 μm. After that, the coating film of the pressure-sensitive adhesive was dried to form a first pressure-sensitive adhesive layer.
Further, the second pressure-sensitive adhesive layer was formed in the same manner as the formation of the first pressure-sensitive adhesive layer, except that the pressure-sensitive adhesive layer was applied so as to have a thickness of 15 μm after drying.
[実施例1~9および比較例1~2]
セパレータフィルムの表面に形成した第1の粘着剤層を偏光板に転写して、粘着剤層付偏光板を作製した。また、セパレータフィルムの表面に形成した第2の粘着剤層を位相差フィルムに転写して、粘着剤層付位相差フィルムを作製した。
そして、粘着剤層付偏光板と粘着剤層付位相差フィルムとを、偏光板、第1の位相差フィルム(位相差層)、第2の位相差フィルム(液晶固化層)ならびに粘着剤(第1の粘着剤層および第2の粘着剤層)が表1に示す順となるように組み合わせて、位相差層および粘着剤層付偏光板を作製した。ここで、偏光板と第1の位相差層(位相差フィルム)とは、偏光子の吸収軸と位相差フィルムの遅相軸とが45°の角度をなすようにして貼り合わせた。得られた位相差層および粘着剤層付偏光板を上記色ムラ、光漏れおよび耐久性の評価に供した。結果を、第1の粘着剤層の糊ずれ量および第2の粘着剤層のクリープ値と併せて表1に示す。 [Examples 1 to 9 and Comparative Examples 1 to 2]
The first pressure-sensitive adhesive layer formed on the surface of the separator film was transferred to a polarizing plate to prepare a polarizing plate with a pressure-sensitive adhesive layer. Further, the second pressure-sensitive adhesive layer formed on the surface of the separator film was transferred to the retardation film to prepare a retardation film with a pressure-sensitive adhesive layer.
Then, the polarizing plate with the pressure-sensitive adhesive layer and the retardation film with the pressure-sensitive adhesive layer are used as a polarizing plate, a first retardation film (phase difference layer), a second retardation film (liquid crystal solidifying layer), and a pressure-sensitive adhesive (first). The pressure-sensitive adhesive layer (1) and the pressure-sensitive adhesive layer (2) were combined in the order shown in Table 1 to prepare a retardation layer and a polarizing plate with a pressure-sensitive adhesive layer. Here, the polarizing plate and the first retardation layer (phase difference film) are bonded so that the absorption axis of the polarizing element and the slow axis of the retardation film form an angle of 45 °. The obtained retardation layer and the polarizing plate with the pressure-sensitive adhesive layer were subjected to the evaluation of the above-mentioned color unevenness, light leakage and durability. The results are shown in Table 1 together with the amount of glue slippage of the first pressure-sensitive adhesive layer and the creep value of the second pressure-sensitive adhesive layer.
セパレータフィルムの表面に形成した第1の粘着剤層を偏光板に転写して、粘着剤層付偏光板を作製した。また、セパレータフィルムの表面に形成した第2の粘着剤層を位相差フィルムに転写して、粘着剤層付位相差フィルムを作製した。
そして、粘着剤層付偏光板と粘着剤層付位相差フィルムとを、偏光板、第1の位相差フィルム(位相差層)、第2の位相差フィルム(液晶固化層)ならびに粘着剤(第1の粘着剤層および第2の粘着剤層)が表1に示す順となるように組み合わせて、位相差層および粘着剤層付偏光板を作製した。ここで、偏光板と第1の位相差層(位相差フィルム)とは、偏光子の吸収軸と位相差フィルムの遅相軸とが45°の角度をなすようにして貼り合わせた。得られた位相差層および粘着剤層付偏光板を上記色ムラ、光漏れおよび耐久性の評価に供した。結果を、第1の粘着剤層の糊ずれ量および第2の粘着剤層のクリープ値と併せて表1に示す。 [Examples 1 to 9 and Comparative Examples 1 to 2]
The first pressure-sensitive adhesive layer formed on the surface of the separator film was transferred to a polarizing plate to prepare a polarizing plate with a pressure-sensitive adhesive layer. Further, the second pressure-sensitive adhesive layer formed on the surface of the separator film was transferred to the retardation film to prepare a retardation film with a pressure-sensitive adhesive layer.
Then, the polarizing plate with the pressure-sensitive adhesive layer and the retardation film with the pressure-sensitive adhesive layer are used as a polarizing plate, a first retardation film (phase difference layer), a second retardation film (liquid crystal solidifying layer), and a pressure-sensitive adhesive (first). The pressure-sensitive adhesive layer (1) and the pressure-sensitive adhesive layer (2) were combined in the order shown in Table 1 to prepare a retardation layer and a polarizing plate with a pressure-sensitive adhesive layer. Here, the polarizing plate and the first retardation layer (phase difference film) are bonded so that the absorption axis of the polarizing element and the slow axis of the retardation film form an angle of 45 °. The obtained retardation layer and the polarizing plate with the pressure-sensitive adhesive layer were subjected to the evaluation of the above-mentioned color unevenness, light leakage and durability. The results are shown in Table 1 together with the amount of glue slippage of the first pressure-sensitive adhesive layer and the creep value of the second pressure-sensitive adhesive layer.
[評価]
表1から明らかなように、第1の粘着剤層の糊ずれ量および第2の粘着剤層のクリープ値を組み合わせて制御することにより、高温環境下における色ムラおよび光漏れが抑制された画像表示装置を実現し得る位相差層および粘着剤層付偏光板が得られることがわかる。 [evaluation]
As is clear from Table 1, an image in which color unevenness and light leakage in a high temperature environment are suppressed by controlling the amount of glue slippage of the first pressure-sensitive adhesive layer and the creep value of the second pressure-sensitive adhesive layer in combination. It can be seen that a polarizing plate with a retardation layer and an adhesive layer that can realize a display device can be obtained.
表1から明らかなように、第1の粘着剤層の糊ずれ量および第2の粘着剤層のクリープ値を組み合わせて制御することにより、高温環境下における色ムラおよび光漏れが抑制された画像表示装置を実現し得る位相差層および粘着剤層付偏光板が得られることがわかる。 [evaluation]
As is clear from Table 1, an image in which color unevenness and light leakage in a high temperature environment are suppressed by controlling the amount of glue slippage of the first pressure-sensitive adhesive layer and the creep value of the second pressure-sensitive adhesive layer in combination. It can be seen that a polarizing plate with a retardation layer and an adhesive layer that can realize a display device can be obtained.
本発明の位相差層および粘着剤層付偏光板は画像表示装置(代表的には、液晶表示装置、有機EL表示装置)に好適に用いられ得る。
The polarizing plate with the retardation layer and the pressure-sensitive adhesive layer of the present invention can be suitably used for an image display device (typically, a liquid crystal display device or an organic EL display device).
10 偏光板
11 偏光子
12 第1の保護層
13 第2の保護層
20 第1の粘着剤層
30 位相差層
40 第2の粘着剤層
100 位相差層および粘着剤層付偏光板 10Polarizing plate 11 Polarizer 12 First protective layer 13 Second protective layer 20 First pressure-sensitive adhesive layer 30 Phase difference layer 40 Second pressure-sensitive adhesive layer 100 Phase difference layer and polarizing plate with pressure-sensitive adhesive layer
11 偏光子
12 第1の保護層
13 第2の保護層
20 第1の粘着剤層
30 位相差層
40 第2の粘着剤層
100 位相差層および粘着剤層付偏光板 10
Claims (11)
- 偏光子を含む偏光板と、該偏光板に第1の粘着剤層を介して貼り合わせられた位相差層と、該位相差層の該偏光板と反対側に最外層として設けられた第2の粘着剤層と、を有し、
該位相差層が、樹脂フィルムの延伸フィルムで構成され、Re(450)<Re(550)の関係を満足し、
該第1の粘着剤層の85℃および500時間の加熱試験後の糊ずれ量が900μm以下であり、
該第2の粘着剤層の85℃におけるクリープ値が40μm以下である、
位相差層および粘着剤層付偏光板:
ここで、Re(450)およびRe(550)は、それぞれ、23℃における波長450nmおよび550nmの光で測定した面内位相差である。 A polarizing plate containing a polarizing element, a retardation layer bonded to the polarizing plate via a first pressure-sensitive adhesive layer, and a second layer provided as an outermost layer on the opposite side of the retardation layer to the polarizing plate. With an adhesive layer,
The retardation layer is composed of a stretched film of a resin film, and satisfies the relationship of Re (450) <Re (550).
The amount of glue slippage of the first pressure-sensitive adhesive layer after a heating test at 85 ° C. and 500 hours is 900 μm or less.
The creep value of the second pressure-sensitive adhesive layer at 85 ° C. is 40 μm or less.
Polarizing plate with retardation layer and adhesive layer:
Here, Re (450) and Re (550) are in-plane phase differences measured with light having wavelengths of 450 nm and 550 nm at 23 ° C., respectively. - 前記位相差層のRe(550)が100nm~200nmであり、該位相差層の遅相軸と前記偏光子の吸収軸とのなす角度が40°~50°または130°~140°である、請求項1に記載の位相差層および粘着剤層付偏光板。 The Re (550) of the retardation layer is 100 nm to 200 nm, and the angle formed by the slow axis of the retardation layer and the absorption axis of the polarizing element is 40 ° to 50 ° or 130 ° to 140 °. The polarizing plate with a retardation layer and an adhesive layer according to claim 1.
- 前記位相差層の厚みが15μm~60μmである、請求項1または2に記載の位相差層および粘着剤層付偏光板。 The polarizing plate with a retardation layer and an adhesive layer according to claim 1 or 2, wherein the thickness of the retardation layer is 15 μm to 60 μm.
- 前記第1の粘着剤層の85℃および500時間の加熱試験後の糊ずれ量が250μm以下である、請求項1から3のいずれかに記載の位相差層および粘着剤層付偏光板。 The polarizing plate with the retardation layer and the pressure-sensitive adhesive layer according to any one of claims 1 to 3, wherein the amount of glue slippage of the first pressure-sensitive adhesive layer after a heating test at 85 ° C. and 500 hours is 250 μm or less.
- 前記第2の粘着剤層を構成する粘着剤組成物が、ベースポリマー100重量部に対して架橋剤を1.5重量部以上含む、請求項1から4のいずれかに記載の位相差層および粘着剤層付偏光板。 The retardation layer according to any one of claims 1 to 4, wherein the pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer contains 1.5 parts by weight or more of a cross-linking agent with respect to 100 parts by weight of the base polymer. Polarizing plate with adhesive layer.
- 前記第2の粘着剤層を構成する粘着剤組成物が、ベースポリマー100重量部に対して架橋剤を5重量部以上含む、請求項5に記載の位相差層および粘着剤層付偏光板。 The polarizing plate with a retardation layer and a pressure-sensitive adhesive layer according to claim 5, wherein the pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer contains 5 parts by weight or more of a cross-linking agent with respect to 100 parts by weight of the base polymer.
- 前記位相差層が、カーボネート結合およびエステル結合からなる群から選択される少なくとも1つの結合基と、下記一般式(1)で表される構造単位および下記一般式(2)で表される構造単位からなる群から選択される少なくとも1つの構造単位とを含み、正の屈折率異方性を有する樹脂と;アクリル系樹脂と;を含有し、該アクリル系樹脂の含有量が0.5質量%~2.0質量%であり、該アクリル系樹脂が、メタクリル酸メチル由来の構造単位を70質量%以上含有し、その重量平均分子量Mwが10,000~200,000である、請求項1から6のいずれかに記載の位相差層および粘着剤層付偏光板:
- 前記位相差層は、25℃/50%RH、60℃/50%RH、60℃/85%RHの順に環境を変化させる加湿TMA試験において遅相軸方向の寸法変化率が0.28%以下である、請求項1から7のいずれかに記載の位相差層および粘着剤層付偏光板。 The retardation layer has a dimensional change rate of 0.28% or less in the slow axial direction in a humidified TMA test in which the environment is changed in the order of 25 ° C / 50% RH, 60 ° C / 50% RH, and 60 ° C / 85% RH. The polarizing plate with the retardation layer and the pressure-sensitive adhesive layer according to any one of claims 1 to 7.
- 前記位相差層と前記第2の粘着剤層との間に、屈折率特性がnz>nx=nyの関係を示す別の位相差層をさらに有する、請求項1から8のいずれかに記載の位相差層および粘着剤層付偏光板。 The aspect according to any one of claims 1 to 8, further comprising another retardation layer having a refractive index characteristic of nz> nx = ny between the retardation layer and the second pressure-sensitive adhesive layer. Polarizing plate with retardation layer and adhesive layer.
- 前記位相差層は、前記別の位相差層が貼り合わされた状態で、25℃/50%RH、60℃/50%RH、60℃/85%RHの順に環境を変化させる加湿TMA試験において遅相軸方向の寸法変化率が0.28%以下である、請求項9に記載の位相差層および粘着剤層付偏光板。 The retardation layer is delayed in a humidifying TMA test in which the environment is changed in the order of 25 ° C./50% RH, 60 ° C./50% RH, and 60 ° C./85% RH with the other retardation layer bonded to each other. The polarizing plate with a retardation layer and an adhesive layer according to claim 9, wherein the dimensional change rate in the phase axis direction is 0.28% or less.
- 請求項1から10のいずれかに記載の位相差層および粘着剤層付偏光板を備える、画像表示装置。 An image display device comprising the polarizing plate with the retardation layer and the pressure-sensitive adhesive layer according to any one of claims 1 to 10.
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JP2001272541A (en) * | 2000-03-27 | 2001-10-05 | Nitto Denko Corp | Polarizing plate with optical compensating film and liquid crystal display device |
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JP2001272541A (en) * | 2000-03-27 | 2001-10-05 | Nitto Denko Corp | Polarizing plate with optical compensating film and liquid crystal display device |
JP2008031212A (en) * | 2006-07-26 | 2008-02-14 | Lintec Corp | Adhesive for bonding optical function film, optical function film having adhesive and method for producing the same |
JP2010085802A (en) * | 2008-10-01 | 2010-04-15 | Sony Corp | Retardation film polarizing plate laminate and liquid crystal display device |
JP2013072951A (en) * | 2011-09-27 | 2013-04-22 | Sumitomo Chemical Co Ltd | Polarizing plate and method for manufacturing the same |
JP2013101281A (en) * | 2011-11-09 | 2013-05-23 | Keio Gijuku | Polarizer with pressure-sensitive adhesive, method of designing polarizer with pressure-sensitive adhesive, method of manufacturing liquid crystal panel, method of manufacturing polarizer, and method of manufacturing polarizer with pressure-sensitive adhesive |
JP2020076968A (en) * | 2018-10-15 | 2020-05-21 | 日東電工株式会社 | Polarizing plate with retardation layer and image display using the same |
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