WO2017195506A1 - Optical film for organic el display devices, polarizing film for organic el display devices, polarizing film with adhesive layer for organic el display devices, and organic el display device - Google Patents

Optical film for organic el display devices, polarizing film for organic el display devices, polarizing film with adhesive layer for organic el display devices, and organic el display device Download PDF

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Publication number
WO2017195506A1
WO2017195506A1 PCT/JP2017/014222 JP2017014222W WO2017195506A1 WO 2017195506 A1 WO2017195506 A1 WO 2017195506A1 JP 2017014222 W JP2017014222 W JP 2017014222W WO 2017195506 A1 WO2017195506 A1 WO 2017195506A1
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organic
film
adhesive layer
display device
sensitive adhesive
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PCT/JP2017/014222
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French (fr)
Japanese (ja)
Inventor
良平 澤▲崎▼
真理 松本
淳 保井
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日東電工株式会社
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Priority to CN201780025832.0A priority Critical patent/CN109121431B/en
Priority to SG11201809771SA priority patent/SG11201809771SA/en
Priority to KR1020187030433A priority patent/KR102339860B1/en
Publication of WO2017195506A1 publication Critical patent/WO2017195506A1/en

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to an optical film for an organic EL display device.
  • the present invention provides a polarizing film for an organic EL display device including a polarizer and the optical film for an organic EL display device, and an adhesive for an organic EL display device in which an adhesive layer is further provided on the polarizing film for the organic EL display device.
  • the present invention relates to a polarizing film with a layer.
  • the present invention also relates to an organic EL display device using the polarizing film for an organic EL display device or the polarizing film with an adhesive layer for an organic EL display device.
  • organic EL display devices OLEDs
  • organic EL Electro Luminescence
  • a circularly polarizing plate is usually disposed on the viewing side surface of the organic EL panel in order to prevent external light from being reflected by a metal electrode (cathode) and viewed as a mirror surface.
  • the constituent members of the organic EL display device such as the circularly polarizing plate are usually laminated via a bonding material such as a pressure-sensitive adhesive layer or an adhesive layer.
  • a laminate of a polarizing plate and a ⁇ / 4 plate is generally used.
  • a polarizer and two retardation layers having specific refractive index characteristics are stacked.
  • the thing is also known (for example, refer patent document 1).
  • the organic EL element mounted on the organic EL display device is very weak to moisture and oxygen in the atmosphere, an optical film having a barrier layer and a barrier function is usually provided on the surface of the organic EL panel, In addition, it is required that the optical film constituting the organic EL display device and the pressure-sensitive adhesive layer for bonding these films do not transmit moisture or the like (low moisture permeability).
  • Patent Document 1 a polarizing plate with a retardation layer that suppresses changes in viewing angle characteristics and display characteristics is provided, and no consideration is given to imparting low moisture permeability to an optical film such as a retardation film. It was not.
  • a barrier layer is deposited on a retardation film ( ⁇ / 4 plate) constituting a circularly polarizing plate (antireflection film) used in an organic EL display device. It is possible to do. However, the method of depositing the barrier layer on the retardation film is not sufficient in terms of cost. Further, when the barrier layer is deposited on the retardation film, the retardation film is heated and the retardation film is broken. The phase difference value may change, which is not sufficient.
  • an object of the present invention is to provide an optical film for an organic EL display device having a more excellent low moisture permeability without forming a barrier layer made of an inorganic material formed by vapor deposition or the like.
  • the present invention provides a polarizing film for an organic EL display device including a polarizer and the optical film for an organic EL display device, and an adhesive for an organic EL display device having the polarizing film for an organic EL display device and an adhesive layer.
  • Another object is to provide a polarizing film with an agent layer.
  • Another object of the present invention is to provide an organic EL display device using the polarizing film for an organic EL display device or the polarizing film with an adhesive layer for an organic EL display device.
  • the present invention relates to a retardation film functioning as a ⁇ / 4 plate, a 40 ° C., 92% R.D. H. And an adhesive layer having a moisture permeability of 50 g / (m 2 ⁇ day) or less.
  • the adhesive layer is preferably a pressure-sensitive adhesive layer formed from a rubber-based pressure-sensitive adhesive composition containing polyisobutylene and a hydrogen abstraction type photopolymerization initiator.
  • the present invention also relates to a polarizing film for an organic EL display device comprising a polarizer and the optical film for an organic EL display device.
  • the thickness of the polarizer is preferably 15 ⁇ m or less.
  • the present invention also relates to a polarizing film with an adhesive layer for an organic EL display device, further comprising an adhesive layer on the polarizer side of the polarizing film for an organic EL display device.
  • the present invention relates to an organic EL display device comprising the polarizing film for an organic EL display device or the polarizing film with an adhesive layer for the organic EL display device.
  • the optical film for an organic EL display device of the present invention has a retardation film and an adhesive layer having a specific moisture permeability, and is excellent without forming a barrier layer made of an inorganic material by vapor deposition or the like. Moreover, low moisture permeability can be expressed.
  • the optical film for organic EL display devices of the present invention can constitute an antireflection film for organic EL display devices (polarizing film for organic EL display devices) together with a polarizer. Moreover, the optical film for organic EL display devices of the present invention is advantageous in terms of cost.
  • this invention can provide the polarizing film for organic EL display apparatuses which has the outstanding low moisture permeability, and the polarizing film with an adhesive layer for organic EL display apparatuses.
  • the present invention provides an organic EL display device excellent in optical reliability by using the polarizing film for organic EL display devices or the polarizing film with an adhesive layer for organic EL display devices further comprising an adhesive layer. Can do.
  • optical film for organic EL display device comprises a retardation film functioning as a ⁇ / 4 plate, 40 ° C., 92% R.D. H. And a pressure-sensitive adhesive layer having a moisture permeability of 50 g / (m 2 ⁇ day) or less.
  • the optical film 1 for an organic EL display device of the present invention has an adhesive layer 2 on at least one surface of a retardation film 3a that functions as a ⁇ / 4 plate.
  • a retardation film 3a that functions as a ⁇ / 4 plate.
  • surface of the phase difference film 3a is disclosed, you may have the adhesive layer 2 on both surfaces of the phase difference film 3a.
  • connect is described in FIG. 1, this invention is not limited to such an aspect, and another layer is included between each said layer. You may go out. The same applies to FIGS.
  • the optical film 1 for an organic EL display device of the present invention includes a retardation film 3a (also referred to as a first retardation film) that functions as a ⁇ / 4 plate.
  • 2 retardation films 3b may be included. Specifically, it is composed of (retardation film 3 a functioning as a ⁇ / 4 plate) / adhesive layer or pressure-sensitive adhesive layer 4 / second retardation film 3 b / adhesive layer 2.
  • the moisture permeability of the optical film for organic EL display devices is preferably 50 g / (m 2 ⁇ day) or less, more preferably 30 g / (m 2 ⁇ day) or less, and 20 g / (m 2 ⁇ day) or less. Is more preferable, and 15 g / (m 2 ⁇ day) or less is particularly preferable. Further, the lower limit value of moisture permeability is not particularly limited, but ideally, it is preferable that water vapor is not permeated at all (that is, 0 g / (m 2 ⁇ day)).
  • the water vapor transmission rate of the optical film for organic EL display devices is within the above range, when the optical film for organic EL display devices is applied to an organic EL element, it is possible to prevent moisture from being transferred to the organic EL element. As a result, it is preferable because deterioration due to moisture of the organic EL element can be suppressed.
  • the measuring method of the moisture permeability can be measured by the method described in the examples.
  • the retardation film 3a used in the present invention is a film that can function as a ⁇ / 4 plate.
  • the in-plane retardation Re (550) of such retardation film 3a measured with light having a wavelength of 550 nm at 23 ° C. is preferably 100 to 180 nm, more preferably 110 to 170 nm, and more preferably 120 to 160 nm. More preferably, the thickness is 135 to 155 nm.
  • nx is the refractive index in the direction in which the in-plane refractive index is maximum (that is, the slow axis direction), and ny is in the direction orthogonal to the slow axis in the plane (that is, the fast axis direction). It is a refractive index, and nz is a refractive index in the thickness direction.
  • the Nz coefficient of the retardation film 3a is, for example, preferably 0.9 to 2, more preferably 1 to 1.5, and still more preferably 1 to 1.3.
  • the thickness of the retardation film 3a can be appropriately set so as to obtain a desired in-plane retardation, and is not particularly limited, but is preferably 10 to 80 ⁇ m, for example. It is more preferably 10 to 60 ⁇ m, and further preferably 30 to 55 ⁇ m.
  • the retardation film 3a may exhibit reverse dispersion wavelength characteristics in which the retardation value increases in accordance with the wavelength of the measurement light, and exhibits positive chromatic dispersion characteristics in which the retardation value decreases in accordance with the wavelength of the measurement light.
  • the phase difference value may exhibit a flat chromatic dispersion characteristic that hardly changes depending on the wavelength of the measurement light, but preferably exhibits a flat chromatic dispersion characteristic.
  • Re (450) / Re (550) of the retardation film 3a is preferably 0.85 to 1.03, and Re (650) / Re (550) is preferably 0.98 to 1.02. preferable.
  • Re ( ⁇ ) is an in-plane phase difference measured with light having a wavelength ⁇ nm at 23 ° C.
  • Re (450) represents an in-plane phase difference measured with light having a wavelength of 450 nm at 23 ° C. .
  • the retardation film 3a can be composed of any appropriate resin film that can satisfy the optical characteristics as described above.
  • Any appropriate resin can be used as the resin for forming the resin film, and specifically, cycloolefin resins such as polynorbornene, polycarbonate resins, cellulose resins, polyvinyl alcohol resins, polysulfone resins.
  • the resin include resins. Among these, polynorbornene and polycarbonate resin are preferable.
  • the above polynorbornene means a (co) polymer obtained by using a norbornene-based monomer having a norbornene ring as a part or all of a starting material (monomer).
  • the polycarbonate-based resin contains at least a structural unit derived from a dihydroxy compound having a bond structure represented by the following structural formula (1), and has at least one bond structure “—CH 2 —O—” in the molecule. It is produced by reacting a dihydroxy compound containing at least a dihydroxy compound having a carbonic acid diester in the presence of a polymerization catalyst.
  • the dihydroxy compound having a bond structure represented by the structural formula (1) includes a structure having two alcoholic hydroxyl groups and a linking group “—CH 2 —O—” in the molecule, Any compound having any structure can be used as long as it is a compound capable of reacting with a carbonic acid diester in the presence to form a polycarbonate, and a plurality of compounds may be used in combination. Moreover, you may use together the dihydroxy compound which does not have the coupling
  • dihydroxy compound (A) a dihydroxy compound having a bond structure represented by Structural Formula (1)
  • dihydroxy compound (B) a dihydroxy compound having no bond structure represented by Structural Formula (1)
  • the linking group “—CH 2 —O—” in the dihydroxy compound (A) means a structure constituting a molecule by bonding to atoms other than hydrogen atoms. In this linking group, at least an atom to which an oxygen atom can be bonded or an atom to which a carbon atom and an oxygen atom can be bonded simultaneously is most preferably a carbon atom.
  • the number of linking groups “—CH 2 —O—” in the dihydroxy compound (A) is 1 or more, preferably 2 to 4.
  • examples of the dihydroxy compound (A) include 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy-2-). Methyl) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9- Bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3
  • dihydroxy compound represented by the formula (2) examples include isosorbide, isomannide and isoidet which are in a stereoisomeric relationship, and these may be used alone or in combination of two or more. May be.
  • dihydroxy compound (A) for example, oxyalkylene glycols and diols having a cyclic ether structure can be suitably used.
  • Examples of the oxyalkylene glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol.
  • Examples of the diols having a cyclic ether structure include spiroglycols and dioxane glycols.
  • isosorbide obtained by dehydrating condensation of sorbitol produced from various starches that are abundant as resources and are readily available is easy to obtain and produce, and optical characteristics From the viewpoint of moldability, it is preferable. Also, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and polyethylene glycol are preferable.
  • Liquid form such as a powder form and flake form, a molten state and aqueous solution, may be sufficient. .
  • dihydroxy compound (B) examples include alicyclic dihydroxy compounds, aliphatic dihydroxy compounds, and aromatic dihydroxy compounds.
  • the alicyclic dihydroxy compound is not particularly limited, but a compound containing a 5-membered ring structure or a 6-membered ring structure is preferable.
  • the 6-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond.
  • the alicyclic dihydroxy compound having a 5-membered or 6-membered ring structure is preferable because the heat resistance of the resulting polycarbonate can be increased.
  • the number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, and more preferably 30 or less. The higher this value, the higher the heat resistance, but the synthesis becomes difficult, the purification becomes difficult, and the cost is expensive. The smaller the number of carbon atoms, the easier the purification and the easier it is to obtain.
  • alicyclic dihydroxy compound containing a 5-membered ring structure or a 6-membered ring structure include alicyclic dihydroxy compounds represented by the following general formula (I) or (II).
  • HOCH 2 —R 1 —CH 2 OH (I) HO—R 2 —OH (II) (In formulas (I) and (II), R 1 and R 2 each represent a cycloalkylene group having 4 to 20 carbon atoms.)
  • R 1 is represented by the following general formula (Ia) (wherein R 3 has 1 carbon atom) To 12 alkyl groups or hydrogen atoms). Specific examples include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and the like.
  • R 1 is represented by the following general formula (Ib) (wherein , N represents 0 or 1).
  • R 1 is represented by the following general formula (Ic) (wherein m represents 0 or 1). Specific examples thereof include 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, and the like.
  • norbornanedimethanol which is an alicyclic dihydroxy compound represented by the above general formula (I)
  • various isomers in which R 1 is represented by the following general formula (Id) in the general formula (I) include 2,3-norbornane dimethanol and 2,5-norbornane dimethanol.
  • the adamantane dimethanol which is an alicyclic dihydroxy compound represented by the general formula (I), includes various isomers in which R 1 is represented by the following general formula (Ie) in the general formula (I). Specific examples of such compounds include 1,3-adamantane dimethanol.
  • cyclohexanediol which is an alicyclic dihydroxy compound represented by the general formula (II), in the general formula (II), R 2 is represented by the following general formula (IIa) (wherein, R 3 is C 1 -C To 12 alkyl groups or hydrogen atoms).
  • R 3 is C 1 -C To 12 alkyl groups or hydrogen atoms.
  • Specific examples of such compounds include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and the like.
  • R 2 is represented by the following general formula (IIb) (wherein n Represents 0 or 1).
  • R 2 is represented by the following general formula (IIc) (where m is 0 Or various isomers represented by 1). Specifically, 2,6-decalindiol, 1,5-decalindiol, 2,3-decalindiol and the like are used as such.
  • the norbornanediol which is an alicyclic dihydroxy compound represented by the above general formula (II) includes various isomers in which R 2 is represented by the following general formula (IId) in the general formula (II). Specifically, 2,3-norbornanediol, 2,5-norbornanediol and the like are used as such.
  • the adamantanediol which is an alicyclic dihydroxy compound represented by the above general formula (II) includes various isomers in which R 2 is represented by the following general formula (IIe) in the general formula (II). Specifically, 1,3-adamantanediol or the like is used as such.
  • cyclohexane dimethanols examples include tricyclodecane dimethanols, adamantanediols, and pentacyclopentadecane dimethanols are preferable, and are easily available and easy to handle. From this viewpoint, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and tricyclodecane dimethanol are preferable.
  • Examples of the aliphatic dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1, Examples include 5-heptanediol and 1,6-hexanediol.
  • the above exemplary compounds are examples of alicyclic dihydroxy compounds, aliphatic dihydroxy compounds, and aromatic dihydroxy compounds that can be used in the present invention, and are not limited thereto. These compounds can be used individually by 1 type or in mixture of 2 or more types.
  • the ratio of the dihydroxy compound (A) to the total dihydroxy compound constituting the polycarbonate resin is not particularly limited, but is preferably 10 mol% or more, more preferably 40 mol% or more, and further preferably 60 mol% or more. Moreover, as an upper limit, 100 mol% or less is preferable. When the content ratio of the structural unit derived from the dihydroxy compound (B) is too large, performance such as optical characteristics may be deteriorated.
  • the ratio of the total of the dihydroxy compound (A) and each of these dihydroxy compounds to the total dihydroxy compound constituting the polycarbonate is not particularly limited, You can select any ratio.
  • the content rate of the structural unit derived from the dihydroxy compound (A) and the structural unit derived from each of these dihydroxy compounds is not particularly limited, and can be selected at an arbitrary ratio.
  • Carbonated diester examples of the carbonic acid diester used in the method for producing the polycarbonate resin include diphenyl carbonate, substituted diphenyl carbonate typified by ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Among these, Diphenyl carbonate and substituted diphenyl carbonate are particularly preferred. These carbonic acid diesters may be used alone or in combination of two or more.
  • the carbonic acid diester is preferably used in a molar ratio of 0.90 to 1.10, more preferably in a molar ratio of 0.96 to 1.04, based on all dihydroxy compounds used in the reaction.
  • this molar ratio is less than 0.90, the terminal OH group of the produced polycarbonate increases, and the thermal stability of the polymer may deteriorate, or the desired high molecular weight product may not be obtained.
  • the molar ratio is greater than 1.10, the rate of the transesterification reaction decreases under the same conditions, and it becomes difficult to produce a polycarbonate having a desired molecular weight.
  • the amount of residual carbonic acid diester increases, and this residual carbonic acid diester may cause odor during molding or in the molded product.
  • the glass transition temperature (Tg) of the polycarbonate-based resin is preferably 45 ° C. or higher, more preferably 45 to 130 ° C.
  • the polycarbonate resin can be produced by a melt polymerization method in which a dihydroxy compound containing the dihydroxy compound (A) is reacted with a carbonic acid diester in the presence of a polymerization catalyst.
  • a polymerization catalyst As the type of polymerization catalyst and the addition amount thereof, conventionally known ones and addition amounts can be appropriately employed, and conventionally known methods can be appropriately employed for the solution polymerization method.
  • the retardation film 3a is obtained, for example, by stretching a film formed from the above resin.
  • Any appropriate forming method can be adopted as a method for forming a film from the resin. Specific examples include compression molding methods, transfer molding methods, injection molding methods, extrusion molding methods, blow molding methods, powder molding methods, FRP molding methods, cast coating methods (for example, casting methods), calendar molding methods, and hot presses. Law.
  • the extrusion molding method or the cast coating method is preferable because the smoothness of the resulting film can be improved and good optical uniformity can be obtained.
  • the molding conditions can be appropriately set according to the composition and type of the resin used, the properties desired for the retardation film, and the like.
  • the said commercial film can also be used for a extending
  • the stretching ratio of the film can be appropriately set according to the in-plane retardation value and thickness desired for the retardation film 3a, the type of resin used, the thickness of the film used, the stretching temperature, and the like. Specifically, the draw ratio is preferably about 1.75 times to 3.00 times, more preferably about 1.80 times to 2.80 times, and further preferably about 1.85 times to 2.60 times.
  • the stretching temperature of the film can be appropriately set according to the in-plane retardation value and thickness desired for the retardation film 3a, the type of resin used, the thickness of the film used, the stretching ratio, and the like. Specifically, the stretching temperature is preferably about 125 ° C. to 150 ° C., more preferably about 130 ° C. to 140 ° C.
  • any appropriate stretching method can be adopted as the stretching method of the film.
  • various stretching methods such as free end stretching, fixed end stretching, free end contraction, and fixed end contraction can be used singly or simultaneously or sequentially.
  • the stretching direction can also be performed in various directions and dimensions such as a horizontal direction, a vertical direction, a thickness direction, and a diagonal direction.
  • the retardation film 3a is formed by stretching a resin film uniaxially at a free end or uniaxially at a fixed end.
  • the free end uniaxial stretching there is a method of stretching between rolls having different peripheral speeds while running the resin film in the longitudinal direction.
  • the fixed end uniaxial stretching there is a method of stretching in the width direction (lateral direction) while running the resin film in the longitudinal direction.
  • the retardation film 3a is produced by continuously stretching a long resin film obliquely in a direction at a predetermined angle with respect to the longitudinal direction.
  • a long stretched film having an orientation angle of a predetermined angle with respect to the longitudinal direction of the film is obtained.
  • a roll toe roll means the system laminated
  • Examples of the stretching machine used for the oblique stretching include a tenter type stretching machine capable of adding a feed force, a pulling force, or a pulling force at different speeds in the lateral and / or longitudinal directions.
  • the tenter type stretching machine includes a horizontal uniaxial stretching machine, a simultaneous biaxial stretching machine, and the like, but any suitable stretching machine can be used as long as a long resin film can be continuously stretched obliquely.
  • the optical film for an organic EL display device of the present invention does not have a barrier layer containing an inorganic thin film, and the retardation film 3a does not have a barrier layer containing an inorganic thin film.
  • Such an inorganic thin film is usually formed by sputtering or the like, and generates heat during the formation process. By providing such an inorganic thin film on the retardation film 3a, the retardation value of the retardation film 3a may be changed by heat, or the retardation film 3a may be broken, which is not preferable.
  • the inorganic thin film include those containing at least one inorganic compound selected from the group consisting of oxides, nitrides, hydrides, and complex compounds thereof.
  • Examples of the inorganic compound that forms the inorganic thin film include diamond-like carbon (DLC), silicon nitride (SiNx), silicon oxide (SiOy), aluminum oxide (AlOz), and aluminum nitride.
  • the second retardation film 3b has a refractive index characteristic of nz> nx ⁇ ny.
  • the angle dependency of the effect of absorbing the reflected light is reduced, and the reflected light reflected at various angles is prevented from being emitted. This is preferable.
  • the thickness direction retardation Rth (550) of the second retardation film 3b is preferably ⁇ 260 nm to ⁇ 10 nm, more preferably ⁇ 230 nm to ⁇ 15 nm, and further preferably ⁇ 215 nm to ⁇ 20 nm. Such a range is preferable because the above-described effect becomes remarkable.
  • Re (550) is less than 10 nm.
  • the second retardation film 3b has a relationship in which the refractive index is nx> ny.
  • the in-plane retardation Re (550) of the second retardation film 3b is preferably 10 nm to 150 nm, and more preferably 10 nm to 80 nm.
  • the second retardation film 3b can be formed of any appropriate material, and is not particularly limited, but is preferably a liquid crystal layer fixed in homeotropic alignment.
  • the liquid crystal material (liquid crystal compound) that can be homeotropically aligned may be a liquid crystal monomer or a liquid crystal polymer.
  • Specific examples of the liquid crystal compound and the method for forming the liquid crystal layer include, for example, the liquid crystal compounds and methods described in JP-A-2002-333642, [0020] to [0042].
  • the thickness is preferably 0.1 ⁇ m to 5 ⁇ m, more preferably 0.2 ⁇ m to 3 ⁇ m.
  • the second retardation film 3b may be a retardation film formed of a fumaric acid diester resin described in JP 2012-32784 A.
  • the thickness is preferably 5 ⁇ m to 50 ⁇ m, more preferably 10 ⁇ m to 35 ⁇ m.
  • the in-plane retardation (550) Re of the laminated retardation film composed of the first retardation film 3a and the second retardation film 3b is preferably 120 nm to 160 nm, and more preferably 130 nm to 150 nm. 135 nm to 145 nm is more preferable.
  • the thickness direction retardation Rth (550) of the laminated retardation film composed of the first retardation film 3a and the second retardation film 3b is preferably 40 nm to 100 nm, and more preferably 50 nm to 90 nm. More preferred is 60 nm to 80 nm.
  • first retardation film 3a and the second retardation film 3b can be laminated via an arbitrary adhesive layer or pressure-sensitive adhesive layer 4.
  • adhesive layer or the pressure-sensitive adhesive layer 4 those described in the present specification can be suitably used.
  • an acrylic pressure-sensitive adhesive based on a (meth) acrylic polymer is optically transparent. It is preferable because it exhibits excellent wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and is excellent in weather resistance, heat resistance, and the like.
  • any known adhesive layer or pressure-sensitive adhesive layer can be used.
  • Adhesive layer used in the present invention is 40 ° C., 92% R.D. H.
  • the water vapor transmission rate in the case of 50 g / (m 2 ⁇ day) or less is not particularly limited.
  • the “adhesive layer” refers to an adhesive layer or a pressure-sensitive adhesive layer.
  • the moisture permeability of the adhesive layer is, 50g / (m 2 ⁇ day ) or less, preferably 30g / (m 2 ⁇ day) or less, 20g / (m 2 ⁇ day ) , more preferably less, 15 g / (M 2 ⁇ day) or less is more preferable.
  • the lower limit value of moisture permeability is not particularly limited, but ideally, it is preferable that water vapor is not permeated at all (that is, 0 g / (m 2 ⁇ day)).
  • the moisture permeability is 40 ° C. and 92% R.D. H.
  • the water vapor transmission rate (moisture permeability) under the conditions can be measured by the method described in the examples.
  • Adhesive Layer As the adhesive layer, 40 ° C., 92% R.D. H.
  • the water vapor transmission rate may be 50 g / (m 2 ⁇ day) or less, and the composition is not particularly limited, and a layer made of any appropriate adhesive may be adopted.
  • adhesives include natural rubber adhesives, ⁇ -olefin adhesives, urethane resin adhesives, ethylene-vinyl acetate resin emulsion adhesives, ethylene-vinyl acetate resin hot melt adhesives, and epoxy resins.
  • Adhesives vinyl chloride resin solvent adhesives, chloroprene rubber adhesives, cyanoacrylate adhesives, silicone adhesives, styrene-butadiene rubber solvent adhesives, nitrile rubber adhesives, nitrocellulose adhesives, Reactive hot melt adhesives, phenol resin adhesives, modified silicone adhesives, polyester hot melt adhesives, polyamide resin hot melt adhesives, polyimide adhesives, polyurethane resin hot melt adhesives, polyolefin resin hot melt adhesives
  • Adhesive polyvinyl acetate resin solvent-based adhesive, Styrene resin solvent adhesive, polyvinyl alcohol adhesive, polyvinyl pyrrolidone resin adhesive, polyvinyl butyral adhesive, polybenzimidazole adhesive, polymethacrylate resin solvent adhesive, melamine resin adhesive, urea resin adhesive Agents, resorcinol adhesives, and the like.
  • Such an adhesive agent can be used individually by 1 type or in mixture of 2 or more types.
  • adhesives include, for example, thermosetting adhesives and hot-melt adhesives when classified according to the adhesive form. Only one kind of such an adhesive may be used, or two or more kinds thereof may be used.
  • thermosetting adhesive exhibits an adhesive force when cured by heating and solidified.
  • thermosetting adhesive include an epoxy thermosetting adhesive, a urethane thermosetting adhesive, and an acrylic thermosetting adhesive.
  • the curing temperature of the thermosetting adhesive is, for example, 100 to 200 ° C.
  • the hot melt adhesive is melted or softened by heating, thermally fused to the adherend, and then solidified by cooling to adhere to the adherend.
  • hot melt adhesives include rubber hot melt adhesives, polyester hot melt adhesives, polyolefin hot melt adhesives, ethylene-vinyl acetate resin hot melt adhesives, polyamide resin hot melt adhesives, and polyurethane resins. Examples thereof include hot melt adhesives.
  • the softening temperature (ring ball method) of the hot melt adhesive is, for example, 100 to 200 ° C.
  • the melt viscosity of the hot melt adhesive is 180 ° C., for example, 100 to 30000 mPa ⁇ s.
  • the thickness of the adhesive layer is not particularly limited, but is preferably about 0.01 to 10 ⁇ m, and more preferably about 0.05 to 8 ⁇ m.
  • Adhesive layer As the adhesive layer, 40 ° C, 92% R.D. H.
  • the water vapor transmission rate may be 50 g / (m 2 ⁇ day) or less, and the composition thereof is not particularly limited, and a layer made of any appropriate pressure-sensitive adhesive composition can be adopted.
  • the adhesive composition include rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide.
  • a pressure-sensitive adhesive, a cellulose-based pressure-sensitive adhesive, and the like can be mentioned.
  • a rubber-based pressure-sensitive adhesive composition is preferable from the viewpoint of moisture permeability.
  • the rubber-based pressure-sensitive adhesive composition only needs to contain a rubber-based polymer, and the composition is not particularly limited.
  • the rubber polymer used in the present invention is a polymer exhibiting rubber elasticity in a temperature range near room temperature.
  • Specific examples include styrene-based thermoplastic elastomers and isobutylene-based polymers.
  • polyisobutylene which is a homopolymer of isobutylene, is used. Is preferred. This is because polyisobutylene has excellent light resistance because it does not contain a double bond in the main chain.
  • polystylene for example, commercially available products such as OPPANOL manufactured by BASF can be used.
  • the weight average molecular weight (Mw) of the polyisobutylene is preferably 100,000 or more, more preferably 300,000 or more, further preferably 600,000 or more, and particularly preferably 700,000 or more. .
  • the upper limit of the weight average molecular weight is not particularly limited, but is preferably 5 million or less, more preferably 3 million or less, and even more preferably 2 million or less.
  • the content of the polyisobutylene is not particularly limited, but is preferably 50% by weight or more, more preferably 60% by weight or more in the total solid content of the rubber-based pressure-sensitive adhesive composition. It is further preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 85% by weight or more, and particularly preferably 90% by weight or more.
  • the upper limit of the content of polyisobutylene is not particularly limited, and is preferably 99% by weight or less, and more preferably 98% by weight or less. It is preferable that polyisobutylene is contained in the above range because it is excellent in low moisture permeability.
  • the rubber-based pressure-sensitive adhesive composition used in the present invention may contain a polymer, an elastomer, or the like other than the polyisobutylene.
  • copolymers of isobutylene and normal butylene for example, butyl rubbers such as regular butyl rubber, chlorinated butyl rubber, brominated butyl rubber, and partially crosslinked butyl rubber), and vulcanization thereof
  • modified products for example, those modified with a functional group such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • SIS Styrene-butadiene-styrene block copolymer
  • SBS Styrene-ethylene-propylene-s
  • the rubber-based pressure-sensitive adhesive composition used in the present invention particularly preferably contains the polyisobutylene and a hydrogen abstraction type photopolymerization initiator.
  • the hydrogen abstraction type photopolymerization initiator is capable of drawing a hydrogen from the polyisobutylene and creating a reactive site in the polyisobutylene without irradiating the initiator itself by irradiating active energy rays. . By forming the reaction point, the crosslinking reaction of polyisobutylene can be started.
  • the photopolymerization initiator in addition to the hydrogen abstraction type photopolymerization initiator used in the present invention, there are also cleavage type photopolymerization initiators that generate radicals by cleavage of the photopolymerization initiator itself upon irradiation with active energy rays.
  • cleavage type photopolymerization initiators that generate radicals by cleavage of the photopolymerization initiator itself upon irradiation with active energy rays.
  • the main chain of polyisobutylene is cleaved by the photopolymerization initiator in which radicals are generated, and cannot be crosslinked.
  • polyisobutylene can be crosslinked as described above.
  • Examples of the hydrogen abstraction type photopolymerization initiator include acetophenone, benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4,4′-dimethoxybenzophenone, 4,4 '-Dichlorobenzophenone, 4,4'-dimethylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 3,3′-dimethyl-4-methoxybenzophenone; thioxanes such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Compounds such as 4,
  • the content of the hydrogen abstraction type photopolymerization initiator is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 10 parts by weight with respect to 100 parts by weight of the polyisobutylene. More preferably, it is 0.01 to 10 parts by weight. It is preferable to include a hydrogen abstraction type photopolymerization initiator in the above-mentioned range since the crosslinking reaction can proceed to a target density.
  • a cleavage type photopolymerization initiator may be used together with the hydrogen abstraction type photopolymerization initiator as long as the effects of the present invention are not impaired.
  • the rubber-based pressure-sensitive adhesive composition used in the present invention can further contain a polyfunctional radical polymerizable compound.
  • the polyfunctional radically polymerizable compound functions as a crosslinking agent for polyisobutylene.
  • the polyfunctional radical polymerizable compound is a compound having at least two radical polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
  • Specific examples of the polyfunctional radical polymerizable compound include, for example, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol.
  • the content of the polyfunctional radically polymerizable compound is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and further preferably 10 parts by weight or less based on 100 parts by weight of the polyisobutylene.
  • the lower limit value of the content of the polyfunctional radical polymerizable compound is not particularly limited. For example, it is preferably 0.1 parts by weight or more with respect to 100 parts by weight of the polyisobutylene, More preferably, it is more than 1 part by weight, and still more preferably 1 part by weight. It is preferable from a viewpoint of durability of the obtained rubber-type adhesive layer that content of a polyfunctional radically polymerizable compound exists in the said range.
  • the molecular weight of the polyfunctional radically polymerizable compound is not particularly limited, but is preferably about 1000 or less, and more preferably about 500 or less.
  • the rubber-based pressure-sensitive adhesive composition used in the present invention comprises at least one tackifier selected from the group consisting of a tackifier containing a terpene skeleton, a tackifier containing a rosin skeleton, and a hydrogenated product thereof. Can be included.
  • a tackifier in the rubber-based pressure-sensitive adhesive composition, a rubber-based pressure-sensitive adhesive layer having high adhesion to various adherends and having high durability even in a high temperature environment is formed. Is preferable.
  • tackifier containing the terpene skeleton examples include terpene polymers such as ⁇ -pinene polymer, ⁇ -pinene polymer and dipentene polymer, and modified terpene polymers (phenol-modified, styrene-modified, aromatic). Modified terpene resin and the like).
  • modified terpene resin examples include terpene phenol resin, styrene modified terpene resin, aromatic modified terpene resin, hydrogenated terpene resin (hydrogenated terpene resin) and the like.
  • Examples of the hydrogenated terpene resin herein include a hydride of a terpene polymer and other modified terpene resins and hydrogenated terpene phenol resins.
  • a hydrogenated product of terpene phenol resin is preferable from the viewpoint of compatibility with the rubber-based pressure-sensitive adhesive composition and pressure-sensitive adhesive properties.
  • tackifier containing the rosin skeleton examples include rosin resin, polymerized rosin resin, hydrogenated rosin resin, rosin ester resin, hydrogenated rosin ester resin, rosin phenol resin, and the like.
  • rosin resin polymerized rosin resin
  • hydrogenated rosin resin rosin ester resin
  • hydrogenated rosin ester resin rosin phenol resin
  • gum rosin, wood rosin Unmodified rosin such as tall oil rosin (raw rosin), hydrogenated, disproportionated, polymerized, other chemically modified modified rosin, and derivatives thereof can be used.
  • tackifier for example, commercially available products such as the Clearon series, Polystar series, Superester series, Pencel series, Pine Crystal series, etc. manufactured by Yashara Chemical Co., Ltd. may be used. it can.
  • the hydrogenation may be a partially hydrogenated product that has been partially hydrogenated, and all the double bonds in the compound are fully hydrogenated. It may be a hydrogenated product. In the present invention, a completely hydrogenated product is preferred from the viewpoints of adhesive properties, weather resistance and hue.
  • the tackifier preferably contains a cyclohexanol skeleton from the viewpoint of adhesive properties. Although the detailed principle is unknown, it is thought that the cyclohexanol skeleton is more compatible with the base polymer polyisobutylene than the phenol skeleton.
  • a tackifier containing a cyclohexanol skeleton for example, hydrogenated products such as terpene phenol resin and rosin phenol resin are preferable, and complete hydrogenated products such as terpene phenol resin and rosin phenol resin are more preferable.
  • the softening point (softening temperature) of the tackifier is not particularly limited, but is preferably about 80 ° C. or higher, and more preferably about 100 ° C. or higher. It is preferable that the tackifier has a softening point of 80 ° C. or higher because the tackifier can be kept soft without being softened even at high temperatures.
  • the upper limit value of the softening point of the tackifier is not particularly limited, but if the softening point becomes too high, the molecular weight becomes higher, the compatibility deteriorates, and problems such as whitening may occur.
  • the temperature is preferably about 200 ° C. or less, and preferably about 180 ° C. or less.
  • the softening point of the tackifier resin here is defined as a value measured by a softening point test method (ring ball method) defined in either JIS K5902 or JIS K2207.
  • the weight average molecular weight (Mw) of the tackifier is not particularly limited, but is preferably 50,000 or less, preferably 30,000 or less, and more preferably 10,000 or less, It is more preferably 8000 or less, and particularly preferably 5000 or less.
  • the lower limit of the weight average molecular weight of the tackifier is not particularly limited, but is preferably 500 or more, more preferably 1000 or more, and further preferably 2000 or more. It is preferable that the weight average molecular weight of the tackifier is in the above range because the compatibility with polyisobutylene is good and problems such as whitening do not occur.
  • the addition amount of the tackifier is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, and further preferably 20 parts by weight or less with respect to 100 parts by weight of the polyisobutylene. .
  • the lower limit of the addition amount of the tackifier is not particularly limited, but is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and 5 parts by weight or more. More preferably.
  • tackifiers other than the tackifier containing the terpene skeleton and the tackifier containing the rosin skeleton can be added to the rubber-based pressure-sensitive adhesive composition used in the present invention.
  • the tackifier include petroleum resin-based tackifiers.
  • the petroleum-based tackifier include aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins (aliphatic cyclic petroleum resins), aliphatic / aromatic petroleum resins, aliphatic / aliphatic resins. Examples thereof include cyclic petroleum resins, hydrogenated petroleum resins, coumarone resins, coumarone indene resins, and the like.
  • the petroleum resin tackifier can be used within a range that does not impair the effects of the present invention.
  • it can be used in an amount of about 30 parts by weight or less with respect to 100 parts by weight of the polyisobutylene.
  • An organic solvent can be added as a diluent to the rubber-based pressure-sensitive adhesive composition.
  • the diluent is not particularly limited, and examples thereof include toluene, xylene, n-heptane, dimethyl ether, and the like. These may be used alone or in combination of two or more. it can. Among these, toluene is preferable.
  • the addition amount of the diluent is not particularly limited, but it is preferably added to the rubber-based pressure-sensitive adhesive composition at about 50 to 95% by weight, and more preferably about 70 to 90% by weight. When the addition amount of the diluent is within the above range, it is preferable from the viewpoint of coatability to a support or the like.
  • Additives other than those described above can also be added to the rubber-based pressure-sensitive adhesive composition used in the present invention as long as the effects of the present invention are not impaired.
  • the additive include a softening agent, a crosslinking agent (for example, polyisocyanate, epoxy compound, alkyl etherified melamine compound, etc.), filler, anti-aging agent, ultraviolet absorber and the like.
  • the kind, combination, addition amount, and the like of the additive added to the rubber-based pressure-sensitive adhesive composition can be appropriately set according to the purpose.
  • the content (total amount) of the additive in the rubber-based pressure-sensitive adhesive composition is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less.
  • the pressure-sensitive adhesive layer used in the present invention can be formed from the pressure-sensitive adhesive composition, and its production method is not particularly limited, but the pressure-sensitive adhesive composition is applied to various supports, etc.
  • the pressure-sensitive adhesive layer can be formed by irradiation or the like.
  • the pressure-sensitive adhesive composition contains polyisobutylene
  • the pressure-sensitive adhesive composition is preferably irradiated with active energy rays to crosslink the polyisobutylene.
  • the active energy ray is applied to the coating layer obtained by applying the rubber-based pressure-sensitive adhesive composition to various supports.
  • the active energy ray may be irradiated directly on the coating layer (without bonding other members, etc.), or after bonding various members such as an optical film such as a separator or glass to the coating layer. May be.
  • active energy rays may be irradiated through the optical film or various members, and the optical film or various members are peeled off, and the peeled surface is used. You may irradiate an active energy ray.
  • Various methods are used as a method for applying the pressure-sensitive adhesive composition. Specifically, for example, by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
  • the heat-drying temperature is preferably about 30 ° C. to 200 ° C., more preferably 40 ° C. to 180 ° C., and further preferably 80 ° C. to 150 ° C.
  • the heating temperature in the above range, an adhesive layer having excellent adhesive properties can be obtained.
  • the drying time an appropriate time can be adopted as appropriate.
  • the drying time is preferably about 5 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and further preferably 1 minute to 8 minutes.
  • the adhesive or the pressure-sensitive adhesive composition contains an organic solvent as a diluent, after application, before the irradiation with the active energy ray In addition, it is preferable to remove the solvent and the like by heating and drying.
  • the heating and drying temperature is not particularly limited, but is preferably about 30 ° C. to 90 ° C., more preferably about 60 ° C. to 80 ° C. from the viewpoint of reducing the residual solvent.
  • As the drying time an appropriate time can be adopted as appropriate.
  • the drying time is preferably about 5 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and further preferably 1 minute to 8 minutes.
  • Examples of the active energy rays include visible light, ultraviolet rays, and electron beams. Among these, ultraviolet rays are preferable.
  • the irradiation condition of ultraviolet rays is not particularly limited, and can be set to any appropriate condition depending on the composition of the rubber-based pressure-sensitive adhesive composition to be crosslinked.
  • the integrated irradiation light amount is 100 mJ / cm 2. ⁇ 2000 mJ / cm 2 is preferred.
  • a peeled sheet (separator) or the aforementioned retardation film can be used as the support.
  • constituent material of the separator examples include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof. Although an appropriate thin leaf body etc. can be mentioned, a plastic film is used suitably from the point which is excellent in surface smoothness.
  • plastic film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene.
  • plastic film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene.
  • -Vinyl acetate copolymer film and the like.
  • the thickness of the separator is usually about 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
  • An antistatic treatment such as a mold can also be performed.
  • the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the separator.
  • the adhesive layer is formed on a release-treated sheet (separator)
  • the adhesive layer is transferred onto a retardation film to form the optical film with an adhesive layer of the present invention.
  • the release-treated sheet used in the production of the optical film with the pressure-sensitive adhesive layer can be used as it is as a separator for the optical film with the rubber-based pressure-sensitive adhesive layer, and the process can be simplified.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited and can be appropriately set depending on the application, but is preferably 250 ⁇ m or less, more preferably 100 ⁇ m or less, and 55 ⁇ m or less. More preferably.
  • the lower limit of the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 ⁇ m or more and more preferably 5 ⁇ m or more from the viewpoint of durability.
  • the gel fraction of the pressure-sensitive adhesive layer used in the present invention is not particularly limited, but is preferably about 10 to 98%, more preferably about 25 to 98%, and further preferably about 45 to 90%. It is preferable for the gel fraction to be in the above range since both durability and adhesive strength can be achieved.
  • the measuring method of a gel fraction can be measured by the method as described in an Example.
  • a retardation film functioning as a ⁇ / 4 plate constituting the optical film for an organic EL display device of the present invention and 40 ° C., 92% R.D. H.
  • the adhesive layer having a moisture permeability of 50 g / (m 2 ⁇ day) or less may be laminated so that they are in contact with each other, or may have another layer therebetween.
  • the other layers include an adhesive layer other than the adhesive layer and an adhesive layer (that is, an adhesive layer having a moisture permeability of 50 g / (m 2 ⁇ day) at 40 ° C. and 92% RH). And interstitial layers such as an undercoat layer (primer layer).
  • the adhesive layer is formed of an adhesive.
  • the type of the adhesive is not particularly limited, and various types can be used.
  • the adhesive layer is not particularly limited as long as it is optically transparent. Examples of the adhesive include water-based, solvent-based, hot-melt-based, active energy ray-curable types, and the like. Or an active energy ray hardening-type adhesive agent is suitable.
  • an easy adhesion layer can be provided between them.
  • the easy adhesion layer can be formed of, for example, various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone-based, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, and the like. These polymer resins can be used alone or in combination of two or more. Moreover, you may add another additive for formation of an easily bonding layer. Specifically, stabilizers such as a tackifier, an ultraviolet absorber, an antioxidant, and a heat stabilizer may be further used.
  • the optical film of the present invention is used for an organic EL display device, and constitutes an antireflection film for an organic EL display device (polarizing film for an organic EL display device) together with a polarizer described later. Can do.
  • Polarizing film for organic EL display device comprises a polarizer and the optical film for organic EL display device.
  • the structure will not be specifically limited if the polarizing film for organic EL display devices of this invention contains a polarizer and the said optical film for organic EL display devices,
  • the said polarizer, retardation film 3a, A configuration including the adhesive layer 2 in this order and a configuration including the polarizer, the adhesive layer 2 and the retardation film 3a in this order can be given.
  • the polarizer 5a can be used as a single-sided protective polarizing film having a protective film only on one side of the polarizer 5a, or a double-sided protective polarizing film having protective films on both sides of the polarizer 5a.
  • the protective film 5b / polarizer 5a / adhesive layer or pressure-sensitive adhesive layer 4 / retardation film 3a / adhesive agent It can be set as the polarizing film comprised from the layer 2.
  • FIG. 3 (b) when using as the double-sided protective polarizing film 5B containing the polarizer 5a, as shown in FIG.3 (b), as shown in FIG.3 (b), protective film 5b / polarizer 5a / protective film 5b / adhesive layer or adhesive layer 4 / phase difference It can be set as the polarizing film comprised from the film 3a / adhesive layer 2.
  • the angle formed between the absorption axis of the polarizer 5a and the slow axis of the retardation film 3a is preferably 35 ° to 55 °, and preferably 38 ° to 52 °. Is more preferable, 40 ° to 50 ° is more preferable, 42 ° to 48 ° is further preferable, and 44 ° to 46 ° is particularly preferable. If the said angle is such a range, since a desired circular polarization function can be implement
  • each said structure is protective film 5b / polarizer 5a / adhesive layer or adhesive layer 4 / retardation film 3a / adhesive layer or adhesive layer 4 / retardation film 3b / adhesive layer 2.
  • the angle between the absorption axis of the polarizer 5a and the slow axis of the first retardation film 3a is preferably 65 ° to 85 °, preferably 72 ° to 78 ° is more preferable, and 74 ° to 76 ° is even more preferable.
  • the angle formed by the absorption axis of the polarizer 5a and the slow axis of the second retardation film 3b is preferably 10 ° to 20 °, more preferably 13 ° to 17 °, and further preferably 14 ° to 16 °. preferable.
  • Arranging the two retardation films at the axial angles as described above is preferable because a circularly polarizing plate having very excellent circular polarization characteristics (as a result, very excellent antireflection characteristics) in a wide band can be obtained. .
  • optical film for organic EL display The above-mentioned thing can be mentioned for the optical film for organic EL display apparatuses.
  • the polarizer is not particularly limited, and various types can be used.
  • polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
  • hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
  • examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
  • a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable.
  • the thickness of these polarizers is not particularly limited, but is generally about 5 to 80 ⁇ m.
  • a polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
  • the polyvinyl alcohol film In addition to washing the polyvinyl alcohol film surface with stains and antiblocking agents by washing the polyvinyl alcohol film with water, the polyvinyl alcohol film is also swollen to prevent unevenness such as uneven coloring. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even in an aqueous solution of boric acid or potassium iodide or in a water bath.
  • a thin polarizer having a thickness of 15 ⁇ m or less it is preferable to use a thin polarizer having a thickness of 10 ⁇ m or less.
  • the thickness is preferably 1 to 7 ⁇ m.
  • Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.
  • the thin polarizer typically, Japanese Patent Application Laid-Open No. 51-069644, Japanese Patent Application Laid-Open No. 2000-338329, International Publication No. 2010/100917 pamphlet, Japanese Patent Application Laid-Open No. 2014-59328, and Japanese Patent Application Laid-Open No. 2014-59328 are disclosed.
  • the thin polarizing film described in 2012-73563 gazette can be mentioned.
  • These thin polarizing films can be obtained by a production method including a step of stretching and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin substrate in the state of a laminate. With this production method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.
  • PVA-based resin polyvinyl alcohol-based resin
  • a material for forming a protective film provided on one side or both sides of the polarizer a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable.
  • polyester polymers such as polyethylene terephthalate and polyethylene naphthalate
  • cellulose polymers such as diacetyl cellulose and triacetyl cellulose
  • acrylic polymers such as polymethyl methacrylate
  • styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin)
  • AS resin acrylonitrile / styrene copolymer
  • polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the protective film include blends of the polymer.
  • the protective film can also be formed as a cured layer of an acrylic, urethane, acrylic urethane, epoxy, silicone, or other thermosetting or ultraviolet curable resin.
  • a protective film made of the same polymer material may be used on the front and back, or a protective film made of a different polymer material or the like may be used.
  • the thickness of the protective film can be determined as appropriate, but is generally about 1 to 500 ⁇ m from the viewpoints of workability such as strength and handleability, and thin film properties.
  • the polarizer and the protective film are usually in close contact with each other through an aqueous adhesive or the like.
  • the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester.
  • examples of the adhesive between the polarizer and the protective film include an ultraviolet curable adhesive and an electron beam curable adhesive.
  • the electron beam curable polarizing film adhesive exhibits suitable adhesion to the various protective films.
  • the adhesive used in the present invention can contain a metal compound filler.
  • the surface of the protective film to which the polarizer is not adhered may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.
  • the adhesive layer or the pressure-sensitive adhesive layer 4 used for adhesion between the polarizing film 5 and the retardation film 3a, or adhesion between the retardation film 3a and the retardation film 3b is not particularly limited. Those described can be preferably used. Specifically, for adhesion between the retardation film 3a and the retardation film 3b, for example, an acrylic pressure-sensitive adhesive having a (meth) acrylic polymer as a base polymer is excellent in optical transparency and has an appropriate wettability. It is preferable because it exhibits cohesive and adhesive adhesive properties and is excellent in weather resistance, heat resistance, and the like. Examples of the adhesion between the polarizing film 5 and the retardation film 3a include the water-based adhesive used for the adhesion between the polarizer and the protective film. Specifically, a polyvinyl alcohol-based adhesive is preferable.
  • the polarizing film for an organic EL display device of the present invention may contain an intervening layer such as an adhesive layer, a pressure-sensitive adhesive layer, and an undercoat layer (primer layer) other than those described above, and an easily adhesive layer.
  • an intervening layer such as an adhesive layer, a pressure-sensitive adhesive layer, and an undercoat layer (primer layer) other than those described above, and an easily adhesive layer.
  • the intervening layer and the easy-adhesive layer may include those described above.
  • a functional layer can be provided in the polarizing film for organic EL display devices of the present invention. Providing the functional layer is preferable because generation of defects such as through cracks and nano slits generated in the polarizer can be suppressed.
  • the functional layer can be formed from various forming materials. The functional layer can be formed, for example, by applying a resin material to the polarizer.
  • the resin material forming the functional layer examples include polyester resins, polyether resins, polycarbonate resins, polyurethane resins, silicone resins, polyamide resins, polyimide resins, PVA resins, acrylic resins, and the like. Can be mentioned. These resin materials can be used alone or in combination of two or more, but among these, one or more selected from the group consisting of polyurethane-based resins and polyvinyl alcohol (PVA) -based resins are preferable, PVA resin is more preferable.
  • the form of the resin may be either water-based or solvent-based.
  • the resin is preferably a water-based resin, and is preferably a PVA-based resin.
  • As the water-based resin an acrylic resin aqueous solution or a urethane resin aqueous solution can be used.
  • the thickness of the functional layer is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, further preferably 8 ⁇ m or less, and 6 ⁇ m or less. Is more preferably 5 ⁇ m or less, and particularly preferably 3 ⁇ m or less.
  • the thickness of the functional layer is preferably 0.2 ⁇ m or more, more preferably 0.5 ⁇ m or more, and further preferably 0.7 ⁇ m or more. Since the generation of cracks can be suppressed by the functional layer having the thickness, it is preferable.
  • the total thickness of the polarizing film is preferably 3 to 115 ⁇ m, more preferably 43 to 60 ⁇ m, and more preferably 14 to 48 ⁇ m from the viewpoint of thinning. Further preferred.
  • the polarizing film for an organic EL display device of the present invention has excellent low moisture permeability because the optical film for an organic EL display device is used.
  • the adhesive layer 2 is disposed near the organic EL element, and the organic EL element It is possible to sufficiently suppress the transfer of moisture and the like.
  • Polarizing film with pressure-sensitive adhesive layer for organic EL display device The polarizing film with a pressure-sensitive adhesive layer of the present invention further comprises a pressure-sensitive adhesive layer on the polarizer side of the polarizing film for organic EL display device.
  • the polarizing film 8 with an adhesive layer for organic EL display devices of the present invention has an adhesive layer 7 on the polarizing film 5 side of the polarizing film 6 for organic EL display devices of the present invention, as shown in FIG. .
  • Examples of the polarizing film for organic EL display devices include those mentioned above.
  • the pressure-sensitive adhesive layer 7 is not particularly limited, and a known layer can be used. Moreover, the above-mentioned low moisture-permeable pressure-sensitive adhesive layer can also be used as the pressure-sensitive adhesive layer.
  • an adhesive layer specifically, for example, a (meth) acrylic polymer, a silicone-based polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine-based or rubber-based polymer is used as a base polymer.
  • acrylic pressure-sensitive adhesives based on (meth) acrylic polymers are excellent in optical transparency, exhibiting moderate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, weather resistance and heat resistance. Etc. are preferable.
  • the (meth) acrylic polymer is not particularly limited, and can be obtained by polymerizing a monomer component containing an alkyl (meth) acrylate having an alkyl group having 4 to 24 carbon atoms at the terminal of the ester group. Can be mentioned.
  • Alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.
  • alkyl (meth) acrylate examples include those having a linear or branched alkyl group having 4 to 24 carbon atoms, and having a linear or branched alkyl group having 4 to 9 carbon atoms.
  • Alkyl (meth) acrylates are preferred because they are easy to balance the adhesive properties. These alkyl (meth) acrylates can be used alone or in combination of two or more.
  • the monomer component forming the (meth) acrylic polymer can contain a copolymerizable monomer other than the alkyl (meth) acrylate as a monofunctional monomer component.
  • copolymerizable monomers include cyclic nitrogen-containing monomers, hydroxyl group-containing monomers, carboxyl group-containing monomers, and monomers having a cyclic ether group.
  • the monomer component forming the (meth) acrylic polymer can contain a polyfunctional monomer as necessary in order to adjust the cohesive force of the pressure-sensitive adhesive.
  • the polyfunctional monomer is a monomer having at least two polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, such as dipentaerythritol hexa (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate.
  • a polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.
  • the production of such a (meth) acrylic polymer can be appropriately selected from known production methods such as radiation polymerization such as solution polymerization and ultraviolet polymerization, various radical polymerizations such as bulk polymerization and emulsion polymerization. Further, the (meth) acrylic polymer obtained may be a random copolymer, a block copolymer, a graft copolymer or the like.
  • the polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited, and known ones commonly used in this field can be appropriately selected and used.
  • the weight average molecular weight of the (meth) acrylic polymer can be controlled by the amount of polymerization initiator, the amount of chain transfer agent used, and the reaction conditions, and the amount used is appropriately adjusted according to these types.
  • the weight average molecular weight of the (meth) acrylic polymer used in the present invention is preferably 400,000 to 4,000,000. By making the weight average molecular weight larger than 400,000, it is possible to satisfy the durability of the pressure-sensitive adhesive layer, or to suppress the occurrence of adhesive residue due to the reduced cohesive force of the pressure-sensitive adhesive layer. On the other hand, when the weight average molecular weight is larger than 4 million, the bonding property tends to be lowered. Furthermore, in the solution system, the viscosity becomes too high, and coating may be difficult.
  • the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene. In addition, it is difficult to measure the molecular weight of the (meth) acrylic polymer obtained by radiation polymerization.
  • the pressure-sensitive adhesive composition used in the present invention can contain a crosslinking agent.
  • crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyletherified melamine crosslinking agents, metal chelate crosslinking agents,
  • the crosslinking agent include oxides, and these can be used alone or in combination of two or more.
  • an isocyanate type crosslinking agent and an epoxy-type crosslinking agent are used preferably.
  • the crosslinking agent may be used alone or in combination of two or more, but the total content is based on 100 parts by weight of the (meth) acrylic polymer.
  • the crosslinking agent is preferably contained in the range of 0.01 to 10 parts by weight.
  • a (meth) acrylic oligomer can be contained in order to improve the adhesive force.
  • the pressure-sensitive adhesive composition used in the present invention may contain a silane coupling agent in order to increase the water resistance at the interface when applied to a hydrophilic adherend such as glass of the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive composition used in the present invention may contain other known additives, such as polyether compounds of polyalkylene glycols such as polypropylene glycol, powders of colorants and pigments, dyes, and the like. , Surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, UV absorbers, polymerization inhibitors, inorganic or organic fillers, It can be added as appropriate depending on the application in which metal powder, particles, foil, etc. are used. Moreover, you may employ
  • the formation method of the adhesive layer 7 can be performed by a well-known method.
  • Organic EL Display Device The organic EL display device of the present invention is characterized by having the polarizing plate for an organic EL display device or the polarizing plate with an adhesive layer.
  • the organic EL display device of the present invention includes the polarizing plate for an organic EL display device of the present invention or a polarizing plate with an adhesive layer, and is bonded to the organic EL element via the adhesive layer 2. Can do. About the other structure of the organic electroluminescence display of this invention, the thing similar to the conventional organic electroluminescence display can be mentioned.
  • the organic EL display device of the present invention includes the polarizing plate for an organic EL display device or the polarizing plate with an adhesive layer, the organic EL display device has high optical reliability.
  • Production Example 1 (Production of first retardation film) Isosorbide (ISB) 37.5 parts by mass, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BHEPF) 91.5 parts by mass, polyethylene glycol (PEG) 8.4 parts by mass with an average molecular weight of 400 , 105.7 parts by weight of diphenyl carbonate (DPC) and 0.594 parts by weight of cesium carbonate (0.2% by weight aqueous solution) as a catalyst were put in a reaction vessel, respectively, and the first stage of the reaction in a nitrogen atmosphere.
  • the temperature of the heat medium in the reaction vessel was set to 150 ° C., and the raw materials were dissolved while stirring as necessary (about 15 minutes).
  • the pressure in the reaction vessel was changed from normal pressure to 13.3 kPa, and the generated phenol was extracted out of the reaction vessel while raising the temperature of the heat medium in the reaction vessel to 190 ° C. over 1 hour.
  • the pressure in the reaction vessel is set to 6.67 kPa, and the heat medium temperature of the reaction vessel is increased to 230 ° C. in 15 minutes.
  • the generated phenol was extracted out of the reaction vessel. Since the stirring torque of the stirrer increased, the temperature was raised to 250 ° C. in 8 minutes, and the pressure in the reaction vessel was reduced to 0.200 kPa or less in order to remove the generated phenol.
  • a polycarbonate resin A containing a structural unit derived from a dihydroxy compound at a mol% ratio was obtained.
  • the obtained polycarbonate resin A had a glass transition temperature of 126 ° C. and a reduced viscosity of 0.372 dL / g.
  • the obtained polycarbonate resin A was vacuum dried at 80 ° C.
  • a polycarbonate resin film having a length of 3 m, a width of 300 mm, and a thickness of 120 ⁇ m was prepared using a film forming apparatus equipped with a setting temperature: 220 ° C., a chill roll (setting temperature: 120 to 130 ° C.) and a winder.
  • the water absorption of the obtained polycarbonate resin film was 1.2%.
  • the obtained polycarbonate resin film was cut into a length of 300 mm and a width of 300 mm, and longitudinally stretched at a temperature of 136 ° C. and a magnification of 2 times using a lab stretcher KARO IV (manufactured by Bruckner) to obtain a retardation film.
  • Re (550) of the obtained retardation film is 141 nm
  • Rth (550) is 141 nm (nx: 1.5969, ny: 1.5942, nz: 1.5942)
  • refractive index of nx> ny nz.
  • the characteristics are shown.
  • Re (450) / Re (550) of the obtained retardation film was 0.89 (further, the retardation fluctuation due to the environmental test was 5 nm).
  • Production Example 2 (Production of second retardation layer (second retardation film)) 20 parts by weight of a side chain type liquid crystal polymer represented by the following chemical formula (I) (numbers 65 and 35 in the formula indicate mol% of the monomer unit and are represented by a block polymer for convenience) 80 parts by weight of a polymerizable liquid crystal exhibiting a nematic liquid crystal phase (trade name: Paliocolor LC242, manufactured by BASF) and 5 parts by weight of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) are added to 200 parts by weight of cyclopentanone. A liquid crystal coating solution was prepared by dissolving in the part.
  • a side chain type liquid crystal polymer represented by the following chemical formula (I) (numbers 65 and 35 in the formula indicate mol% of the monomer unit and are represented by a block polymer for convenience) 80 parts by weight of a polymerizable liquid crystal exhibiting a nematic
  • the liquid crystal is dried by heating at 80 ° C. for 4 minutes. Oriented.
  • the liquid crystal layer was irradiated with ultraviolet rays to cure the liquid crystal layer, thereby forming a liquid crystal solidified layer (thickness: 0.58 ⁇ m) serving as the second retardation layer on the substrate.
  • Production Example 3 After bonding the second retardation layer (liquid crystal solidified layer) obtained in Production Example 2 to the first retardation film obtained in Production Example 1 via an acrylic pressure-sensitive adhesive, the substrate The film was removed to obtain a laminate (retardation film A) in which the liquid crystal solidified layer was transferred to the first retardation film.
  • the obtained retardation film A was composed of a first retardation film / acrylic pressure-sensitive adhesive layer / second retardation layer.
  • Re (550) of the obtained retardation film A was 141 nm, and Rth (550) was 70 nm.
  • Production Example 4 (Production of retardation film B) A long norbornene-based resin film (trade name: ZEONOR, thickness: 50 ⁇ m, manufactured by Nippon Zeon Co., Ltd.) is stretched 1.52 times, whereby Re (550) is a retardation film B (thickness: 140 nm). 35 ⁇ m) was obtained.
  • a first oxide layer (thickness: 30 nm) is formed on the first retardation film of the base material by a DC magnetron sputtering method using a sputtering target containing Al, SiO 2 and ZnO. ) was formed.
  • a second oxide layer (thickness: 50 nm) was formed on the first oxide layer of the base material / first oxide layer stack using a Si target.
  • Production Example 6 (Production of optical film laminate) A stretched laminate was produced by air-assisted stretching at a stretching temperature of 130 ° C. from a laminate in which a 9 ⁇ m-thick polyvinyl alcohol (PVA) layer was formed on an amorphous polyethylene terephthalate (PET) substrate. Next, a colored laminate is produced by dyeing the stretched laminate, and the colored laminate is further stretched in boric acid in water at a stretching temperature of 65 ° C. so that the total stretch ratio becomes 5.94 times. An optical film laminate comprising a 5 ⁇ m thick PVA layer stretched together was produced.
  • PVA polyvinyl alcohol
  • PET amorphous polyethylene terephthalate
  • the PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex.
  • an optical film laminate including a PVA layer having a thickness of 5 ⁇ m constituting a highly functional polarizing film (polarizer) was produced.
  • Production Example 7 (Production of rubber-based pressure-sensitive adhesive composition) 100 parts by weight of polyisobutylene (trade name: OPPANOL B80, Mw: about 750,000, manufactured by BASF) and tricyclodecane dimethanol diacrylate (trade name: NK ester A-DCP, 2) as a polyfunctional radical polymerizable compound Functional acrylate, molecular weight: 304, 5 parts by weight, Shin-Nakamura Chemical Co., Ltd.), 0.5 parts of benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.), a hydrogen abstraction photopolymerization initiator, fully hydrogenated terpene phenol A toluene solution (adhesive solution) containing 10 parts by weight was adjusted to a solid content of 15% by weight to prepare a rubber-based adhesive composition (solution).
  • polyisobutylene trade name: OPPANOL B80, Mw: about 750,000, manufactured by BASF
  • NK ester A-DCP tricyclodecane dim
  • Production Example 8 (Production of rubber-based pressure-sensitive adhesive composition) 100 parts by weight of polyisobutylene (trade name: OPPANOL B80, Mw: about 750,000, manufactured by BASF) and tricyclodecane dimethanol diacrylate (trade name: NK ester A-DCP, 2) as a polyfunctional radical polymerizable compound Functional acrylate, molecular weight: 304, manufactured by Shin-Nakamura Chemical Co., Ltd.) 10 parts by weight, benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.) 0.5 parts hydrogenated photopolymerization initiator, fully hydrogenated terpene phenol A toluene solution (adhesive solution) containing 10 parts by weight was adjusted to a solid content of 15% by weight to prepare a rubber-based adhesive composition (solution).
  • polyisobutylene trade name: OPPANOL B80, Mw: about 750,000, manufactured by BASF
  • NK ester A-DCP tricyclodecane dimethanol
  • Production Example 9 (Preparation of acrylic pressure-sensitive adhesive composition)
  • a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube 99 parts by weight of butyl acrylate (BA), 1 part by weight of 4-hydroxybutyl acrylate (4HBA) as a monomer component, and a polymerization initiator
  • BA butyl acrylate
  • 4HBA 4-hydroxybutyl acrylate
  • a polymerization initiator After 0.2 parts by weight of azobisisobutyronitrile and ethyl acetate as a polymerization solvent were added so as to have a solid content of 20%, nitrogen substitution was performed for about 1 hour while flowing nitrogen gas and stirring. Thereafter, the flask was heated to 60 ° C.
  • an acrylic polymer having a weight average molecular weight (Mw) of 1.1 million.
  • solid content 100 parts by weight
  • 0.8 parts by weight of trimethylolpropane tolylene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) as an isocyanate-based crosslinking agent
  • silane coupling agent An acrylic pressure-sensitive adhesive composition was prepared by adding 0.1 parts by weight (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the obtained acrylic pressure-sensitive adhesive composition was applied to the release-treated surface of a 38 ⁇ m-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone. Formed. Next, the coating layer was dried at 120 ° C. for 3 minutes to form a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet having a thickness of 50 ⁇ m was prepared. Also, the adhesive surface of the pressure-sensitive adhesive sheet is a 38 ⁇ m thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone, and the peel-treated surface and the pressure-sensitive adhesive layer are in contact with each other. Thus, an acrylic pressure-sensitive adhesive sheet was obtained.
  • the polyester film coated on both sides of the pressure-sensitive adhesive layer functions as a release liner (separator).
  • Example 1 (Preparation of adhesive sheet)
  • the rubber-based pressure-sensitive adhesive composition (solution) obtained in Production Example 7 was applied to the release-treated surface of a 38 ⁇ m-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) whose one side was peel-treated with silicone.
  • the coating layer was formed by coating. Subsequently, the coating layer was dried at 80 ° C. for 3 minutes to form a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet having a thickness of 50 ⁇ m was prepared.
  • the adhesive surface of the pressure-sensitive adhesive sheet is a 38 ⁇ m thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone, and the peel-treated surface and the pressure-sensitive adhesive layer are in contact with each other. Were pasted together.
  • the polyester film coated on both sides of the pressure-sensitive adhesive layer functions as a release liner (separator).
  • One separator was peeled off, and ultraviolet rays were irradiated at room temperature from the side where the separator was peeled off to obtain a pressure-sensitive adhesive sheet comprising a rubber-based pressure-sensitive adhesive layer / separator.
  • the UV irradiation was a light amount of 1000 mJ / cm 2 .
  • an amorphous PET substrate A piece protective polarizing film using a thin polarizer was prepared, and the retardation film A of the laminate was placed on the polarizing film side of the obtained piece protective polarizing film via a polyvinyl alcohol-based adhesive.
  • the retardation film A was laminated so that the slow axis of the retardation film A was 45 ° counterclockwise with respect to the absorption axis of the polarizer. It had a structure consisting of adhesive layer / polarizer / adhesive layer / retardation film A / rubber-based pressure-sensitive adhesive layer / separator.
  • Example 2 (Preparation of retardation film with adhesive layer) A laminate comprising retardation film B / rubber-based adhesive layer / separator was obtained in the same manner as in Example 1 except that the retardation film B obtained in Production Example 4 was used as the retardation film.
  • a polarizing film was produced in the same manner as in Example 1 except that the obtained laminate was used.
  • the obtained polarizing film had a structure consisting of TAC film / adhesive layer / polarizer / adhesive layer / retardation film B / rubber pressure-sensitive adhesive layer / separator.
  • Comparative Example 1 (Preparation of retardation film with adhesive layer) Laminated film composed of retardation film A / acrylic pressure-sensitive adhesive layer / separator in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive layer obtained in Production Example 9 was used instead of the rubber-based pressure-sensitive adhesive layer. Got the body.
  • a polarizing film was produced in the same manner as in Example 1 except that the obtained laminate was used.
  • the obtained polarizing film had a structure consisting of TAC film / adhesive layer / polarizer / adhesive layer / retardation film A / acrylic pressure-sensitive adhesive layer / separator.
  • ⁇ Durability> The separator of the polarizing film with a pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off, the test piece was bonded to a glass plate, and the state after being put in an environment of 85 ° C. for 300 hours was visually or magnified (20 times). ). Evaluation was performed according to the following evaluation criteria. A: Even when confirmed with a loupe, no defects (foaming, peeling, etc.) occurred. ⁇ : Although no defects could be confirmed by visual observation, some defects occurred to the extent that they were not problematic for use when confirmed with a magnifying glass. X: Defects could be confirmed visually.
  • the polarizing films obtained in the examples and comparative examples were cut into dimensions of 50 mm ⁇ 50 mm.
  • the organic EL panel is taken out from the organic EL display (product name: 15EL9500, manufactured by LG), the polarizing film attached to the organic EL panel is peeled off, and the cut out polarizing film is pasted in place to attach the organic EL panel. Obtained.
  • the measurement results of the reflection hue of this organic EL panel are shown in the table.
  • the “viewing angle characteristic” is the distance between two points of the reflected hue in the front direction and the reflected hue in the oblique direction (maximum value or minimum value at 45 ° polar angle) on the xy chromaticity diagram of the CIE color system.
  • ⁇ xy is shown.
  • a black image was displayed on the obtained organic EL panel, and the reflection hue was measured using a viewing angle measurement evaluation apparatus conoscope manufactured by Auoronic-MERCHERS.

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Abstract

The present invention is an optical film for organic EL display devices, which is characterized by comprising: a retardation film that functions as a λ/4 plate; and an adhesive layer that has a water vapor permeability of 50 g/(m2·day) or less at 40°C at 92% RH. This optical film for organic EL display devices according to the present invention has more excellently low water vapor permeability without forming a barrier layer which is composed of an inorganic material and is formed by vapor deposition or the like.

Description

有機ＥＬ表示装置用光学フィルム、有機ＥＬ表示装置用偏光フィルム、有機ＥＬ表示装置用粘着剤層付き偏光フィルム、及び有機ＥＬ表示装置Optical film for organic EL display device, polarizing film for organic EL display device, polarizing film with adhesive layer for organic EL display device, and organic EL display device
　本発明は、有機ＥＬ表示装置用光学フィルムに関する。また、本発明は、偏光子と前記有機ＥＬ表示装置用光学フィルムを含む有機ＥＬ表示装置用偏光フィルム、前記有機ＥＬ表示装置用偏光フィルムにさらに粘着剤層を設けた有機ＥＬ表示装置用粘着剤層付き偏光フィルムに関する。また、本発明は、前記有機ＥＬ表示装置用偏光フィルム又は有機ＥＬ表示装置用粘着剤層付き偏光フィルムを用いた有機ＥＬ表示装置に関する。 The present invention relates to an optical film for an organic EL display device. In addition, the present invention provides a polarizing film for an organic EL display device including a polarizer and the optical film for an organic EL display device, and an adhesive for an organic EL display device in which an adhesive layer is further provided on the polarizing film for the organic EL display device. The present invention relates to a polarizing film with a layer. The present invention also relates to an organic EL display device using the polarizing film for an organic EL display device or the polarizing film with an adhesive layer for an organic EL display device.
　近年、有機ＥＬ（Ｅｌｅｃｔｒｏ　Ｌｕｍｉｎｅｓｃｅｎｃｅ）パネルを搭載した有機ＥＬ表示装置（ＯＬＥＤ）が、携帯電話、カーナビゲーション装置、パソコン用モニタ、テレビ等の各種用途において広く用いられるようになってきた。有機ＥＬ表示装置は、通常、外光が金属電極（陰極）で反射されて鏡面のように視認されることを抑止するために、有機ＥＬパネルの視認側表面に円偏光板が配置される。前記円偏光板等の有機ＥＬ表示装置の構成部材は、通常、粘着剤層や接着剤層等の接合材料を介して積層される。 In recent years, organic EL display devices (OLEDs) equipped with organic EL (Electro Luminescence) panels have been widely used in various applications such as mobile phones, car navigation devices, personal computer monitors, and televisions. In an organic EL display device, a circularly polarizing plate is usually disposed on the viewing side surface of the organic EL panel in order to prevent external light from being reflected by a metal electrode (cathode) and viewed as a mirror surface. The constituent members of the organic EL display device such as the circularly polarizing plate are usually laminated via a bonding material such as a pressure-sensitive adhesive layer or an adhesive layer.
　前記円偏光板としては、一般的には偏光板とλ／４板の積層体が用いられているが、例えば、偏光子と、特定の屈折率特性を有する２枚の位相差層を積層したものも知られている（例えば、特許文献１参照）。 As the circularly polarizing plate, a laminate of a polarizing plate and a λ / 4 plate is generally used. For example, a polarizer and two retardation layers having specific refractive index characteristics are stacked. The thing is also known (for example, refer patent document 1).
　前記有機ＥＬ表示装置に搭載された有機ＥＬ素子は、大気中の水分や酸素に非常に弱いため、通常、有機ＥＬパネル表面にはバリア層やバリア機能を持つ光学用フィルムが設けられており、また、有機ＥＬ表示装置を構成する光学フィルムやこれらを貼り合せるための粘着剤層等にも水分等を透過させないこと（低透湿性）が求められている。 Since the organic EL element mounted on the organic EL display device is very weak to moisture and oxygen in the atmosphere, an optical film having a barrier layer and a barrier function is usually provided on the surface of the organic EL panel, In addition, it is required that the optical film constituting the organic EL display device and the pressure-sensitive adhesive layer for bonding these films do not transmit moisture or the like (low moisture permeability).
　特に、近年、曲げられる表示装置として、フレキシブル有機ＥＬ表示装置が注目されている。フレキシブル有機ＥＬ表示装置においては、最外層がガラスではなく、フィルムが用いられる。しかしながら、前述の通り、有機ＥＬ素子は、大気中の水分や酸素に非常に弱く、最外層が低透湿特性に優れるガラスからフィルムに変更されると、有機ＥＬ素子がダメージを受けることが懸念され、フレキシブル有機ＥＬ表示装置に用いる光学フィルムや粘着剤層において、さらに高い低透湿性が要求されている。 In particular, in recent years, flexible organic EL display devices have attracted attention as display devices that can be bent. In the flexible organic EL display device, the outermost layer is not glass but a film is used. However, as described above, the organic EL element is very vulnerable to moisture and oxygen in the atmosphere, and there is a concern that the organic EL element may be damaged when the outermost layer is changed from a glass excellent in low moisture permeability to a film. In addition, in an optical film and an adhesive layer used in a flexible organic EL display device, higher moisture permeability is required.
特許第５５２８６０６号公報Japanese Patent No. 5528606
　特許文献１では、視野角特性と表示特性の変化を抑制する位相差層付偏光板を提供するものであり、位相差フィルム等の光学フィルムに低透湿性を付与することについては何ら検討されていないものであった。 In Patent Document 1, a polarizing plate with a retardation layer that suppresses changes in viewing angle characteristics and display characteristics is provided, and no consideration is given to imparting low moisture permeability to an optical film such as a retardation film. It was not.
　光学フィルムに低透湿性を付与する方法としては、例えば、有機ＥＬ表示装置に使用されている円偏光板（反射防止フィルム）を構成する位相差フィルム（λ／４板）にバリア層の蒸着をすることが考えられる。しかしながら、位相差フィルムにバリア層を蒸着する方法では、コストの点で十分ではなく、さらに、バリア層を位相差フィルムに蒸着する際に位相差フィルムに熱がかかり、位相差フィルムが破断したり、位相差値が変化したりする場合があり、十分ではなかった。 As a method for imparting low moisture permeability to an optical film, for example, a barrier layer is deposited on a retardation film (λ / 4 plate) constituting a circularly polarizing plate (antireflection film) used in an organic EL display device. It is possible to do. However, the method of depositing the barrier layer on the retardation film is not sufficient in terms of cost. Further, when the barrier layer is deposited on the retardation film, the retardation film is heated and the retardation film is broken. The phase difference value may change, which is not sufficient.
　そこで、本発明は、蒸着等により形成する無機物からなるバリア層を形成することなく、より優れた低透湿性を有する有機ＥＬ表示装置用光学フィルムを提供することを目的とする。また、本発明は、偏光子と、前記有機ＥＬ表示装置用光学フィルムを含む、有機ＥＬ表示装置用偏光フィルムや、前記有機ＥＬ表示装置用偏光フィルムと粘着剤層を有する有機ＥＬ表示装置用粘着剤層付き偏光フィルムを提供することも目的とする。さらに、本発明は、前記有機ＥＬ表示装置用偏光フィルム、又は有機ＥＬ表示装置用粘着剤層付き偏光フィルムを用いた有機ＥＬ表示装置を提供することも目的とする。 Therefore, an object of the present invention is to provide an optical film for an organic EL display device having a more excellent low moisture permeability without forming a barrier layer made of an inorganic material formed by vapor deposition or the like. In addition, the present invention provides a polarizing film for an organic EL display device including a polarizer and the optical film for an organic EL display device, and an adhesive for an organic EL display device having the polarizing film for an organic EL display device and an adhesive layer. Another object is to provide a polarizing film with an agent layer. Another object of the present invention is to provide an organic EL display device using the polarizing film for an organic EL display device or the polarizing film with an adhesive layer for an organic EL display device.
　本発明者らは前記課題を解決すべく鋭意検討を重ねた結果、下記有機ＥＬ表示装置用光学フィルムを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found the following optical film for an organic EL display device and have completed the present invention.
　すなわち、本発明は、λ／４板として機能する位相差フィルムと、４０℃、９２％Ｒ．Ｈ．における透湿度が５０ｇ／（ｍ２・ｄａｙ）以下の粘接着剤層とを備えることを特徴とする有機ＥＬ表示装置用光学フィルムに関する。 That is, the present invention relates to a retardation film functioning as a λ / 4 plate, a 40 ° C., 92% R.D. H. And an adhesive layer having a moisture permeability of 50 g / (m 2 · day) or less.
　前記粘接着剤層が、ポリイソブチレン、及び水素引抜型光重合開始剤を含むゴム系粘着剤組成物から形成された粘着剤層であることが好ましい。 The adhesive layer is preferably a pressure-sensitive adhesive layer formed from a rubber-based pressure-sensitive adhesive composition containing polyisobutylene and a hydrogen abstraction type photopolymerization initiator.
　また、本発明は、偏光子と、前記有機ＥＬ表示装置用光学フィルムを含むことを特徴とする有機ＥＬ表示装置用偏光フィルムに関する。 The present invention also relates to a polarizing film for an organic EL display device comprising a polarizer and the optical film for an organic EL display device.
　前記偏光子の厚みが、１５μｍ以下であることが好ましい。 The thickness of the polarizer is preferably 15 μm or less.
　本発明の有機ＥＬ表示装置用偏光フィルムにおいて、前記偏光子と、λ／４板として機能する位相差フィルムと、４０℃、９２％Ｒ．Ｈ．における透湿度が５０ｇ／（ｍ２・ｄａｙ）以下の粘接着剤層とをこの順に備えていてもよく、前記偏光子と、４０℃、９２％Ｒ．Ｈ．における透湿度が５０ｇ／（ｍ２・ｄａｙ）以下の粘接着剤層と、λ／４板として機能する位相差フィルムとをこの順に備えていてもよい。 In the polarizing film for an organic EL display device of the present invention, the polarizer, a retardation film functioning as a λ / 4 plate, 40 ° C., 92% R.D. H. And a pressure-sensitive adhesive layer having a moisture permeability of 50 g / (m 2 · day) or less in this order, and the polarizer and 40 ° C., 92% R.D. H. May be provided with an adhesive layer having a moisture permeability of 50 g / (m 2 · day) or less and a retardation film functioning as a λ / 4 plate in this order.
　また、本発明は、前記有機ＥＬ表示装置用偏光フィルムの偏光子側に、さらに粘着剤層を有することを特徴とする有機ＥＬ表示装置用粘着剤層付き偏光フィルムに関する。 The present invention also relates to a polarizing film with an adhesive layer for an organic EL display device, further comprising an adhesive layer on the polarizer side of the polarizing film for an organic EL display device.
　さらに、本発明は、前記有機ＥＬ表示装置用偏光フィルム、又は前記有機ＥＬ表示装置用粘着剤層付き偏光フィルムを有することを特徴とする有機ＥＬ表示装置に関する。 Furthermore, the present invention relates to an organic EL display device comprising the polarizing film for an organic EL display device or the polarizing film with an adhesive layer for the organic EL display device.
　本発明の有機ＥＬ表示装置用光学フィルムは、位相差フィルムと、特定の透湿度を有する粘接着剤層を有することで、蒸着等により形成する無機物からなるバリア層を形成することなく、優れた低透湿性を発現することができる。本発明の有機ＥＬ表示装置用光学フィルムは、偏光子と伴に、有機ＥＬ表示装置の反射防止フィルム（有機ＥＬ表示装置用偏光フィルム）を構成することができる。また、本発明の有機ＥＬ表示装置用光学フィルムは、コストの面でも有利である。 The optical film for an organic EL display device of the present invention has a retardation film and an adhesive layer having a specific moisture permeability, and is excellent without forming a barrier layer made of an inorganic material by vapor deposition or the like. Moreover, low moisture permeability can be expressed. The optical film for organic EL display devices of the present invention can constitute an antireflection film for organic EL display devices (polarizing film for organic EL display devices) together with a polarizer. Moreover, the optical film for organic EL display devices of the present invention is advantageous in terms of cost.
　また、本発明は、優れた低透湿性を有する有機ＥＬ表示装置用偏光フィルムや、有機ＥＬ表示装置用粘着剤層付き偏光フィルムを提供することができる。 Moreover, this invention can provide the polarizing film for organic EL display apparatuses which has the outstanding low moisture permeability, and the polarizing film with an adhesive layer for organic EL display apparatuses.
　さらに、本発明は、前記有機ＥＬ表示装置用偏光フィルム又はさらに粘着剤層を含む有機ＥＬ表示装置用粘着剤層付き偏光フィルムを用いることで、光学信頼に優れた有機ＥＬ表示装置を提供することができる。 Furthermore, the present invention provides an organic EL display device excellent in optical reliability by using the polarizing film for organic EL display devices or the polarizing film with an adhesive layer for organic EL display devices further comprising an adhesive layer. Can do.
本発明の有機ＥＬ表示装置用光学フィルムの一実施形態を模式的に示す断面図である。It is sectional drawing which shows typically one Embodiment of the optical film for organic EL display apparatuses of this invention. 本発明の有機ＥＬ表示装置用光学フィルムの一実施形態を模式的に示す断面図である。It is sectional drawing which shows typically one Embodiment of the optical film for organic EL display apparatuses of this invention. （ａ）本発明の有機ＥＬ表示装置用偏光フィルムの一実施形態を模式的に示す断面図である。（ｂ）本発明の有機ＥＬ表示装置用偏光フィルムの一実施形態を模式的に示す断面図である。(A) It is sectional drawing which shows typically one Embodiment of the polarizing film for organic EL display apparatuses of this invention. (B) It is sectional drawing which shows typically one Embodiment of the polarizing film for organic EL display apparatuses of this invention. 本発明の有機ＥＬ表示装置用粘着剤層付き偏光フィルムの一実施形態を模式的に示す断面図である。It is sectional drawing which shows typically one Embodiment of the polarizing film with an adhesive layer for organic EL display apparatuses of this invention.
　１．有機ＥＬ表示装置用光学フィルム
　本発明の有機ＥＬ表示装置用光学フィルムは、λ／４板として機能する位相差フィルムと、４０℃、９２％Ｒ．Ｈ．における透湿度が５０ｇ／（ｍ２・ｄａｙ）以下の粘接着剤層とを備えることを特徴とする。 1. Optical film for organic EL display device The optical film for organic EL display device of the present invention comprises a retardation film functioning as a λ / 4 plate, 40 ° C., 92% R.D. H. And a pressure-sensitive adhesive layer having a moisture permeability of 50 g / (m 2 · day) or less.
　図１に示すように、本発明の有機ＥＬ表示装置用光学フィルム１は、λ／４板として機能する位相差フィルム３ａの少なくとも片面に、粘接着剤層２を有するものである。図１では、位相差フィルム３ａの片面にのみ粘接着剤層２を有する形態を開示しているが、位相差フィルム３ａの両面に粘接着剤層２を有していてもよい。なお、図１では、各構成要素が接するように積層されている態様を記載しているが、本発明はこのような態様に限定されるものではなく、前記各層の間に他の層を含んでいてもよい。図２～４においても同様である。 As shown in FIG. 1, the optical film 1 for an organic EL display device of the present invention has an adhesive layer 2 on at least one surface of a retardation film 3a that functions as a λ / 4 plate. In FIG. 1, although the form which has the adhesive layer 2 only on the single side | surface of the phase difference film 3a is disclosed, you may have the adhesive layer 2 on both surfaces of the phase difference film 3a. In addition, although the aspect laminated | stacked so that each component may contact | connect is described in FIG. 1, this invention is not limited to such an aspect, and another layer is included between each said layer. You may go out. The same applies to FIGS.
　また、図２に示すように、本発明の有機ＥＬ表示装置用光学フィルム１は、λ／４板として機能する位相差フィルム３ａ（第１の位相差フィルムということもある）の他に、第２の位相差フィルム３ｂを含んでいてもよい。具体的には、（λ／４板として機能する位相差フィルム３ａ）／接着剤層又は粘着剤層４／第２の位相差フィルム３ｂ／粘接着剤層２から構成される。 As shown in FIG. 2, the optical film 1 for an organic EL display device of the present invention includes a retardation film 3a (also referred to as a first retardation film) that functions as a λ / 4 plate. 2 retardation films 3b may be included. Specifically, it is composed of (retardation film 3 a functioning as a λ / 4 plate) / adhesive layer or pressure-sensitive adhesive layer 4 / second retardation film 3 b / adhesive layer 2.
　前記有機ＥＬ表示装置用光学フィルムの透湿度は、５０ｇ／（ｍ２・ｄａｙ）以下であることが好ましく、３０ｇ／（ｍ２・ｄａｙ）以下がより好ましく、２０ｇ／（ｍ２・ｄａｙ）以下がさらに好ましく、１５ｇ／（ｍ２・ｄａｙ）以下が特に好ましい。また、透湿度の下限値は特に限定されるものではないが、理想的には、水蒸気を全く透過させないこと（すなわち、０ｇ／（ｍ２・ｄａｙ））が好ましい。有機ＥＬ表示装置用光学フィルムの透湿度が前記範囲であれば、当該有機ＥＬ表示装置用光学フィルムを有機ＥＬ素子に適用した際に、当該有機ＥＬ素子に水分が移行することを抑制することができ、その結果、有機ＥＬ素子の水分による劣化等を抑制することができるため好ましい。前記透湿度の測定方法は実施例に記載の方法により測定することができる。 The moisture permeability of the optical film for organic EL display devices is preferably 50 g / (m 2 · day) or less, more preferably 30 g / (m 2 · day) or less, and 20 g / (m 2 · day) or less. Is more preferable, and 15 g / (m 2 · day) or less is particularly preferable. Further, the lower limit value of moisture permeability is not particularly limited, but ideally, it is preferable that water vapor is not permeated at all (that is, 0 g / (m 2 · day)). If the water vapor transmission rate of the optical film for organic EL display devices is within the above range, when the optical film for organic EL display devices is applied to an organic EL element, it is possible to prevent moisture from being transferred to the organic EL element. As a result, it is preferable because deterioration due to moisture of the organic EL element can be suppressed. The measuring method of the moisture permeability can be measured by the method described in the examples.
　以下、本発明の有機ＥＬ表示装置用光学フィルム１を構成する各構成要素について説明する。 Hereinafter, each component constituting the optical film 1 for an organic EL display device of the present invention will be described.
　（１）位相差フィルム
　（１－１）λ／４板として機能する位相差フィルム
　本発明で使用する位相差フィルム３ａは、λ／４板として機能し得るフィルムである。このような位相差フィルム３ａの２３℃における波長５５０ｎｍの光で測定した面内位相差Ｒｅ（５５０）は、１００～１８０ｎｍであることが好ましく、１１０～１７０ｎｍであることがより好ましく、１２０～１６０ｎｍであることがさらに好ましく、１３５～１５５ｎｍであることが特に好ましい。面内位相差Ｒｅは、Ｒｅ＝（ｎｘ－ｎｙ）×ｄ（ｄ：フィルムの厚み（ｎｍ））によって求められる。 (1) Retardation film (1-1) Retardation film functioning as a λ / 4 plate The retardation film 3a used in the present invention is a film that can function as a λ / 4 plate. The in-plane retardation Re (550) of such retardation film 3a measured with light having a wavelength of 550 nm at 23 ° C. is preferably 100 to 180 nm, more preferably 110 to 170 nm, and more preferably 120 to 160 nm. More preferably, the thickness is 135 to 155 nm. The in-plane retardation Re is obtained by Re = (nx−ny) × d (d: film thickness (nm)).
　また、位相差フィルム３ａは、代表的には、ｎｘ＞ｎｙ＝ｎｚ、又は、ｎｘ＞ｎｙ＞ｎｚの屈折率楕円体を有する。ここで、ｎｘは面内の屈折率が最大となる方向（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。また、本明細書において、ｎｙ＝ｎｚは厳密に等しい場合のみならず、実質的に等しいものを含む。 The retardation film 3a typically has a refractive index ellipsoid of nx> ny = nz or nx> ny> nz. Here, nx is the refractive index in the direction in which the in-plane refractive index is maximum (that is, the slow axis direction), and ny is in the direction orthogonal to the slow axis in the plane (that is, the fast axis direction). It is a refractive index, and nz is a refractive index in the thickness direction. Further, in the present specification, ny = nz includes not only strictly equal but also substantially equal.
　位相差フィルム３ａのＮｚ係数は、例えば、０．９～２であることが好ましく、１～１．５がより好ましく、１～１．３がさらに好ましい。ここで、Ｎｚ係数は、Ｎｚ＝Ｒｔｈ／Ｒｅによって求められる。前記、Ｒｔｈは、厚み方向の位相差であり、Ｒｔｈ＝（ｎｘ－ｎｚ）×ｄ（ｄ：フィルムの厚み（ｎｍ））によって求められる。 The Nz coefficient of the retardation film 3a is, for example, preferably 0.9 to 2, more preferably 1 to 1.5, and still more preferably 1 to 1.3. Here, the Nz coefficient is obtained by Nz = Rth / Re. The Rth is a retardation in the thickness direction, and is obtained by Rth = (nx−nz) × d (d: film thickness (nm)).
　前記位相差フィルム３ａの厚みは、所望の面内位相差が得られるように適宜設定することができるものであり、特に限定されるものではないが、例えば、１０～８０μｍであることが好ましく、１０～６０μｍであることがより好ましく、３０～５５μｍであることがさらに好ましい。 The thickness of the retardation film 3a can be appropriately set so as to obtain a desired in-plane retardation, and is not particularly limited, but is preferably 10 to 80 μm, for example. It is more preferably 10 to 60 μm, and further preferably 30 to 55 μm.
　位相差フィルム３ａは、位相差値が測定光の波長に応じて大きくなる逆分散波長特性を示していてもよく、位相差値が測定光の波長に応じて小さくなる正の波長分散特性を示してもよく、位相差値が測定光の波長によってもほとんど変化しないフラットな波長分散特性を示していてもよいが、フラットな波長分散特性を示すことが好ましい。フラットな波長分散特性を有するλ／４板を採用することにより、優れた反射防止特性、及び斜め方向の反射色相を実現することができる。位相差フィルム３ａのＲｅ（４５０）／Ｒｅ（５５０）は、０．８５～１．０３であることが好ましく、Ｒｅ（６５０）／Ｒｅ（５５０）は０．９８～１．０２であることが好ましい。ここで、Ｒｅ（λ）は、２３℃における波長λｎｍの光で測定した面内位相差であり、例えば、Ｒｅ（４５０）は、２３℃における波長４５０ｎｍの光で測定した面内位相差を示す。 The retardation film 3a may exhibit reverse dispersion wavelength characteristics in which the retardation value increases in accordance with the wavelength of the measurement light, and exhibits positive chromatic dispersion characteristics in which the retardation value decreases in accordance with the wavelength of the measurement light. Alternatively, the phase difference value may exhibit a flat chromatic dispersion characteristic that hardly changes depending on the wavelength of the measurement light, but preferably exhibits a flat chromatic dispersion characteristic. By adopting a λ / 4 plate having flat wavelength dispersion characteristics, it is possible to realize excellent antireflection characteristics and oblique reflection hues. Re (450) / Re (550) of the retardation film 3a is preferably 0.85 to 1.03, and Re (650) / Re (550) is preferably 0.98 to 1.02. preferable. Here, Re (λ) is an in-plane phase difference measured with light having a wavelength λ nm at 23 ° C., for example, Re (450) represents an in-plane phase difference measured with light having a wavelength of 450 nm at 23 ° C. .
　前記位相差フィルム３ａは、上記のような光学的特性を満足し得る任意の適切な樹脂フィルムで構成することができる。上記樹脂フィルムを形成する樹脂としては、任意の適切な樹脂を用いることができ、具体的には、ポリノルボルネン等のシクロオレフィン系樹脂、ポリカーボネート系樹脂、セルロース系樹脂、ポリビニルアルコール系樹脂、ポリスルホン系樹脂等の樹脂が挙げられる。これらの中でも、ポリノルボルネン、ポリカーボネート系樹脂が好ましい。 The retardation film 3a can be composed of any appropriate resin film that can satisfy the optical characteristics as described above. Any appropriate resin can be used as the resin for forming the resin film, and specifically, cycloolefin resins such as polynorbornene, polycarbonate resins, cellulose resins, polyvinyl alcohol resins, polysulfone resins. Examples of the resin include resins. Among these, polynorbornene and polycarbonate resin are preferable.
　上記ポリノルボルネンとは、出発原料（モノマー）の一部又は全部に、ノルボルネン環を有するノルボルネン系モノマーを用いて得られる（共）重合体をいう。 The above polynorbornene means a (co) polymer obtained by using a norbornene-based monomer having a norbornene ring as a part or all of a starting material (monomer).
　上記ポリノルボルネンとしては、種々の製品が市販されている。具体例としては、日本ゼオン（株）製の商品名「ゼオネックス」、「ゼオノア」、ＪＳＲ（株）製の商品名「アートン（Ａｒｔｏｎ）」、ＴＩＣＯＮＡ社製の商品名「トーパス」、三井化学（株）製の商品名「ＡＰＥＬ」が挙げられる。 Various products are commercially available as the polynorbornene. As specific examples, trade names “ZEONEX” and “ZEONOR” manufactured by ZEON CORPORATION, trade names “ARTON” manufactured by JSR Corporation, “TOPASS” manufactured by TICONA, Mitsui Chemicals ( Trade name “APEL” manufactured by Co., Ltd. may be mentioned.
　前記ポリカーボネート系樹脂は、下記構造式（１）で表される結合構造を有するジヒドロキシ化合物に由来する構成単位を少なくとも含むものであり、分子内に少なくとも一つの結合構造「－ＣＨ２－Ｏ－」を有するジヒドロキシ化合物を少なくとも含むジヒドロキシ化合物と、炭酸ジエステルとを、重合触媒の存在下反応させることにより製造される。 The polycarbonate-based resin contains at least a structural unit derived from a dihydroxy compound having a bond structure represented by the following structural formula (1), and has at least one bond structure “—CH 2 —O—” in the molecule. It is produced by reacting a dihydroxy compound containing at least a dihydroxy compound having a carbonic acid diester in the presence of a polymerization catalyst.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　上記構造式（１）で表される結合構造を有するジヒドロキシ化合物としては、２個のアルコール性水酸基をもち、分子内に連結基「－ＣＨ２－Ｏ－」を有する構造を含み、重合触媒の存在下、炭酸ジエステルと反応してポリカーボネートを生成し得る化合物であればいかなる構造の化合物であっても使用することが可能であり、複数種併用しても構わない。また、上記ポリカーボネート系樹脂に用いるジヒドロキシ化合物として、構造式（１）で表される結合構造を有さないジヒドロキシ化合物を併用してもよい。以下、構造式（１）で表される結合構造を有するジヒドロキシ化合物をジヒドロキシ化合物（Ａ）、構造式（１）で表される結合構造を有さないジヒドロキシ化合物をジヒドロキシ化合物（Ｂ）と略記することがある。 The dihydroxy compound having a bond structure represented by the structural formula (1) includes a structure having two alcoholic hydroxyl groups and a linking group “—CH 2 —O—” in the molecule, Any compound having any structure can be used as long as it is a compound capable of reacting with a carbonic acid diester in the presence to form a polycarbonate, and a plurality of compounds may be used in combination. Moreover, you may use together the dihydroxy compound which does not have the coupling | bonding structure represented by Structural formula (1) as a dihydroxy compound used for the said polycarbonate-type resin. Hereinafter, a dihydroxy compound having a bond structure represented by Structural Formula (1) is abbreviated as dihydroxy compound (A), and a dihydroxy compound having no bond structure represented by Structural Formula (1) is abbreviated as dihydroxy compound (B). Sometimes.
　（ジヒドロキシ化合物（Ａ））
　ジヒドロキシ化合物（Ａ）における連結基「－ＣＨ２－Ｏ－」とは、水素原子以外の原子と互いに結合して分子を構成する構造を意味する。この連結基において、少なくとも酸素原子が結合し得る原子又は炭素原子と酸素原子が同時に結合し得る原子としては、炭素原子が最も好ましい。ジヒドロキシ化合物（Ａ）中の連結基「－ＣＨ２－Ｏ－」の数は１以上であり、好ましくは２～４である。 (Dihydroxy compound (A))
The linking group “—CH 2 —O—” in the dihydroxy compound (A) means a structure constituting a molecule by bonding to atoms other than hydrogen atoms. In this linking group, at least an atom to which an oxygen atom can be bonded or an atom to which a carbon atom and an oxygen atom can be bonded simultaneously is most preferably a carbon atom. The number of linking groups “—CH 2 —O—” in the dihydroxy compound (A) is 1 or more, preferably 2 to 4.
　さらに具体的には、ジヒドロキシ化合物（Ａ）としては、例えば、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－（２－ヒドロキシエトキシ－２－メチル）フェニル）フルオレン、９，９－ビス（４－（２－ヒドロキシエトキシ）－３－メチルフェニル）フルオレン、９，９－ビス（４－（２－ヒドロキシエトキシ）－３－イソプロピルフェニル）フルオレン、９，９－ビス（４－（２－ヒドロキシエトキシ）－３－イソブチルフェニル）フルオレン、９，９－ビス（４－（２－ヒドロキシエトキシ）－３－ｔｅｒｔ－ブチルフェニル）フルオレン、９，９－ビス（４－（２－ヒドロキシエトキシ）－３－シクロヘキシルフェニル）フルオレン、９，９－ビス（４－（２－ヒドロキシエトキシ）－３－フェニルフェニル）フルオレン、９，９－ビス（４－（２－ヒドロキシエトキシ）－３，５－ジメチルフェニル）フルオレン、９，９－ビス（４－（２－ヒドロキシエトキシ）－３－ｔｅｒｔ－ブチル－６－メチルフェニル）フルオレン、９，９－ビス（４－（３－ヒドロキシ－２，２－ジメチルプロポキシ）フェニル）フルオレン等の、側鎖に芳香族基を有し、主鎖に芳香族基に結合したエーテル基を有する化合物；ビス［４－（２－ヒドロキシエトキシ）フェニル］メタン、ビス［４－（２－ヒドロキシエトキシ）フェニル］ジフェニルメタン、１，１－ビス［４－（２－ヒドロキシエトキシ）フェニル］エタン、１，１－ビス［４－（２－ヒドロキシエトキシ）フェニル］－１－フェニルエタン、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－ヒドロキシエトキシ）－３－メチルフェニル］プロパン、２，２－ビス［３，５－ジメチル－４－（２－ヒドロキシエトキシ）フェニル］プロパン、１，１－ビス［４－（２－ヒドロキシエトキシ）フェニル］－３，３，５－トリメチルシクロヘキサン、１，１－ビス［４－（２－ヒドロキシエトキシ）フェニル］シクロヘキサン、１，４－ビス［４－（２－ヒドロキシエトキシ）フェニル］シクロヘキサン、１，３－ビス［４－（２－ヒドロキシエトキシ）フェニル］シクロヘキサン、２，２－ビス［４－（２－ヒドロキシエトキシ）－３－フェニルフェニル］プロパン、２，２－ビス［（２－ヒドロキシエトキシ）－３－イソプロピルフェニル］プロパン、２，２－ビス［３－ｔｅｒｔ－ブチル－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－ヒドロキシエトキシ）フェニル］ブタン、２，２－ビス［４－（２－ヒドロキシエトキシ）フェニル］－４－メチルペンタン、２，２－ビス［４－（２－ヒドロキシエトキシ）フェニル］オクタン、１，１－ビス［４－（２－ヒドロキシエトキシ）フェニル］デカン、２，２－ビス［３－ブロモ－４－（２－ヒドロキシエトキシ）フェニル］プロパン、２，２－ビス［３－シクロヘキシル－４－（２－ヒドロキシエトキシ）フェニル］プロパン等の、ビス（ヒドロキシアルコキシアリール）アルカン類；１，１－ビス［４－（２－ヒドロキシエトキシ）フェニル］シクロヘキサン、１，１－ビス［３－シクロヘキシル－４－（２－ヒドロキシエトキシ）フェニル］シクロヘキサン、１，１－ビス［４－（２－ヒドロキシエトキシ）フェニル］シクロペンタン等の、ビス（ヒドロキシアルコキシアリール）シクロアルカン類；４，４’－ビス（２－ヒドロキシエトキシ）ジフェニルエ－テル、４，４’－ビス（２－ヒドロキシエトキシ）－３，３’－ジメチルジフェニルエ－テル、４，４’－ジヒドロキシ－２，５－ジエトキシジフェニルエーテル等の、ジヒドロキシアルコキシジアリールエーテル類；４，４’－ビス（２－ヒドロキエトキシフェニル）スルフィド、４，４’－ビス［４－（２－ジヒドロキシエトキシ）－３－メチルフェニル］スルフィド等の、ビスヒドロキシアルコキシアリールスルフィド類；４，４’－ビス（２－ヒドロキエトキシフェニル）スルホキシド、４，４’－ビス［４－（２－ジヒドロキシエトキシ）－３－メチルフェニル］スルホキシド等の、ビスヒドロキシアルコキシアリールスルホキシド類；４，４’－ビス（２－ヒドロキエトキシフェニル）スルホン、４，４’－ビス［４－（２－ジヒドロキシエトキシ）－３－メチルフェニル］スルホン等の、ビスヒドロキシアルコキシアリールスルホン類；１，４－ビスヒドロキシエトキシベンゼン、１，３－ビスヒドロキシエトキシベンゼン、１，２－ビスヒドロキシエトキシベンゼン、１，３－ビス［２－［４－（２－ヒドロキシエトキシ）フェニル］プロピル］ベンゼン、１，４－ビス［２－［４－（２－ヒドロキシエトキシ）フェニル］プロピル］ベンゼン、４，４’－ビス（２－ヒドロキシエトキシ）ビフェニル、１，３－ビス［４－（２－ヒドロキシエトキシ）フェニル］－５，７－ジメチルアダマンタン、下記式（２）で表されるジヒドロキシ化合物に代表される無水糖アルコール、及び下記一般式（３）で表されるスピログリコール等の環状エーテル構造を有する化合物が挙げられ、これらは単独で用いても良く、２種以上を組み合わせて用いても良い。 More specifically, examples of the dihydroxy compound (A) include 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy-2-). Methyl) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9- Bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert -Butyl-6-methylphenyl) fluorene, 9,9-bis (4- (3-hydroxy-2,2-dimethylpropoxy) phenyl) fluorene, etc. have aromatic groups in the side chain and aromatic in the main chain Compounds having an ether group bonded to an aromatic group; bis [4- (2-hydroxyethoxy) phenyl] methane, bis [4- (2-hydroxyethoxy) phenyl] diphenylmethane, 1,1-bis [4- (2- Hydroxyethoxy) phenyl] ethane, 1,1-bis [4- (2-hydroxyethoxy) phenyl] -1-phenylethane, 2,2-bis [4- (2- Loxyethoxy) phenyl] propane, 2,2-bis [4- (2-hydroxyethoxy) -3-methylphenyl] propane, 2,2-bis [3,5-dimethyl-4- (2-hydroxyethoxy) phenyl ] Propane, 1,1-bis [4- (2-hydroxyethoxy) phenyl] -3,3,5-trimethylcyclohexane, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 1,4 -Bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 1,3-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 2,2-bis [4- (2-hydroxyethoxy) -3- Phenylphenyl] propane, 2,2-bis [(2-hydroxyethoxy) -3-isopropylphenyl] propane, 2,2-bis [3-tert-butyl-4- (2-hydroxyethoxy) phenyl] propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] butane, 2,2-bis [4- (2-hydroxyethoxy) ) Phenyl] -4-methylpentane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] octane, 1,1-bis [4- (2-hydroxyethoxy) phenyl] decane, 2,2-bis Bis (hydroxyalkoxyaryl) alkanes such as [3-bromo-4- (2-hydroxyethoxy) phenyl] propane, 2,2-bis [3-cyclohexyl-4- (2-hydroxyethoxy) phenyl] propane; 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 1,1-bis [3-cyclohexyl-4- (2-hydroxy) Bis (hydroxyalkoxyaryl) cycloalkanes such as loxyethoxy) phenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclopentane; 4,4′-bis (2-hydroxyethoxy) Dihydroxyalkoxy diaryl ethers such as diphenyl ether, 4,4'-bis (2-hydroxyethoxy) -3,3'-dimethyldiphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether Bishydroxyalkoxyaryl sulfides such as 4,4′-bis (2-hydroxyethoxyphenyl) sulfide, 4,4′-bis [4- (2-dihydroxyethoxy) -3-methylphenyl] sulfide; , 4'-bis (2-hydroxyethoxyphenyl) sulfoxy Bishydroxyalkoxyaryl sulfoxides such as 4,4′-bis [4- (2-dihydroxyethoxy) -3-methylphenyl] sulfoxide; 4,4′-bis (2-hydroxyethoxyphenyl) sulfone, 4 Bishydroxyalkoxyaryl sulfones such as 1,4′-bis [4- (2-dihydroxyethoxy) -3-methylphenyl] sulfone; 1,4-bishydroxyethoxybenzene, 1,3-bishydroxyethoxybenzene, 1 , 2-bishydroxyethoxybenzene, 1,3-bis [2- [4- (2-hydroxyethoxy) phenyl] propyl] benzene, 1,4-bis [2- [4- (2-hydroxyethoxy) phenyl] Propyl] benzene, 4,4′-bis (2-hydroxyethoxy) biphenyl, 1,3-biphenyl [4- (2-hydroxyethoxy) phenyl] -5,7-dimethyladamantane, an anhydrous sugar alcohol represented by the dihydroxy compound represented by the following formula (2), and the following general formula (3) The compound which has cyclic ether structures, such as spiroglycol, is mentioned, These may be used independently and may be used in combination of 2 or more type.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　前記式（２）で表される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、イソマンニド、イソイデットが挙げられ、これらは１種を単独で用いても良く、２種以上を組み合わせて用いても良い。 Examples of the dihydroxy compound represented by the formula (2) include isosorbide, isomannide and isoidet which are in a stereoisomeric relationship, and these may be used alone or in combination of two or more. May be.
　また、ジヒドロキシ化合物（Ａ）として、例えば、オキシアルキレングリコール類、環状エーテル構造を有するジオール類も好適に用いることができる。 Also, as the dihydroxy compound (A), for example, oxyalkylene glycols and diols having a cyclic ether structure can be suitably used.
　前記オキシアルキレングリコール類としては、例えば、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等が挙げられる。前記環状エーテル構造を有するジオール類としては、例えば、スピログリコール類、ジオキサングルコール類が挙げられる。 Examples of the oxyalkylene glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol. Examples of the diols having a cyclic ether structure include spiroglycols and dioxane glycols.
　これらのジヒドロキシ化合物（Ａ）のうち、資源として豊富に存在し、容易に入手可能な種々のデンプンから製造されるソルビトールを脱水縮合して得られるイソソルビドが、入手及び製造のし易さ、光学特性、成形性の面から好ましい。また、９，９－ビス［４－（２－ヒドロキシエトキシ）フェニル］フルオレンや、ポリエチレングリコールも好ましい。 Of these dihydroxy compounds (A), isosorbide obtained by dehydrating condensation of sorbitol produced from various starches that are abundant as resources and are readily available is easy to obtain and produce, and optical characteristics From the viewpoint of moldability, it is preferable. Also, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and polyethylene glycol are preferable.
　なお、ジヒドロキシ化合物（Ａ）を、後述する炭酸ジエステルとの反応に供する場合、その形態は特に限定されず、粉末状、フレーク状であっても、溶融状態や水溶液等の液状であってもよい。 In addition, when using a dihydroxy compound (A) for reaction with the carbonic acid diester mentioned later, the form is not specifically limited, Liquid form, such as a powder form and flake form, a molten state and aqueous solution, may be sufficient. .
　（ジヒドロキシ化合物（Ｂ））
　ジヒドロキシ化合物（Ｂ）としては、例えば、脂環式ジヒドロキシ化合物、脂肪族ジヒドロキシ化合物、芳香族ジヒドロキシ化合物等を挙げることができる。 (Dihydroxy compound (B))
Examples of the dihydroxy compound (B) include alicyclic dihydroxy compounds, aliphatic dihydroxy compounds, and aromatic dihydroxy compounds.
　前記脂環式ジヒドロキシ化合物としては、特に限定されないが、５員環構造又は６員環構造を含む化合物が好ましい。また、６員環構造は共有結合によって椅子形もしくは舟形に固定されていてもよい。脂環式ジヒドロキシ化合物が５員環又は６員環構造であることにより、得られるポリカーボネートの耐熱性を高くすることができるため、好ましい。脂環式ジヒドロキシ化合物に含まれる炭素原子数は、通常７０以下であり、５０以下が好ましく、３０以下がより好ましい。この値が大きくなるほど、耐熱性が高くなるが、合成が困難になったり、精製が困難になったり、コストが高価だったりする。炭素原子数が小さくなるほど、精製しやすく、入手しやすくなる。 The alicyclic dihydroxy compound is not particularly limited, but a compound containing a 5-membered ring structure or a 6-membered ring structure is preferable. The 6-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond. The alicyclic dihydroxy compound having a 5-membered or 6-membered ring structure is preferable because the heat resistance of the resulting polycarbonate can be increased. The number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, and more preferably 30 or less. The higher this value, the higher the heat resistance, but the synthesis becomes difficult, the purification becomes difficult, and the cost is expensive. The smaller the number of carbon atoms, the easier the purification and the easier it is to obtain.
　５員環構造又は６員環構造を含む脂環式ジヒドロキシ化合物としては、具体的には、下記一般式（Ｉ）又は（ＩＩ）で表される脂環式ジヒドロキシ化合物が挙げられる。
　ＨＯＣＨ２－Ｒ１－ＣＨ２ＯＨ　　　（Ｉ）
　ＨＯ－Ｒ２－ＯＨ　　　　　（ＩＩ）
（式（Ｉ）、（ＩＩ）中、Ｒ１、Ｒ２はそれぞれ、炭素数４～２０のシクロアルキレン基を示す。） Specific examples of the alicyclic dihydroxy compound containing a 5-membered ring structure or a 6-membered ring structure include alicyclic dihydroxy compounds represented by the following general formula (I) or (II).
HOCH 2 —R 1 —CH 2 OH (I)
HO—R 2 —OH (II)
(In formulas (I) and (II), R 1 and R 2 each represent a cycloalkylene group having 4 to 20 carbon atoms.)
　上記一般式（Ｉ）で表される脂環式ジヒドロキシ化合物であるシクロヘキサンジメタノールとしては、一般式（Ｉ）において、Ｒ１が下記一般式（Ｉａ）（式中、Ｒ３は、炭素数１～１２のアルキル基又は水素原子を示す）で表される種々の異性体を包含する。具体的には、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等が挙げられる。 As cyclohexanedimethanol which is an alicyclic dihydroxy compound represented by the above general formula (I), in general formula (I), R 1 is represented by the following general formula (Ia) (wherein R 3 has 1 carbon atom) To 12 alkyl groups or hydrogen atoms). Specific examples include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and the like.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　上記一般式（Ｉ）で表される脂環式ジヒドロキシ化合物である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としては、一般式（Ｉ）において、Ｒ１が下記一般式(Ｉｂ)（式中、ｎは０又は１を示す）で表される種々の異性体を包含する。 As tricyclodecane dimethanol and pentacyclopentadecane dimethanol, which are alicyclic dihydroxy compounds represented by the above general formula (I), in general formula (I), R 1 is represented by the following general formula (Ib) (wherein , N represents 0 or 1).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　上記一般式（Ｉ）で表される脂環式ジヒドロキシ化合物であるデカリンジメタノール又は、トリシクロテトラデカンジメタノールとしては、一般式（Ｉ）において、Ｒ１が下記一般式(Ｉｃ)（式中、ｍは０、又は１を示す）で表される種々の異性体を包含する。このようなものとしては、具体的には、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等が挙げられる。 As decalin dimethanol or tricyclotetradecane dimethanol, which is an alicyclic dihydroxy compound represented by the above general formula (I), in general formula (I), R 1 is represented by the following general formula (Ic) (wherein m represents 0 or 1). Specific examples thereof include 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, and the like.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　また、上記一般式（Ｉ）で表される脂環式ジヒドロキシ化合物であるノルボルナンジメタノールとしては、一般式（Ｉ）において、Ｒ１が下記一般式(Ｉｄ)で表される種々の異性体を包含する。このようなものとしては、具体的には、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等が挙げられる。 Moreover, as norbornanedimethanol which is an alicyclic dihydroxy compound represented by the above general formula (I), various isomers in which R 1 is represented by the following general formula (Id) in the general formula (I) Include. Specific examples thereof include 2,3-norbornane dimethanol and 2,5-norbornane dimethanol.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　　一般式（Ｉ）で表される脂環式ジヒドロキシ化合物であるアダマンタンジメタノールとしては、一般式（Ｉ）において、Ｒ１が下記一般式(Ｉｅ)で表される種々の異性体を包含する。このようなものとしては、具体的には、１，３－アダマンタンジメタノール等が挙げられる。 The adamantane dimethanol, which is an alicyclic dihydroxy compound represented by the general formula (I), includes various isomers in which R 1 is represented by the following general formula (Ie) in the general formula (I). Specific examples of such compounds include 1,3-adamantane dimethanol.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　また、上記一般式（ＩＩ）で表される脂環式ジヒドロキシ化合物であるシクロヘキサンジオールは、一般式（ＩＩ）において、Ｒ２が下記一般式(ＩＩａ)（式中、Ｒ３は，炭素数１～１２のアルキル基又は水素原子を示す）で表される種々の異性体を包含する。このようなものとしては、具体的には、１，２－シクロヘキサンジオール、１，３－シクロヘキサンジオール、１，４－シクロヘキサンジオール、２－メチル－１，４－シクロヘキサンジオール等が挙げられる。 Further, cyclohexanediol, which is an alicyclic dihydroxy compound represented by the general formula (II), in the general formula (II), R 2 is represented by the following general formula (IIa) (wherein, R 3 is C 1 -C To 12 alkyl groups or hydrogen atoms). Specific examples of such compounds include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and the like.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　上記一般式（ＩＩ）で表される脂環式ジヒドロキシ化合物であるトリシクロデカンジオール、ペンタシクロペンタデカンジオールとしては、一般式（ＩＩ）において、Ｒ２が下記一般式(ＩＩｂ)（式中、ｎは０又は１を示す）で表される種々の異性体を包含する。 As tricyclodecanediol and pentacyclopentadecanediol, which are alicyclic dihydroxy compounds represented by the above general formula (II), in general formula (II), R 2 is represented by the following general formula (IIb) (wherein n Represents 0 or 1).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　上記一般式（ＩＩ）で表される脂環式ジヒドロキシ化合物であるデカリンジオール又はトリシクロテトラデカンジオールとしては、一般式（ＩＩ）において、Ｒ２が下記一般式(ＩＩｃ)（式中、ｍは０、又は１を示す）で表される種々の異性体を包含する。このようなものとしては、具体的には、２，６－デカリンジオール、１，５－デカリンジオール、２，３－デカリンジオール等が用いられる。 As decalin diol or tricyclotetradecane diol which is an alicyclic dihydroxy compound represented by the above general formula (II), in general formula (II), R 2 is represented by the following general formula (IIc) (where m is 0 Or various isomers represented by 1). Specifically, 2,6-decalindiol, 1,5-decalindiol, 2,3-decalindiol and the like are used as such.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　上記一般式（ＩＩ）で表される脂環式ジヒドロキシ化合物であるノルボルナンジオールとしては、一般式（ＩＩ）において、Ｒ２が下記一般式（ＩＩｄ）で表される種々の異性体を包含する。このようなものとしては、具体的には、２，３－ノルボルナンジオール、２，５－ノルボルナンジオール等が用いられる。 The norbornanediol which is an alicyclic dihydroxy compound represented by the above general formula (II) includes various isomers in which R 2 is represented by the following general formula (IId) in the general formula (II). Specifically, 2,3-norbornanediol, 2,5-norbornanediol and the like are used as such.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　上記一般式（ＩＩ）で表される脂環式ジヒドロキシ化合物であるアダマンタンジオールとしては、一般式（ＩＩ）において、Ｒ２が下記一般式（ＩＩｅ）で表される種々の異性体を包含する。このようなものとしては具体的には、１，３－アダマンタンジオール等が用いられる。 The adamantanediol which is an alicyclic dihydroxy compound represented by the above general formula (II) includes various isomers in which R 2 is represented by the following general formula (IIe) in the general formula (II). Specifically, 1,3-adamantanediol or the like is used as such.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　前記脂環式ジヒドロキシ化合物の具体例のうち、特に、シクロヘキサンジメタノール類、トリシクロデカンジメタノール類、アダマンタンジオール類、ペンタシクロペンタデカンジメタノール類が好ましく、入手のしやすさ、取り扱いのしやすさという観点から、１，４－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、１，２－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が好ましい。 Among specific examples of the alicyclic dihydroxy compound, cyclohexane dimethanols, tricyclodecane dimethanols, adamantanediols, and pentacyclopentadecane dimethanols are preferable, and are easily available and easy to handle. From this viewpoint, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and tricyclodecane dimethanol are preferable.
　前記脂肪族ジヒドロキシ化合物としては、例えば、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－ヘキサンジオール等が挙げられる。 Examples of the aliphatic dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1, Examples include 5-heptanediol and 1,6-hexanediol.
　前記芳香族ジヒドロキシ化合物としては、例えば、２，２－ビス（４－ヒドロキシフェニル）プロパン［＝ビスフェノールＡ］、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－（３，５－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、２，２－ビス（４－ヒドロキシフェニル）ペンタン、２，４’－ジヒドロキシ－ジフェニルメタン、ビス（４－ヒドロキシフェニル）メタン、ビス（４－ヒドロキシ－５－ニトロフェニル）メタン、１，１－ビス（４－ヒドロキシフェニル）エタン、３，３－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）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、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、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－２－メチルフェニル）フルオレン等が挙げられる。 Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2 -Bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5 -Dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4'-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1 Bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy -3,3'-dichlorodiphenyl ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-2-methylphenyl) fluorene, and the like.
　なお、上記例示化合物は、本発明で使用することができる脂環式ジヒドロキシ化合物、脂肪族ジヒドロキシ化合物、芳香族ジヒドロキシ化合物の一例であって、これらに限定されるものではない。これらの化合物は、１種単独で又は２種以上を混合して使用することができる。 The above exemplary compounds are examples of alicyclic dihydroxy compounds, aliphatic dihydroxy compounds, and aromatic dihydroxy compounds that can be used in the present invention, and are not limited thereto. These compounds can be used individually by 1 type or in mixture of 2 or more types.
　これらのジヒドロキシ化合物（Ｂ）を用いることにより、用途に応じた柔軟性の改善、耐熱性の向上、成形性の改善等の効果を得ることができる。 By using these dihydroxy compounds (B), it is possible to obtain effects such as improvement in flexibility, improvement in heat resistance, improvement in moldability, etc. according to the application.
　ポリカーボネート系樹脂を構成する全ジヒドロキシ化合物に対するジヒドロキシ化合物（Ａ）の割合は特に限定されないが、１０モル％以上が好ましく、４０モル％以上がより好ましく、６０モル％以上がさらに好ましい。また、上限値としては、１００モル％以下が好ましい。ジヒドロキシ化合物（Ｂ）に由来する構成単位の含有割合が多過ぎると、光学特性等の性能を低下させたりすることがある。 The ratio of the dihydroxy compound (A) to the total dihydroxy compound constituting the polycarbonate resin is not particularly limited, but is preferably 10 mol% or more, more preferably 40 mol% or more, and further preferably 60 mol% or more. Moreover, as an upper limit, 100 mol% or less is preferable. When the content ratio of the structural unit derived from the dihydroxy compound (B) is too large, performance such as optical characteristics may be deteriorated.
　さらに、脂環式ジヒドロキシ化合物、脂肪族ジヒドロキシ化合物、芳香族ジヒドロキシ化合物を用いる場合、ポリカーボネートを構成する全ジヒドロキシ化合物に対するジヒドロキシ化合物（Ａ）とこれらの各ジヒドロキシ化合物の合計の割合は特に限定されず、任意の割合で選択できる。また、ジヒドロキシ化合物（Ａ）に由来する構成単位とこれらの各ジヒドロキシ化合物に由来する構成単位との含有割合も特に限定されず、任意の割合で選択できる。 Furthermore, when using an alicyclic dihydroxy compound, an aliphatic dihydroxy compound, and an aromatic dihydroxy compound, the ratio of the total of the dihydroxy compound (A) and each of these dihydroxy compounds to the total dihydroxy compound constituting the polycarbonate is not particularly limited, You can select any ratio. Moreover, the content rate of the structural unit derived from the dihydroxy compound (A) and the structural unit derived from each of these dihydroxy compounds is not particularly limited, and can be selected at an arbitrary ratio.
　（炭酸ジエステル）
　ポリカーボネート樹脂の製造方法で用いられる炭酸ジエステルとしては、例えば、ジフェニルカーボネート、ジトリルカーボネートに代表される置換ジフェニルカーボネート、ジメチルカーボネート、ジエチルカーボネート及びジ－ｔ－ブチルカーボネート等が例示され、これらの中でも、ジフェニルカーボネート及び置換ジフェニルカーボネートが特に好ましい。これらの炭酸ジエステルは、１種を単独で用いても良く、２種以上を混合して用いても良い。 (Carbonated diester)
Examples of the carbonic acid diester used in the method for producing the polycarbonate resin include diphenyl carbonate, substituted diphenyl carbonate typified by ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Among these, Diphenyl carbonate and substituted diphenyl carbonate are particularly preferred. These carbonic acid diesters may be used alone or in combination of two or more.
　炭酸ジエステルは、反応に用いる全ジヒドロキシ化合物に対して、０．９０～１．１０のモル比率で用いることが好ましく、０．９６～１．０４のモル比率であることがより好ましい。このモル比が０．９０より小さくなると、製造されたポリカーボネートの末端ＯＨ基が増加して、ポリマーの熱安定性が悪化したり、所望する高分子量体が得られない場合がある。また、このモル比が１．１０より大きくなると、同一条件下ではエステル交換反応の速度が低下したり、所望する分子量のポリカーボネートの製造が困難となったりするばかりか、製造されたポリカーボネート共重合体中の残存炭酸ジエステル量が増加し、この残存炭酸ジエステルが、成形時、又は成形品の臭気の原因となることもある。 The carbonic acid diester is preferably used in a molar ratio of 0.90 to 1.10, more preferably in a molar ratio of 0.96 to 1.04, based on all dihydroxy compounds used in the reaction. When this molar ratio is less than 0.90, the terminal OH group of the produced polycarbonate increases, and the thermal stability of the polymer may deteriorate, or the desired high molecular weight product may not be obtained. On the other hand, when the molar ratio is greater than 1.10, the rate of the transesterification reaction decreases under the same conditions, and it becomes difficult to produce a polycarbonate having a desired molecular weight. The amount of residual carbonic acid diester increases, and this residual carbonic acid diester may cause odor during molding or in the molded product.
　フィルム用途では通常柔軟性が必要とされるため、ポリカーボネート系樹脂のガラス転移温度（Ｔｇ）は、４５℃以上であることが好ましく、４５～１３０℃がより好ましい。 Since film applications usually require flexibility, the glass transition temperature (Tg) of the polycarbonate-based resin is preferably 45 ° C. or higher, more preferably 45 to 130 ° C.
　ポリカーボネート系樹脂は、上記ジヒドロキシ化合物（Ａ）を含むジヒドロキシ化合物を、重合触媒の存在下、炭酸ジエステルと反応させる溶融重合法により製造することができる。重合触媒の種類やその添加量は、従来公知のものや添加量を適宜採用することができ、溶液重合法についても、従来公知の方法を適宜採用することができる。 The polycarbonate resin can be produced by a melt polymerization method in which a dihydroxy compound containing the dihydroxy compound (A) is reacted with a carbonic acid diester in the presence of a polymerization catalyst. As the type of polymerization catalyst and the addition amount thereof, conventionally known ones and addition amounts can be appropriately employed, and conventionally known methods can be appropriately employed for the solution polymerization method.
　位相差フィルム３ａは、例えば、上記樹脂から形成されたフィルムを延伸することにより得られる。上記樹脂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を採用することができる。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。これらの方法の中でも、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ため、押出成形法又はキャスト塗工法が好ましい。成形条件は、使用される樹脂の組成や種類、位相差フィルムに所望される特性等に応じて適宜設定することができる。なお、上記樹脂は、多くのフィルム製品が市販されているので、当該市販フィルムをそのまま延伸処理に供することもできる。 The retardation film 3a is obtained, for example, by stretching a film formed from the above resin. Any appropriate forming method can be adopted as a method for forming a film from the resin. Specific examples include compression molding methods, transfer molding methods, injection molding methods, extrusion molding methods, blow molding methods, powder molding methods, FRP molding methods, cast coating methods (for example, casting methods), calendar molding methods, and hot presses. Law. Among these methods, the extrusion molding method or the cast coating method is preferable because the smoothness of the resulting film can be improved and good optical uniformity can be obtained. The molding conditions can be appropriately set according to the composition and type of the resin used, the properties desired for the retardation film, and the like. In addition, since many film products are marketed for the said resin, the said commercial film can also be used for a extending | stretching process as it is.
　上記フィルムの延伸倍率は、位相差フィルム３ａに所望される面内位相差値及び厚み、使用される樹脂の種類、使用されるフィルムの厚み、延伸温度等に応じて適宜設定することができる。具体的には、延伸倍率は、１．７５倍～３．００倍程度が好ましく、１．８０倍～２．８０倍程度がより好ましく、１．８５倍～２．６０倍程度がさらに好ましい。 The stretching ratio of the film can be appropriately set according to the in-plane retardation value and thickness desired for the retardation film 3a, the type of resin used, the thickness of the film used, the stretching temperature, and the like. Specifically, the draw ratio is preferably about 1.75 times to 3.00 times, more preferably about 1.80 times to 2.80 times, and further preferably about 1.85 times to 2.60 times.
　上記フィルムの延伸温度は、位相差フィルム３ａに所望される面内位相差値及び厚み、使用される樹脂の種類、使用されるフィルムの厚み、延伸倍率等に応じて適宜設定することができる。具体的には、延伸温度は、１２５℃～１５０℃程度が好ましく、１３０℃～１４０℃程度がより好ましい。 The stretching temperature of the film can be appropriately set according to the in-plane retardation value and thickness desired for the retardation film 3a, the type of resin used, the thickness of the film used, the stretching ratio, and the like. Specifically, the stretching temperature is preferably about 125 ° C. to 150 ° C., more preferably about 130 ° C. to 140 ° C.
　上記フィルムの延伸方法としては、任意の適切な延伸方法が採用され得る。具体的には、自由端延伸、固定端延伸、自由端収縮、固定端収縮等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、水平方向、垂直方向、厚さ方向、対角方向等、様々な方向や次元に行なうことができる。 Any appropriate stretching method can be adopted as the stretching method of the film. Specifically, various stretching methods such as free end stretching, fixed end stretching, free end contraction, and fixed end contraction can be used singly or simultaneously or sequentially. The stretching direction can also be performed in various directions and dimensions such as a horizontal direction, a vertical direction, a thickness direction, and a diagonal direction.
　１つの実施形態においては、位相差フィルム３ａは、樹脂フィルムを自由端一軸延伸もしくは固定端一軸延伸することにより形成される。自由端一軸延伸の具体例としては、樹脂フィルムを長手方向に走行させながら、周速の異なるロール間で延伸する方法が挙げられる。固定端一軸延伸の具体例としては、樹脂フィルムを長手方向に走行させながら、幅方向（横方向）に延伸する方法が挙げられる。 In one embodiment, the retardation film 3a is formed by stretching a resin film uniaxially at a free end or uniaxially at a fixed end. As a specific example of the free end uniaxial stretching, there is a method of stretching between rolls having different peripheral speeds while running the resin film in the longitudinal direction. As a specific example of the fixed end uniaxial stretching, there is a method of stretching in the width direction (lateral direction) while running the resin film in the longitudinal direction.
　別の実施形態においては、位相差フィルム３ａは、長尺状の樹脂フィルムを長手方向に対して所定の角度の方向に連続的に斜め延伸することにより作製される。斜め延伸を採用することにより、フィルムの長手方向に対して所定の角度の配向角（所定の角度の方向に遅相軸）を有する長尺状の延伸フィルムが得られ、例えば、偏光子との積層に際してロールトゥロールが可能となり、製造工程を簡略化することができる。なお、ロールトゥロールとは、フィルムをロール搬送しながら長尺方向を揃えて積層する方式をいう。 In another embodiment, the retardation film 3a is produced by continuously stretching a long resin film obliquely in a direction at a predetermined angle with respect to the longitudinal direction. By adopting oblique stretching, a long stretched film having an orientation angle of a predetermined angle with respect to the longitudinal direction of the film (slow axis in the direction of the predetermined angle) is obtained. For example, with a polarizer Roll-to-roll is possible at the time of lamination, and the manufacturing process can be simplified. In addition, a roll toe roll means the system laminated | stacked by aligning a elongate direction, carrying a film roll.
　斜め延伸に用いる延伸機としては、例えば、横及び／又は縦方向に、左右異なる速度の送り力もしくは引張り力又は引き取り力を付加し得るテンター式延伸機が挙げられる。テンター式延伸機には、横一軸延伸機、同時二軸延伸機等があるが、長尺状の樹脂フィルムを連続的に斜め延伸し得る限り、任意の適切な延伸機が用いられ得る。 Examples of the stretching machine used for the oblique stretching include a tenter type stretching machine capable of adding a feed force, a pulling force, or a pulling force at different speeds in the lateral and / or longitudinal directions. The tenter type stretching machine includes a horizontal uniaxial stretching machine, a simultaneous biaxial stretching machine, and the like, but any suitable stretching machine can be used as long as a long resin film can be continuously stretched obliquely.
　本発明の有機ＥＬ表示装置用光学フィルムは、無機薄膜を含むバリア層を有さないものであって、前記位相差フィルム３ａは、無機薄膜を含むバリア層を有さない。このような無機薄膜は通常スパッタ等により形成され、形成過程において熱を発生する。このような無機薄膜を前記位相差フィルム３ａに設けることで、位相差フィルム３ａの位相差値が熱により変更してしまう場合や、位相差フィルム３ａが破断してしまう場合があり、好ましくない。前記無機薄膜としては、酸化物、窒化物、水素化物及びその複合化合物からなる群から選ばれる少なくとも１種の無機化合物を含むものを挙げることができる。無機薄膜を形成する無機化合物の一例としては、ダイヤモンドライクカーボン（ＤＬＣ）、ケイ素窒化物（ＳｉＮｘ）、ケイ素酸化物（ＳｉＯｙ）、アルミニウム酸化物（ＡｌＯｚ）、アルミニウム窒化物等が挙げられる。 The optical film for an organic EL display device of the present invention does not have a barrier layer containing an inorganic thin film, and the retardation film 3a does not have a barrier layer containing an inorganic thin film. Such an inorganic thin film is usually formed by sputtering or the like, and generates heat during the formation process. By providing such an inorganic thin film on the retardation film 3a, the retardation value of the retardation film 3a may be changed by heat, or the retardation film 3a may be broken, which is not preferable. Examples of the inorganic thin film include those containing at least one inorganic compound selected from the group consisting of oxides, nitrides, hydrides, and complex compounds thereof. Examples of the inorganic compound that forms the inorganic thin film include diamond-like carbon (DLC), silicon nitride (SiNx), silicon oxide (SiOy), aluminum oxide (AlOz), and aluminum nitride.
　（１－２）第２の位相差フィルム
　前記第２の位相差フィルム３ｂは、屈折率特性がｎｚ＞ｎｘ≧ｎｙの関係を示すものが好ましい。このような屈折率特性を有する第２の位相差フィルムを備えることで、反射光を吸収する効果の角度依存性が低減し、様々な角度で反射した反射光に対して、その出射を防止することができるため、好ましい。 (1-2) Second Retardation Film Preferably, the second retardation film 3b has a refractive index characteristic of nz> nx ≧ ny. By providing the second retardation film having such a refractive index characteristic, the angle dependency of the effect of absorbing the reflected light is reduced, and the reflected light reflected at various angles is prevented from being emitted. This is preferable.
　前記第２の位相差フィルム３ｂの厚み方向の位相差Ｒｔｈ（５５０）は、－２６０ｎｍ～－１０ｎｍが好ましく、－２３０ｎｍ～－１５ｎｍがより好ましく、－２１５ｎｍ～－２０ｎｍがさらに好ましい。このような範囲であることで、上記効果が顕著となるため、好ましい。 The thickness direction retardation Rth (550) of the second retardation film 3b is preferably −260 nm to −10 nm, more preferably −230 nm to −15 nm, and further preferably −215 nm to −20 nm. Such a range is preferable because the above-described effect becomes remarkable.
　１つの実施形態においては、前記第２の位相差フィルム３ｂは、その屈折率がｎｘ＝ｎｙの関係を示す。ここで、「ｎｘ＝ｎｙ」は、ｎｘとｎｙが厳密に等しい場合のみならず、ｎｘとｎｙが実質的に等しい場合も包含する。具体的には、Ｒｅ（５５０）が１０ｎｍ未満であることをいう。別の実施形態においては、第２の位相差フィルム３ｂは、その屈折率がｎｘ＞ｎｙの関係を示す。この場合、第２の位相差フィルム３ｂの面内位相差Ｒｅ（５５０）は、１０ｎｍ～１５０ｎｍが好ましく、１０ｎｍ～８０ｎｍがより好ましい。 In one embodiment, the second retardation film 3b has a refractive index of nx = ny. Here, “nx = ny” includes not only the case where nx and ny are exactly equal, but also the case where nx and ny are substantially equal. Specifically, Re (550) is less than 10 nm. In another embodiment, the second retardation film 3b has a relationship in which the refractive index is nx> ny. In this case, the in-plane retardation Re (550) of the second retardation film 3b is preferably 10 nm to 150 nm, and more preferably 10 nm to 80 nm.
　前記第２の位相差フィルム３ｂは、任意の適切な材料で形成することができ、特に限定されるものではないが、ホメオトロピック配向に固定された液晶層であることが好ましい。ホメオトロピック配向させることができる液晶材料（液晶化合物）は、液晶モノマーであっても液晶ポリマーであってもよい。当該液晶化合物及び当該液晶層の形成方法の具体例としては、例えば、特開２００２－３３３６４２号公報の［００２０］～［００４２］に記載の液晶化合物及び形成方法が挙げられる。この場合、厚みは、０．１μｍ～５μｍが好ましく、０．２μｍ～３μｍがより好ましい。 The second retardation film 3b can be formed of any appropriate material, and is not particularly limited, but is preferably a liquid crystal layer fixed in homeotropic alignment. The liquid crystal material (liquid crystal compound) that can be homeotropically aligned may be a liquid crystal monomer or a liquid crystal polymer. Specific examples of the liquid crystal compound and the method for forming the liquid crystal layer include, for example, the liquid crystal compounds and methods described in JP-A-2002-333642, [0020] to [0042]. In this case, the thickness is preferably 0.1 μm to 5 μm, more preferably 0.2 μm to 3 μm.
　別の好ましい具体例として、第２の位相差フィルム３ｂは、特開２０１２－３２７８４号公報に記載のフマル酸ジエステル系樹脂で形成された位相差フィルムであってもよい。この場合、厚みは、５μｍ～５０μｍが好ましく、１０μｍ～３５μｍがより好ましい。 As another preferred specific example, the second retardation film 3b may be a retardation film formed of a fumaric acid diester resin described in JP 2012-32784 A. In this case, the thickness is preferably 5 μm to 50 μm, more preferably 10 μm to 35 μm.
　上記第１の位相差フィルム３ａ及び第２の位相差フィルム３ｂから構成される積層位相差フィルムの面内位相差（５５０）Ｒｅは、１２０ｎｍ～１６０ｎｍであることが好ましく、１３０ｎｍ～１５０ｎｍがより好ましく、１３５ｎｍ～１４５ｎｍがさらに好ましい。 The in-plane retardation (550) Re of the laminated retardation film composed of the first retardation film 3a and the second retardation film 3b is preferably 120 nm to 160 nm, and more preferably 130 nm to 150 nm. 135 nm to 145 nm is more preferable.
　上記第１の位相差フィルム３ａと第２の位相差フィルム３ｂとから構成される積層位相差フィルムの厚み方向の位相差Ｒｔｈ（５５０）は、４０ｎｍ～１００ｎｍであることが好ましく、５０ｎｍ～９０ｎｍがより好ましく、６０ｎｍ～８０ｎｍがさらに好ましい。 The thickness direction retardation Rth (550) of the laminated retardation film composed of the first retardation film 3a and the second retardation film 3b is preferably 40 nm to 100 nm, and more preferably 50 nm to 90 nm. More preferred is 60 nm to 80 nm.
　また、前記第１の位相差フィルム３ａと第２の位相差フィルム３ｂとは、任意の接着剤層又は粘着剤層４を介して積層することができる。接着剤層又は粘着剤層４は、本明細書中に記載のものを好適に使用することができ、例えば、（メタ）アクリル系ポリマーをベースポリマーとするアクリル系粘着剤が、光学的透明性に優れ、適度な濡れ性と凝集性と接着性の粘着特性を示して、耐候性や耐熱性等に優れているため、好ましい。また、公知のいかなる接着剤層又は粘着剤層も使用することができる。 Further, the first retardation film 3a and the second retardation film 3b can be laminated via an arbitrary adhesive layer or pressure-sensitive adhesive layer 4. As the adhesive layer or the pressure-sensitive adhesive layer 4, those described in the present specification can be suitably used. For example, an acrylic pressure-sensitive adhesive based on a (meth) acrylic polymer is optically transparent. It is preferable because it exhibits excellent wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and is excellent in weather resistance, heat resistance, and the like. In addition, any known adhesive layer or pressure-sensitive adhesive layer can be used.
　（２）粘接着剤層
　本発明で使用する粘接着剤層は、４０℃、９２％Ｒ．Ｈ．における透湿度が、５０ｇ／（ｍ２・ｄａｙ）以下であればよく、その組成は特に限定されるものではない。ここで、「粘接着剤層」とは、接着剤層又は粘着剤層のことをいう。 (2) Adhesive layer The adhesive layer used in the present invention is 40 ° C., 92% R.D. H. The water vapor transmission rate in the case of 50 g / (m 2 · day) or less is not particularly limited. Here, the “adhesive layer” refers to an adhesive layer or a pressure-sensitive adhesive layer.
　前記粘接着剤層の透湿度は、５０ｇ／（ｍ２・ｄａｙ）以下であり、３０ｇ／（ｍ２・ｄａｙ）以下が好ましく、２０ｇ／（ｍ２・ｄａｙ）以下がより好ましく、１５ｇ／（ｍ２・ｄａｙ）以下がさらに好ましい。また、透湿度の下限値は特に限定されるものではないが、理想的には、水蒸気を全く透過させないこと（すなわち、０ｇ／（ｍ２・ｄａｙ））が好ましい。粘接着剤層の透湿度が前記範囲であれば、当該粘接着剤層を含む光学フィルム（位相差フィルム）を有機ＥＬ素子に適用した際に、当該有機ＥＬ素子に水分が移行することを抑制することができ、その結果、有機ＥＬ素子の水分による劣化等を抑制することができるため好ましい。前記透湿度は、粘接着剤層の厚み５０μｍにおける４０℃、９２％Ｒ．Ｈ．条件下での水蒸気透過率（透湿度）であって、その測定方法は実施例に記載の方法により測定することができる。 The moisture permeability of the adhesive layer is, 50g / (m 2 · day ) or less, preferably 30g / (m 2 · day) or less, 20g / (m 2 · day ) , more preferably less, 15 g / (M 2 · day) or less is more preferable. Further, the lower limit value of moisture permeability is not particularly limited, but ideally, it is preferable that water vapor is not permeated at all (that is, 0 g / (m 2 · day)). When the moisture permeability of the adhesive layer is within the above range, when an optical film (retardation film) including the adhesive layer is applied to the organic EL element, moisture moves to the organic EL element. As a result, it is preferable because deterioration of the organic EL element due to moisture can be suppressed. The moisture permeability is 40 ° C. and 92% R.D. H. The water vapor transmission rate (moisture permeability) under the conditions can be measured by the method described in the examples.
　（２－１）接着剤層
　接着剤層としては、４０℃、９２％Ｒ．Ｈ．における透湿度が、５０ｇ／（ｍ２・ｄａｙ）以下であればよく、その組成は特に限定されるものではなく、任意の適切な接着剤からなる層を採用し得る。このような接着剤としては、例えば、天然ゴム接着剤、α－オレフィン系接着剤、ウレタン樹脂系接着剤、エチレン－酢酸ビニル樹脂エマルション接着剤、エチレン－酢酸ビニル樹脂系ホットメルト接着剤、エポキシ樹脂系接着剤、塩化ビニル樹脂溶剤系接着剤、クロロプレンゴム系接着剤、シアノアクリレート系接着剤、シリコーン系接着剤、スチレン－ブタジエンゴム溶剤系接着剤、ニトリルゴム系接着剤、ニトロセルロース系接着剤、反応性ホットメルト接着剤、フェノール樹脂系接着剤、変性シリコーン系接着剤、ポリエステル系ホットメルト接着剤、ポリアミド樹脂ホットメルト接着剤、ポリイミド系接着剤、ポリウレタン樹脂ホットメルト接着剤、ポリオレフィン樹脂ホットメルト接着剤、ポリ酢酸ビニル樹脂溶剤系接着剤、ポリスチレン樹脂溶剤系接着剤、ポリビニルアルコール系接着剤、ポリビニルピロリドン樹脂系接着剤、ポリビニルブチラール系接着剤、ポリベンズイミダゾール接着剤、ポリメタクリレート樹脂溶剤系接着剤、メラミン樹脂系接着剤、ユリア樹脂系接着剤、レゾルシノール系接着剤等が挙げられる。このような接着剤は、１種単独又は２種以上を混合して使用することができる。 (2-1) Adhesive Layer As the adhesive layer, 40 ° C., 92% R.D. H. The water vapor transmission rate may be 50 g / (m 2 · day) or less, and the composition is not particularly limited, and a layer made of any appropriate adhesive may be adopted. Examples of such adhesives include natural rubber adhesives, α-olefin adhesives, urethane resin adhesives, ethylene-vinyl acetate resin emulsion adhesives, ethylene-vinyl acetate resin hot melt adhesives, and epoxy resins. Adhesives, vinyl chloride resin solvent adhesives, chloroprene rubber adhesives, cyanoacrylate adhesives, silicone adhesives, styrene-butadiene rubber solvent adhesives, nitrile rubber adhesives, nitrocellulose adhesives, Reactive hot melt adhesives, phenol resin adhesives, modified silicone adhesives, polyester hot melt adhesives, polyamide resin hot melt adhesives, polyimide adhesives, polyurethane resin hot melt adhesives, polyolefin resin hot melt adhesives Adhesive, polyvinyl acetate resin solvent-based adhesive, Styrene resin solvent adhesive, polyvinyl alcohol adhesive, polyvinyl pyrrolidone resin adhesive, polyvinyl butyral adhesive, polybenzimidazole adhesive, polymethacrylate resin solvent adhesive, melamine resin adhesive, urea resin adhesive Agents, resorcinol adhesives, and the like. Such an adhesive agent can be used individually by 1 type or in mixture of 2 or more types.
　接着剤としては、接着形態で分類すると、例えば、熱硬化型接着剤、ホットメルト接着剤等が挙げられる。このような接着剤は、１種のみであっても良いし、２種以上であっても良い。 Examples of adhesives include, for example, thermosetting adhesives and hot-melt adhesives when classified according to the adhesive form. Only one kind of such an adhesive may be used, or two or more kinds thereof may be used.
　熱硬化型接着剤は、加熱により熱硬化して固化することにより接着力を発現する。熱硬化型接着剤としては、例えば、エポキシ系熱硬化型接着剤、ウレタン系熱硬化型接着剤、アクリル系熱硬化型接着剤等が挙げられる。熱硬化型接着剤の硬化温度は、例えば、１００～２００℃である。 A thermosetting adhesive exhibits an adhesive force when cured by heating and solidified. Examples of the thermosetting adhesive include an epoxy thermosetting adhesive, a urethane thermosetting adhesive, and an acrylic thermosetting adhesive. The curing temperature of the thermosetting adhesive is, for example, 100 to 200 ° C.
　ホットメルト接着剤は、加熱により溶融又は軟化して、被着体に熱融着し、その後の冷却によって、固化することにより、被着体に接着する。ホットメルト接着剤としては、例えば、ゴム系ホットメルト接着剤、ポリエステル系ホットメルト接着剤、ポリオレフィン系ホットメルト接着剤、エチレン－酢酸ビニル樹脂系ホットメルト接着剤、ポリアミド樹脂ホットメルト接着剤、ポリウレタン樹脂ホットメルト接着剤等が挙げられる。ホットメルト接着剤の軟化温度（環球法）は、例えば、１００～２００℃である。また、ホットメルト接着剤の溶融粘度は、１８０℃で、例えば、１００～３００００ｍＰａ・ｓである。 The hot melt adhesive is melted or softened by heating, thermally fused to the adherend, and then solidified by cooling to adhere to the adherend. Examples of hot melt adhesives include rubber hot melt adhesives, polyester hot melt adhesives, polyolefin hot melt adhesives, ethylene-vinyl acetate resin hot melt adhesives, polyamide resin hot melt adhesives, and polyurethane resins. Examples thereof include hot melt adhesives. The softening temperature (ring ball method) of the hot melt adhesive is, for example, 100 to 200 ° C. The melt viscosity of the hot melt adhesive is 180 ° C., for example, 100 to 30000 mPa · s.
　接着剤層の厚みは、特に限定されるものではないが、例えば、０．０１～１０μｍ程度であることが好ましく、０．０５～８μｍ程度であることがより好ましい。 The thickness of the adhesive layer is not particularly limited, but is preferably about 0.01 to 10 μm, and more preferably about 0.05 to 8 μm.
　（２－２）粘着剤層
　粘着剤層としては、４０℃、９２％Ｒ．Ｈ．における透湿度が、５０ｇ／（ｍ２・ｄａｙ）以下であればよく、その組成は特に限定されるものではなく、任意の適切な粘着剤組成物からなる層を採用し得る。粘着剤組成物としては、例えば、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、ビニルアルキルエーテル系粘着剤、ポリビニルアルコール系粘着剤、ポリビニルピロリドン系粘着剤、ポリアクリルアミド系粘着剤、セルロース系粘着剤等を挙げることができるが、これらの中でも、透湿度の観点から、ゴム系粘着剤組成物であることが好ましい。 (2-2) Adhesive layer As the adhesive layer, 40 ° C, 92% R.D. H. The water vapor transmission rate may be 50 g / (m 2 · day) or less, and the composition thereof is not particularly limited, and a layer made of any appropriate pressure-sensitive adhesive composition can be adopted. Examples of the adhesive composition include rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide. Among these, a pressure-sensitive adhesive, a cellulose-based pressure-sensitive adhesive, and the like can be mentioned. Among these, a rubber-based pressure-sensitive adhesive composition is preferable from the viewpoint of moisture permeability.
　ゴム系粘着剤組成物としては、ゴム系ポリマーを含むものであればよく、その組成は特に限定されるものではない。 The rubber-based pressure-sensitive adhesive composition only needs to contain a rubber-based polymer, and the composition is not particularly limited.
　本発明で用いるゴム系ポリマーは、室温付近の温度域においてゴム弾性を示すポリマーである。具体的には、スチレン系熱可塑性エラストマー、イソブチレン系ポリマー等を挙げることができることができるが、本発明においては、耐候性の観点から、イソブチレンの単独重合体であるポリイソブチレン（ＰＩＢ）を用いることが好ましい。これは、ポリイソブチレンは、主鎖の中に二重結合を含まないため、耐光性が優れるものである。 The rubber polymer used in the present invention is a polymer exhibiting rubber elasticity in a temperature range near room temperature. Specific examples include styrene-based thermoplastic elastomers and isobutylene-based polymers. In the present invention, from the viewpoint of weather resistance, polyisobutylene (PIB), which is a homopolymer of isobutylene, is used. Is preferred. This is because polyisobutylene has excellent light resistance because it does not contain a double bond in the main chain.
　前記ポリイソブチレンとしては、例えば、ＢＡＳＦ社製のＯＰＰＡＮＯＬ等の市販品を用いることができる。 As the polyisobutylene, for example, commercially available products such as OPPANOL manufactured by BASF can be used.
　前記ポリイソブチレンの重量平均分子量（Ｍｗ）は、１０万以上であることが好ましく、３０万以上であることがより好ましく、６０万以上であることがさらに好ましく、７０万以上であることが特に好ましい。また、重量平均分子量の上限値は特に限定されるものではないが、５００万以下が好ましく、３００万以下がより好ましく、２００万以下がさらに好ましい。前記ポリイソブチレンの重量平均分子量を１０万以上とすることで高温保管時の耐久性がより優れるゴム系粘着剤組成物とすることができる。 The weight average molecular weight (Mw) of the polyisobutylene is preferably 100,000 or more, more preferably 300,000 or more, further preferably 600,000 or more, and particularly preferably 700,000 or more. . The upper limit of the weight average molecular weight is not particularly limited, but is preferably 5 million or less, more preferably 3 million or less, and even more preferably 2 million or less. By setting the weight average molecular weight of the polyisobutylene to 100,000 or more, it is possible to obtain a rubber-based pressure-sensitive adhesive composition that is more excellent in durability during high-temperature storage.
　前記ポリイソブチレンの含有量は、特に限定されるものではないが、ゴム系粘着剤組成物の全固形分中、５０重量％以上であることが好ましく、６０重量％以上であることがより好ましく、７０重量％以上であることがさらに好ましく、８０重量％以上であることがさらに好ましく、８５重量％以上であることがさらに好ましく、９０重量％以上であることが特に好ましい。ポリイソブチレンの含有量の上限は特に限定されるものではなく、９９重量％以下であることが好ましく、９８重量％以下であることがより好ましい。ポリイソブチレンを前記範囲で含むことで、低透湿性に優れるため好ましい。 The content of the polyisobutylene is not particularly limited, but is preferably 50% by weight or more, more preferably 60% by weight or more in the total solid content of the rubber-based pressure-sensitive adhesive composition. It is further preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 85% by weight or more, and particularly preferably 90% by weight or more. The upper limit of the content of polyisobutylene is not particularly limited, and is preferably 99% by weight or less, and more preferably 98% by weight or less. It is preferable that polyisobutylene is contained in the above range because it is excellent in low moisture permeability.
　また、本発明で使用するゴム系粘着剤組成物においては、前記ポリイソブチレン以外のポリマーやエラストマー等を含むこともできる。具体的には、イソブチレンとノルマルブチレンとの共重合体、イソブチレンとイソプレンとの共重合体（例えば、レギュラーブチルゴム、塩素化ブチルゴム、臭素化ブチルゴム、部分架橋ブチルゴム等のブチルゴム類）、これらの加硫物や変性物（例えば、水酸基、カルボキシル基、アミノ基、エポキシ基等の官能基で変性したもの）等のイソブチレン系ポリマー；スチレン－エチレン－ブチレン－スチレンブロック共重合体（ＳＥＢＳ）、スチレン－イソプレン－スチレンブロック共重合体（ＳＩＳ）、スチレン－ブタジエン－スチレンブロック共重合体（ＳＢＳ）、スチレン－エチレン－プロピレン－スチレンブロック共重合体（ＳＥＰＳ、ＳＩＳの水添物）、スチレン－エチレン－プロピレンブロック共重合体（ＳＥＰ、スチレン－イソプレンブロック共重合体の水添物）、スチレン－イソブチレン－スチレンブロック共重合体（ＳＩＢＳ）、スチレン－ブタジエンゴム（ＳＢＲ）等のスチレン系ブロックコポリマー等のスチレン系熱可塑性エラストマー；ブチルゴム（ＩＩＲ）、ブタジエンゴム（ＢＲ）、アクリロニトリル－ブタジエンゴム（ＮＢＲ）、ＥＰＲ（二元系エチレン－プロピレンゴム）、ＥＰＴ（三元系エチレン－プロピレンゴム）、アクリルゴム、ウレタンゴム、ポリウレタン系熱可塑性エラストマー；ポリエステル系熱可塑性エラストマー；ポリプロピレンとＥＰＴ（三元系エチレン－プロピレンゴム）とのポリマーブレンド等のブレンド系熱可塑性エラストマー等が挙げられる。これらは、本発明の効果を損なわない範囲で添加することができるが、前記ポリイソブチレン１００重量部に対して１０重量部程度以下であることが好ましく、耐久性の観点からは、含まないことが好ましい。 Further, the rubber-based pressure-sensitive adhesive composition used in the present invention may contain a polymer, an elastomer, or the like other than the polyisobutylene. Specifically, copolymers of isobutylene and normal butylene, copolymers of isobutylene and isoprene (for example, butyl rubbers such as regular butyl rubber, chlorinated butyl rubber, brominated butyl rubber, and partially crosslinked butyl rubber), and vulcanization thereof And modified products (for example, those modified with a functional group such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group); styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene -Styrene block copolymer (SIS), Styrene-butadiene-styrene block copolymer (SBS), Styrene-ethylene-propylene-styrene block copolymer (SEPS, SIS hydrogenated product), Styrene-ethylene-propylene block Copolymer (SEP, styrene-a Styrene-based thermoplastic elastomers such as styrene-based block copolymers such as styrene-isobutylene-styrene block copolymer (SIBS) and styrene-butadiene rubber (SBR); butyl rubber (IIR), Butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), EPR (binary ethylene-propylene rubber), EPT (ternary ethylene-propylene rubber), acrylic rubber, urethane rubber, polyurethane thermoplastic elastomer; polyester Thermoplastic elastomers; blend thermoplastic elastomers such as polymer blends of polypropylene and EPT (ternary ethylene-propylene rubber). These can be added within a range that does not impair the effects of the present invention, but is preferably about 10 parts by weight or less with respect to 100 parts by weight of the polyisobutylene, and may not be included from the viewpoint of durability. preferable.
　また、本発明で使用するゴム系粘着剤組成物は、前記ポリイソブチレンと水素引抜型光重合開始剤を含むことが特に好ましい。 Further, the rubber-based pressure-sensitive adhesive composition used in the present invention particularly preferably contains the polyisobutylene and a hydrogen abstraction type photopolymerization initiator.
　前記水素引抜型光重合開始剤とは、活性エネルギー線を照射することで、開始剤自身は開裂することなく、前記ポリイソブチレンより水素を引き抜き、ポリイソブチレンに反応点を作ることができるものである。当該反応点形成により、ポリイソブチレンの架橋反応を開始することができるものである。 The hydrogen abstraction type photopolymerization initiator is capable of drawing a hydrogen from the polyisobutylene and creating a reactive site in the polyisobutylene without irradiating the initiator itself by irradiating active energy rays. . By forming the reaction point, the crosslinking reaction of polyisobutylene can be started.
　光重合開始剤としては、本発明で用いる水素引抜型光重合開始剤の他に、活性エネルギー線の照射により、光重合開始剤自身が開裂分解してラジカルを発生させる開裂型光重合開始剤も知られている。しかしながら、本発明で用いるポリイソブチレンに、開裂型光重合開始剤を用いると、ラジカルが発生した光重合開始剤によりポリイソブチレンの主鎖が切断されてしまい、架橋することができないものである。本発明においては、水素引抜型光重合開始剤を用いることで、前述の通りポリイソブチレンの架橋をすることができるものである。 As the photopolymerization initiator, in addition to the hydrogen abstraction type photopolymerization initiator used in the present invention, there are also cleavage type photopolymerization initiators that generate radicals by cleavage of the photopolymerization initiator itself upon irradiation with active energy rays. Are known. However, when a cleavage type photopolymerization initiator is used for the polyisobutylene used in the present invention, the main chain of polyisobutylene is cleaved by the photopolymerization initiator in which radicals are generated, and cannot be crosslinked. In the present invention, by using a hydrogen abstraction type photopolymerization initiator, polyisobutylene can be crosslinked as described above.
　水素引抜型光重合開始剤としては、例えば、アセトフェノン、ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル－４－フェニルベンゾフェノン、４，４’－ジクロロベンゾフェノン、ヒドロキシベンゾフェノン、４，４’－ジメトキシベンゾフェノン、４，４’－ジクロルベンゾフェノン、４，４’－ジメチルベンゾフェノン、４－ベンゾイル－４’－メチル－ジフェニルサルファイド、アクリル化ベンゾフェノン、３，３’，４，４’－テトラ（ｔ－ブチルペルオキシカルボニル）ベンゾフェノン、３，３’－ジメチル－４－メトキシベンゾフェノン等のベンゾフェノン系化合物；２－イソプロピルチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン等のチオキサントン系化合物；４，４’－ビス(ジメチルアミノ)ベンゾフェノン、４，４’－ジエチルアミノベンゾフェノン等のアミノベンゾフェノン系化合物；１０－ブチル－２－クロロアクリドン、２－エチルアンスラキノン、９，１０－フェナンスレンキノン、カンファーキノン等；アセトナフトン、１－ヒドロキシシクロヘキシルフェニルケトン等の芳香族ケトン化合物；テレフタルアルデヒド等の芳香族アルデヒド、メチルアントラキノン等のキノン系芳香族化合物が挙げられる。これらは１種単独で、又は、２種以上を混合して用いることができる。これらの中でも、反応性の点から、ベンゾフェノン系化合物が好ましく、ベンゾフェノンがより好ましい。 Examples of the hydrogen abstraction type photopolymerization initiator include acetophenone, benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4,4′-dimethoxybenzophenone, 4,4 '-Dichlorobenzophenone, 4,4'-dimethylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 3,3′-dimethyl-4-methoxybenzophenone; thioxanes such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Compounds such as 4,4′-bis (dimethylamino) benzophenone and 4,4′-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10- Examples thereof include phenanthrenequinone and camphorquinone; aromatic ketone compounds such as acetonaphthone and 1-hydroxycyclohexyl phenyl ketone; aromatic aldehydes such as terephthalaldehyde; and quinone aromatic compounds such as methylanthraquinone. These can be used individually by 1 type or in mixture of 2 or more types. Among these, from the viewpoint of reactivity, a benzophenone-based compound is preferable, and benzophenone is more preferable.
　前記水素引抜型光重合開始剤の含有量は、前記ポリイソブチレン１００重量部に対して、０．００１～１０重量部であることが好ましく、０．００５～１０重量部であることがより好ましく、０．０１～１０重量部であることがさらに好ましい。水素引抜型光重合開始剤を前記範囲で含むことで、架橋反応を目的の密度まで進行させることができるため好ましい。 The content of the hydrogen abstraction type photopolymerization initiator is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 10 parts by weight with respect to 100 parts by weight of the polyisobutylene. More preferably, it is 0.01 to 10 parts by weight. It is preferable to include a hydrogen abstraction type photopolymerization initiator in the above-mentioned range since the crosslinking reaction can proceed to a target density.
　また、本発明においては、本発明の効果を損なわない範囲で、開裂型光重合開始剤を前記水素引抜型光重合開始剤と伴に用いてもよいが、前述の理由により用いないことが好ましい。 In the present invention, a cleavage type photopolymerization initiator may be used together with the hydrogen abstraction type photopolymerization initiator as long as the effects of the present invention are not impaired. .
　本発明で使用するゴム系粘着剤組成物は、さらに多官能ラジカル重合性化合物を含むことができる。本発明において、多官能ラジカル重合性化合物はポリイソブチレンの架橋剤として機能するものである。 The rubber-based pressure-sensitive adhesive composition used in the present invention can further contain a polyfunctional radical polymerizable compound. In the present invention, the polyfunctional radically polymerizable compound functions as a crosslinking agent for polyisobutylene.
　前記多官能ラジカル重合性化合物は、（メタ）アクリロイル基又はビニル基等の不飽和二重結合を有するラジカル重合性の官能基を少なくも２つ有する化合物である。多官能ラジカル重合性化合物の具体的としては、例えば、トリプロピレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（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、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、２－エチル－２－ブチルプロパンジオールジ（メタ）アクリレート、ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＡエチレンオキサイド付加物ジ（メタ）アクリレート、ビスフェノールＡプロピレンオキサイド付加物ジ（メタ）アクリレート、ビスフェノールＡジグリシジルエーテルジ（メタ）アクリレート、ネオぺンチルグリコールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリート、ジオキサングリコールジ（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、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（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、ＥＯ変性ジグリセリンテトラ（メタ）アクリレート等の（メタ）アクリル酸と多価アルコールとのエステル化物、９，９－ビス［４－（２－（メタ）アクリロイルオキシエトキシ）フェニル］フルオレン等を挙げることができる。これらを１種単独で、又は２種以上の混合物として用いることができる。これらの中でも、ポリイソブチレンに対する相溶性の観点から、（メタ）アクリル酸と多価アルコールとのエステル化物が好ましく、（メタ）アクリロイル基を２つ有する２官能（メタ）アクリレート、（メタ）アクリロイル基を３つ以上有する３官能（メタ）アクリレートがより好ましく、トリシクロデカンジメタノールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレートが特に好ましい。 The polyfunctional radical polymerizable compound is a compound having at least two radical polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group. Specific examples of the polyfunctional radical polymerizable compound include, for example, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol. Di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-ethyl-2-butylpropanediol di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) ) Acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) Cleats, dioxane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meta) ) Acrylate, EO-modified diglycerin tetra (meth) acrylate, etc., esterified products of (meth) acrylic acid and polyhydric alcohol, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, etc. Can be mentioned. These can be used singly or as a mixture of two or more. Among these, from the viewpoint of compatibility with polyisobutylene, an esterified product of (meth) acrylic acid and a polyhydric alcohol is preferable, and a bifunctional (meth) acrylate having two (meth) acryloyl groups, a (meth) acryloyl group. Are more preferable, and tricyclodecane dimethanol di (meth) acrylate and trimethylolpropane tri (meth) acrylate are particularly preferable.
　前記多官能ラジカル重合性化合物の含有量は、前記ポリイソブチレン１００重量部に対して２０重量部以下であることが好ましく、１５重量以下であることがより好ましく、１０重量部以下であることがさらに好ましい。また、多官能ラジカル重合性化合物の含有量の下限値は特に限定されるものではないが、例えば、前記ポリイソブチレン１００重量部に対して０．１重量部以上であることが好ましく、０．５重量部以上であることがより好ましく、１重量部以上であることがさらに好ましい。多官能ラジカル重合性化合物の含有量が前記範囲にあることで、得られたゴム系粘着剤層の耐久性の観点から好ましい。 The content of the polyfunctional radically polymerizable compound is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and further preferably 10 parts by weight or less based on 100 parts by weight of the polyisobutylene. preferable. Further, the lower limit value of the content of the polyfunctional radical polymerizable compound is not particularly limited. For example, it is preferably 0.1 parts by weight or more with respect to 100 parts by weight of the polyisobutylene, More preferably, it is more than 1 part by weight, and still more preferably 1 part by weight. It is preferable from a viewpoint of durability of the obtained rubber-type adhesive layer that content of a polyfunctional radically polymerizable compound exists in the said range.
　多官能ラジカル重合性化合物の分子量は、特に限定されないが、例えば、１０００以下程度であることが好ましく、５００以下程度であることがより好ましい。 The molecular weight of the polyfunctional radically polymerizable compound is not particularly limited, but is preferably about 1000 or less, and more preferably about 500 or less.
　本発明で使用するゴム系粘着剤組成物は、テルペン骨格を含む粘着付与剤、ロジン骨格を含む粘着付与剤、及びこれらの水添物からなる群から選択される少なくとも１種の粘着付与剤を含むことができる。ゴム系粘着剤組成物に粘着付与剤を含むことで、各種被着体に対して高い接着性を有し、かつ、高温環境下においても高い耐久性を有するゴム系粘着剤層を形成することができるため、好ましい。 The rubber-based pressure-sensitive adhesive composition used in the present invention comprises at least one tackifier selected from the group consisting of a tackifier containing a terpene skeleton, a tackifier containing a rosin skeleton, and a hydrogenated product thereof. Can be included. By including a tackifier in the rubber-based pressure-sensitive adhesive composition, a rubber-based pressure-sensitive adhesive layer having high adhesion to various adherends and having high durability even in a high temperature environment is formed. Is preferable.
　前記テルペン骨格を含む粘着付与剤としては、例えば、α－ピネン重合体、β－ピネン重合体、ジペンテン重合体等のテルペン重合体や、前記テルペン重合体を変性（フェノール変性、スチレン変性、芳香族変性、水素添加変性、炭化水素変性等）した変性テルペン樹脂等が挙げられる。上記変性テルペン樹脂の例には、テルペンフェノール樹脂、スチレン変性テルペン樹脂、芳香族変性テルペン樹脂、水素添加テルペン樹脂（水素化テルペン樹脂）等が含まれる。ここでいう水素添加テルペン樹脂の例には、テルペン重合体の水素化物及び他の変性テルペン樹脂、テルペンフェノール樹脂の水素添加物が含まれる。これらの中でも、ゴム系粘着剤組成物への相溶性や粘着特性の観点から、テルペンフェノール樹脂の水素添加物が好ましい。 Examples of the tackifier containing the terpene skeleton include terpene polymers such as α-pinene polymer, β-pinene polymer and dipentene polymer, and modified terpene polymers (phenol-modified, styrene-modified, aromatic). Modified terpene resin and the like). Examples of the modified terpene resin include terpene phenol resin, styrene modified terpene resin, aromatic modified terpene resin, hydrogenated terpene resin (hydrogenated terpene resin) and the like. Examples of the hydrogenated terpene resin herein include a hydride of a terpene polymer and other modified terpene resins and hydrogenated terpene phenol resins. Among these, a hydrogenated product of terpene phenol resin is preferable from the viewpoint of compatibility with the rubber-based pressure-sensitive adhesive composition and pressure-sensitive adhesive properties.
　前記ロジン骨格を含む粘着付与剤としては、ロジン樹脂、重合ロジン樹脂、水添ロジン樹脂、ロジンエステル樹脂、水添ロジンエステル樹脂、ロジンフェノール樹脂等が挙げられ、具体的には、ガムロジン、ウッドロジン、トール油ロジン等の未変性ロジン（生ロジン）や、これらを水添化、不均化、重合、その他の化学的に修飾された変性ロジン、これらの誘導体を使用することができる。 Examples of the tackifier containing the rosin skeleton include rosin resin, polymerized rosin resin, hydrogenated rosin resin, rosin ester resin, hydrogenated rosin ester resin, rosin phenol resin, and the like. Specifically, gum rosin, wood rosin, Unmodified rosin such as tall oil rosin (raw rosin), hydrogenated, disproportionated, polymerized, other chemically modified modified rosin, and derivatives thereof can be used.
　前記粘着付与剤としては、例えば、ヤスハラケミカル（株）製のクリアロンシリーズ、ポリスターシリーズ、荒川化学工業（株）製のスーパーエステルシリーズ、ペンセルシリーズ、パインクリスタルシリーズ等の市販品を使用することができる。 As the tackifier, for example, commercially available products such as the Clearon series, Polystar series, Superester series, Pencel series, Pine Crystal series, etc. manufactured by Yashara Chemical Co., Ltd. may be used. it can.
　前記粘着付与剤が水素添加物である場合、水素添加は、部分的に水素添加されている部分水素添加物であってもよく、化合物中の全ての二重結合に水素添加がされている完全水素添加物であってもよい。本発明においては、粘着特性、耐候性や色相の観点から完全水素添加物であることが好ましい。 When the tackifier is a hydrogenated product, the hydrogenation may be a partially hydrogenated product that has been partially hydrogenated, and all the double bonds in the compound are fully hydrogenated. It may be a hydrogenated product. In the present invention, a completely hydrogenated product is preferred from the viewpoints of adhesive properties, weather resistance and hue.
　前記粘着付与剤が、シクロヘキサノール骨格を含むことが粘着特性の観点から好ましい。これは詳細な原理は不明であるが、フェノール骨格よりシクロヘキサノール骨格の方が、ベースポリマーであるポリイソブチレンとの相溶性のバランスがとれるためと考えられる。シクロヘキサノール骨格を含む粘着付与剤としては、例えば、テルペンフェノール樹脂、ロジンフェノール樹脂等の水添物が好ましく、テルペンフェノール樹脂、ロジンフェノール樹脂等の完全水素添加物がより好ましい。 The tackifier preferably contains a cyclohexanol skeleton from the viewpoint of adhesive properties. Although the detailed principle is unknown, it is thought that the cyclohexanol skeleton is more compatible with the base polymer polyisobutylene than the phenol skeleton. As a tackifier containing a cyclohexanol skeleton, for example, hydrogenated products such as terpene phenol resin and rosin phenol resin are preferable, and complete hydrogenated products such as terpene phenol resin and rosin phenol resin are more preferable.
　前記粘着付与剤の軟化点（軟化温度）は、特に限定されないが、例えば、８０℃以上程度であることが好ましく、１００℃以上程度であることがより好ましい。粘着付与剤の軟化点が８０℃以上であることで、高温においても粘着付与剤が軟化せずに粘着特性を保つことができるため好ましい。粘着付与剤の軟化点の上限値は、特に限定されないが、軟化点が高くなり過ぎると、分子量がより高くなり、相溶性が悪化し、白化等の不具合を生じてしまう場合があるため、例えば、２００℃以下程度であることが好ましく、１８０℃以下程度であることが好ましい。なお、ここでいう粘着付与樹脂の軟化点は、ＪＩＳ　Ｋ５９０２及びＪＩＳ　Ｋ２２０７のいずれかに規定する軟化点試験方法（環球法）によって測定された値として定義される。 The softening point (softening temperature) of the tackifier is not particularly limited, but is preferably about 80 ° C. or higher, and more preferably about 100 ° C. or higher. It is preferable that the tackifier has a softening point of 80 ° C. or higher because the tackifier can be kept soft without being softened even at high temperatures. The upper limit value of the softening point of the tackifier is not particularly limited, but if the softening point becomes too high, the molecular weight becomes higher, the compatibility deteriorates, and problems such as whitening may occur. The temperature is preferably about 200 ° C. or less, and preferably about 180 ° C. or less. In addition, the softening point of the tackifier resin here is defined as a value measured by a softening point test method (ring ball method) defined in either JIS K5902 or JIS K2207.
　前記粘着付与剤の重量平均分子量（Ｍｗ）は、特に限定されるものではないが、５万以下であることが好ましく、３万以下であることが好ましく、１万以下であることがより好ましく、８０００以下であることがさらに好ましく、５０００以下であることが特に好ましい。また、前記粘着付与剤の重量平均分子量の下限値は特に限定されるものではないが、５００以上であることが好ましく、１０００以上であることがより好ましく、２０００以上であることがさらに好ましい。前記粘着付与剤の重量平均分子量が前記範囲にあることで、ポリイソブチレンとの相溶性が良く、白化等の不具合を生じないため好ましい。 The weight average molecular weight (Mw) of the tackifier is not particularly limited, but is preferably 50,000 or less, preferably 30,000 or less, and more preferably 10,000 or less, It is more preferably 8000 or less, and particularly preferably 5000 or less. Moreover, the lower limit of the weight average molecular weight of the tackifier is not particularly limited, but is preferably 500 or more, more preferably 1000 or more, and further preferably 2000 or more. It is preferable that the weight average molecular weight of the tackifier is in the above range because the compatibility with polyisobutylene is good and problems such as whitening do not occur.
　前記粘着付与剤の添加量は、前記ポリイソブチレン１００重量部に対して、４０重量部以下であることが好ましく、３０重量部以下であることがより好ましく、２０重量部以下であることがさらに好ましい。また、粘着付与剤の添加量の下限値は特に限定されるものではないが、０．１重量部以上であることが好ましく、１重量部以上であることがより好ましく、５重量部以上であることがさらに好ましい。粘着付与剤の使用量を前記範囲にすることで、粘着特性を向上できるため好ましい。また、粘着付与剤の使用量が前記範囲を超えて多量添加となると、粘着剤の凝集力が低下してしまう傾向があり、好ましくない。 The addition amount of the tackifier is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, and further preferably 20 parts by weight or less with respect to 100 parts by weight of the polyisobutylene. . Moreover, the lower limit of the addition amount of the tackifier is not particularly limited, but is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and 5 parts by weight or more. More preferably. By making the usage-amount of a tackifier into the said range, since an adhesive characteristic can be improved, it is preferable. Moreover, when the usage-amount of a tackifier exceeds the said range and adds in large quantities, there exists a tendency for the cohesive force of an adhesive to fall, and it is unpreferable.
　また、本発明で使用するゴム系粘着剤組成物には、前記テルペン骨格を含む粘着付与剤、ロジン骨格を含む粘着付与剤以外の粘着付与剤を添加することもできる。当該粘着付与剤としては、石油樹脂系粘着付与剤を挙げることできる。前記石油系粘着付与剤としては、例えば、芳香族系石油樹脂、脂肪族系石油樹脂、脂環族系石油樹脂（脂肪族環状石油樹脂）、脂肪族・芳香族系石油樹脂、脂肪族・脂環族系石油樹脂、水素添加石油樹脂、クマロン系樹脂、クマロンインデン系樹脂等が挙げられる。 Moreover, tackifiers other than the tackifier containing the terpene skeleton and the tackifier containing the rosin skeleton can be added to the rubber-based pressure-sensitive adhesive composition used in the present invention. Examples of the tackifier include petroleum resin-based tackifiers. Examples of the petroleum-based tackifier include aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins (aliphatic cyclic petroleum resins), aliphatic / aromatic petroleum resins, aliphatic / aliphatic resins. Examples thereof include cyclic petroleum resins, hydrogenated petroleum resins, coumarone resins, coumarone indene resins, and the like.
　前記石油樹脂系粘着付与剤は、本発明の効果を損なわない範囲で用いることができるが、例えば、前記ポリイソブチレン１００重量部に対して、３０重量部以下程度で用いることができる。 The petroleum resin tackifier can be used within a range that does not impair the effects of the present invention. For example, it can be used in an amount of about 30 parts by weight or less with respect to 100 parts by weight of the polyisobutylene.
　前記ゴム系粘着剤組成物には、希釈剤として有機溶媒を添加することができる。希釈剤としては、特に限定されるものではないが、例えば、トルエン、キシレン、ｎ－ヘプタン、ジメチルエーテル等を挙げることができ、これらを１種単独で又は２種以上を混合して使用することができる。これらの中でも、トルエンが好ましい。 An organic solvent can be added as a diluent to the rubber-based pressure-sensitive adhesive composition. The diluent is not particularly limited, and examples thereof include toluene, xylene, n-heptane, dimethyl ether, and the like. These may be used alone or in combination of two or more. it can. Among these, toluene is preferable.
　希釈剤の添加量は、特に限定されるものではないが、ゴム系粘着剤組成物中に５０～９５重量％程度で添加することが好ましく、７０～９０重量％程度であることがより好ましい。希釈剤の添加量が前記範囲であることにより、支持体等へ塗工性の観点から好ましい。 The addition amount of the diluent is not particularly limited, but it is preferably added to the rubber-based pressure-sensitive adhesive composition at about 50 to 95% by weight, and more preferably about 70 to 90% by weight. When the addition amount of the diluent is within the above range, it is preferable from the viewpoint of coatability to a support or the like.
　本発明で使用するゴム系粘着剤組成物には、本発明の効果を損なわない範囲で、前記以外の添加剤を添加することもできる。添加剤の具体例としては、軟化剤、架橋剤（例えば、ポリイソシアネート、エポキシ化合物、アルキルエーテル化メラミン化合物等）、充填剤、老化防止剤、紫外線吸収剤等が挙げられる。ゴム系粘着剤組成物に添加される添加剤の種類、組み合わせ、添加量等は、目的に応じて適切に設定され得る。ゴム系粘着剤組成物における前記添加剤の含有量（総量）は、３０重量％以下であることが好ましく、２０重量％以下であることがより好ましく、１０重量％以下であることがさらに好ましい。 Additives other than those described above can also be added to the rubber-based pressure-sensitive adhesive composition used in the present invention as long as the effects of the present invention are not impaired. Specific examples of the additive include a softening agent, a crosslinking agent (for example, polyisocyanate, epoxy compound, alkyl etherified melamine compound, etc.), filler, anti-aging agent, ultraviolet absorber and the like. The kind, combination, addition amount, and the like of the additive added to the rubber-based pressure-sensitive adhesive composition can be appropriately set according to the purpose. The content (total amount) of the additive in the rubber-based pressure-sensitive adhesive composition is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less.
　本発明で用いる粘着剤層は、前記粘着剤組成物から形成することができ、その製造方法は特に限定されないが、各種支持体等に粘着剤組成物を塗布し、加熱乾燥や活性エネルギー線の照射等により、粘着剤層を形成することができる。 The pressure-sensitive adhesive layer used in the present invention can be formed from the pressure-sensitive adhesive composition, and its production method is not particularly limited, but the pressure-sensitive adhesive composition is applied to various supports, etc. The pressure-sensitive adhesive layer can be formed by irradiation or the like.
　前記ゴム系粘着剤組成物として、ポリイソブチレンを含む場合は、粘着剤組成物に、活性エネルギー線を照射して、前記ポリイソブチレンを架橋することが好ましい。活性エネルギー線の照射は、通常、前記ゴム系粘着剤組成物を各種支持体等に塗布し、得られた塗布層に照射される。また、前記活性エネルギー線の照射は、塗布層に（他部材等を貼り合せることなく）直接照射してもよく、塗布層にセパレーター等の光学フィルムやガラス等の各種部材を貼り合せた後に照射してもよい。前記光学フィルムや各種部材に貼り合せた後に照射する場合は、当該光学フィルムや各種部材越しに活性エネルギー線を照射してもよく、当該光学フィルムや各種部材を剥離して、当該剥離した面から活性エネルギー線を照射してもよい。 When the rubber-based pressure-sensitive adhesive composition contains polyisobutylene, the pressure-sensitive adhesive composition is preferably irradiated with active energy rays to crosslink the polyisobutylene. In general, the active energy ray is applied to the coating layer obtained by applying the rubber-based pressure-sensitive adhesive composition to various supports. In addition, the active energy ray may be irradiated directly on the coating layer (without bonding other members, etc.), or after bonding various members such as an optical film such as a separator or glass to the coating layer. May be. In the case of irradiation after bonding to the optical film or various members, active energy rays may be irradiated through the optical film or various members, and the optical film or various members are peeled off, and the peeled surface is used. You may irradiate an active energy ray.
　前記粘着剤組成物の塗布方法としては、各種方法が用いられる。具体的には、例えば、ロールコート、キスロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、ディップロールコート、バーコート、ナイフコート、エアーナイフコート、カーテンコート、リップコート、ダイコーター等による押出しコート法等の方法が挙げられる。 Various methods are used as a method for applying the pressure-sensitive adhesive composition. Specifically, for example, by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
　前記粘着剤組成物の塗布層を加熱乾燥する場合、加熱乾燥温度は、３０℃～２００℃程度が好ましく、４０℃～１８０℃がより好ましく、８０℃～１５０℃がさらに好ましい。加熱温度を上記の範囲とすることによって、優れた粘着特性を有する粘着剤層を得ることができる。乾燥時間は、適宜、適切な時間が採用され得る。上記乾燥時間は、５秒～２０分程度が好ましく、３０秒～１０分がより好ましく、１分～８分がさらに好ましい。 When the coating layer of the pressure-sensitive adhesive composition is heat-dried, the heat-drying temperature is preferably about 30 ° C. to 200 ° C., more preferably 40 ° C. to 180 ° C., and further preferably 80 ° C. to 150 ° C. By setting the heating temperature in the above range, an adhesive layer having excellent adhesive properties can be obtained. As the drying time, an appropriate time can be adopted as appropriate. The drying time is preferably about 5 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and further preferably 1 minute to 8 minutes.
　また、前記粘着剤組成物の塗布層に活性エネルギー線を照射する場合においても、前記接着剤又は粘着剤組成物が、希釈剤として有機溶媒を含有する場合は、塗布後、活性エネルギー線照射前に、加熱乾燥等により溶媒等を除去することが好ましい。 Further, even when the active energy ray is irradiated to the coating layer of the pressure-sensitive adhesive composition, when the adhesive or the pressure-sensitive adhesive composition contains an organic solvent as a diluent, after application, before the irradiation with the active energy ray In addition, it is preferable to remove the solvent and the like by heating and drying.
　前記加熱乾燥温度は、特に限定されないが、残存溶媒を少なくする観点から、３０℃～９０℃程度が好ましく、６０℃～８０℃程度がより好ましい。乾燥時間は、適宜、適切な時間が採用され得る。上記乾燥時間は、５秒～２０分程度が好ましく、３０秒～１０分がより好ましく、１分～８分がさらに好ましい。 The heating and drying temperature is not particularly limited, but is preferably about 30 ° C. to 90 ° C., more preferably about 60 ° C. to 80 ° C. from the viewpoint of reducing the residual solvent. As the drying time, an appropriate time can be adopted as appropriate. The drying time is preferably about 5 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and further preferably 1 minute to 8 minutes.
　前記活性エネルギー線としては、例えば、可視光線、紫外線、電子線等を挙げることができるが、これらの中でも、紫外線が好ましい。 Examples of the active energy rays include visible light, ultraviolet rays, and electron beams. Among these, ultraviolet rays are preferable.
　紫外線の照射条件は、特に限定されるものではなく、架橋させるゴム系粘着剤組成の組成に応じて、任意の適切な条件に設定することができるが、例えば、照射積算光量が１００ｍＪ／ｃｍ２～２０００ｍＪ／ｃｍ２が好ましい。 The irradiation condition of ultraviolet rays is not particularly limited, and can be set to any appropriate condition depending on the composition of the rubber-based pressure-sensitive adhesive composition to be crosslinked. For example, the integrated irradiation light amount is 100 mJ / cm 2. ˜2000 mJ / cm 2 is preferred.
　前記支持体としては、例えば、剥離処理したシート（セパレーター）や、前述の位相差フィルムを用いることができる。 As the support, for example, a peeled sheet (separator) or the aforementioned retardation film can be used.
　前記セパレーターの構成材料としては、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリエステルフィルム等のプラスチックフィルム、紙、布、不織布等の多孔質材料、ネット、発泡シート、金属箔、及びこれらのラミネート体等の適宜な薄葉体等を挙げることができるが、表面平滑性に優れる点からプラスチックフィルムが好適に用いられる。 Examples of the constituent material of the separator include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof. Although an appropriate thin leaf body etc. can be mentioned, a plastic film is used suitably from the point which is excellent in surface smoothness.
　前記プラスチックフィルムとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン－酢酸ビニル共重合体フィルム等が挙げられる。 Examples of the plastic film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene. -Vinyl acetate copolymer film and the like.
　前記セパレーターの厚みは、通常５～２００μｍ、好ましくは５～１００μｍ程度である。前記セパレーターには、必要に応じて、シリコーン系、フッ素系、長鎖アルキル系もしくは脂肪酸アミド系の離型剤、シリカ粉等による離型、及び防汚処理や、塗布型、練り込み型、蒸着型等の帯電防止処理もすることもできる。特に、前記セパレーターの表面にシリコーン処理、長鎖アルキル処理、フッ素処理等の剥離処理を適宜行うことにより、前記粘着剤層からの剥離性をより高めることができる。 The thickness of the separator is usually about 5 to 200 μm, preferably about 5 to 100 μm. For the separator, silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, release by silica powder, and antifouling treatment, coating type, kneading type, vapor deposition, as required An antistatic treatment such as a mold can also be performed. In particular, the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the separator.
　前記粘接着剤層を、剥離処理したシート（セパレーター）上に形成した場合、当該粘着剤層を位相差フィルム上に転写して、本発明の粘接着剤層付光学フィルムを形成することもできる。この場合、前記粘着剤層付光学フィルムの作製にあたって用いた、剥離処理したシートは、そのままゴム系粘着剤層付光学フィルムのセパレーターとして用いることができ、工程面における簡略化ができる。 When the adhesive layer is formed on a release-treated sheet (separator), the adhesive layer is transferred onto a retardation film to form the optical film with an adhesive layer of the present invention. You can also. In this case, the release-treated sheet used in the production of the optical film with the pressure-sensitive adhesive layer can be used as it is as a separator for the optical film with the rubber-based pressure-sensitive adhesive layer, and the process can be simplified.
　前記粘着剤層の厚みは、特に限定されるものではなく、その用途に応じて適宜設定することができるが、２５０μｍ以下であることが好ましく、１００μｍ以下であることがより好ましく、５５μｍ以下であることがさらに好ましい。また、粘着剤層の厚みの下限値は、特に限定されるものではないが、耐久性の観点からは、１μｍ以上であることが好ましく、５μｍ以上であることがより好ましい。 The thickness of the pressure-sensitive adhesive layer is not particularly limited and can be appropriately set depending on the application, but is preferably 250 μm or less, more preferably 100 μm or less, and 55 μm or less. More preferably. The lower limit of the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 μm or more and more preferably 5 μm or more from the viewpoint of durability.
　また、本発明で用いる粘着剤層のゲル分率は、特に限定されないが、１０～９８％程度が好ましく、２５～９８％程度がより好ましく、４５～９０％程度であることがさらに好ましい。ゲル分率が前記範囲にあることで、耐久性と粘着力を両立できるため好ましい。なお、ゲル分率の測定方法は、実施例に記載の方法により測定することができる。 The gel fraction of the pressure-sensitive adhesive layer used in the present invention is not particularly limited, but is preferably about 10 to 98%, more preferably about 25 to 98%, and further preferably about 45 to 90%. It is preferable for the gel fraction to be in the above range since both durability and adhesive strength can be achieved. In addition, the measuring method of a gel fraction can be measured by the method as described in an Example.
　（３）その他の層
　本発明の有機ＥＬ表示装置用光学フィルムを構成する、λ／４板として機能する位相差フィルムと、４０℃、９２％Ｒ．Ｈ．における透湿度が５０ｇ／（ｍ２・ｄａｙ）以下の粘接着剤層は、これらが接するように積層されていてもよく、これらの間に他の層を有していてもよい。 (3) Other layers A retardation film functioning as a λ / 4 plate constituting the optical film for an organic EL display device of the present invention, and 40 ° C., 92% R.D. H. The adhesive layer having a moisture permeability of 50 g / (m 2 · day) or less may be laminated so that they are in contact with each other, or may have another layer therebetween.
　前記その他の層としては、前記接粘着剤層以外の接着剤層や粘着剤層（即ち、４０℃、９２％Ｒ．Ｈ．における透湿度が５０ｇ／（ｍ２・ｄａｙ）を超える接着剤層や粘着剤層）、下塗り層（プライマー層）等の介在層を挙げることができる。 Examples of the other layers include an adhesive layer other than the adhesive layer and an adhesive layer (that is, an adhesive layer having a moisture permeability of 50 g / (m 2 · day) at 40 ° C. and 92% RH). And interstitial layers such as an undercoat layer (primer layer).
　前記接着剤層は接着剤により形成される。接着剤の種類は特に制限されず、種々のものを用いることができる。前記接着剤層は光学的に透明であれば特に制限されず、接着剤としては、水系、溶剤系、ホットメルト系、活性エネルギー線硬化型等の各種形態のものが用いられるが、水系接着剤又は活性エネルギー線硬化型接着剤が好適である。 The adhesive layer is formed of an adhesive. The type of the adhesive is not particularly limited, and various types can be used. The adhesive layer is not particularly limited as long as it is optically transparent. Examples of the adhesive include water-based, solvent-based, hot-melt-based, active energy ray-curable types, and the like. Or an active energy ray hardening-type adhesive agent is suitable.
　また、前記位相差フィルムと接粘着剤層の積層にあたって、これらの間に易接着層を設けることができる。易接着層は、例えば、ポリエステル骨格、ポリエーテル骨格、ポリカーボネート骨格、ポリウレタン骨格、シリコーン系、ポリアミド骨格、ポリイミド骨格、ポリビニルアルコール骨格等を有する各種樹脂により形成することができる。これらポリマー樹脂は１種を単独で、又は２種以上を組み合わせて用いることができる。また易接着層の形成には他の添加剤を加えてもよい。具体的には、粘着付与剤、紫外線吸収剤、酸化防止剤、耐熱安定剤等の安定剤等をさらに用いてもよい。 Moreover, when laminating the retardation film and the pressure-sensitive adhesive layer, an easy adhesion layer can be provided between them. The easy adhesion layer can be formed of, for example, various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone-based, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, and the like. These polymer resins can be used alone or in combination of two or more. Moreover, you may add another additive for formation of an easily bonding layer. Specifically, stabilizers such as a tackifier, an ultraviolet absorber, an antioxidant, and a heat stabilizer may be further used.
　本発明の光学フィルムは、有機ＥＬ表示装置用として使用されるものであって、後述する偏光子と伴に、有機ＥＬ表示装置の反射防止フィルム（有機ＥＬ表示装置用偏光フィルム）を構成することができる。 The optical film of the present invention is used for an organic EL display device, and constitutes an antireflection film for an organic EL display device (polarizing film for an organic EL display device) together with a polarizer described later. Can do.
　２．有機ＥＬ表示装置用偏光フィルム
　本発明の有機ＥＬ表示装置用偏光フィルムは、偏光子と、前記有機ＥＬ表示装置用光学フィルムを含むことを特徴とする。 2. Polarizing film for organic EL display device The polarizing film for organic EL display device of the present invention comprises a polarizer and the optical film for organic EL display device.
　本発明の有機ＥＬ表示装置用偏光フィルムは、偏光子と前記有機ＥＬ表示装置用光学フィルムを含むものであれば、その構成は特に限定されないが、例えば、前記偏光子と、位相差フィルム３ａと、粘接着剤層２とをこの順に備える構成や、前記偏光子と、粘接着剤層２と、位相差フィルム３ａとを、この順に備える構成を挙げることができる。 Although the structure will not be specifically limited if the polarizing film for organic EL display devices of this invention contains a polarizer and the said optical film for organic EL display devices, For example, the said polarizer, retardation film 3a, A configuration including the adhesive layer 2 in this order and a configuration including the polarizer, the adhesive layer 2 and the retardation film 3a in this order can be given.
　また、前記偏光子５ａは、当該偏光子５ａの片面のみに保護フィルムを有する片面保護偏光フィルムや、偏光子５ａの両面に保護フィルムを有する両面保護偏光フィルムとして使用することができる。 The polarizer 5a can be used as a single-sided protective polarizing film having a protective film only on one side of the polarizer 5a, or a double-sided protective polarizing film having protective films on both sides of the polarizer 5a.
　本発明の有機ＥＬ表示装置用偏光フィルムの前記構成について、図３を用いてより詳細に説明する。 The said structure of the polarizing film for organic electroluminescent display devices of this invention is demonstrated in detail using FIG.
　偏光子５ａを含む片面保護偏光フィルム５Ａとして用いる場合、図３（ａ）に示すように、保護フィルム５ｂ／偏光子５ａ／接着剤層又は粘着剤層４／位相差フィルム３ａ／粘接着剤層２から構成される偏光フィルムとすることができる。また、偏光子５ａを含む両面保護偏光フィルム５Ｂとして用いる場合は、図３（ｂ）に示すように、保護フィルム５ｂ／偏光子５ａ／保護フィルム５ｂ／接着剤層又は粘着剤層４／位相差フィルム３ａ／粘接着剤層２から構成される偏光フィルムとすることができる。 When used as a single-sided protective polarizing film 5A including a polarizer 5a, as shown in FIG. 3A, the protective film 5b / polarizer 5a / adhesive layer or pressure-sensitive adhesive layer 4 / retardation film 3a / adhesive agent It can be set as the polarizing film comprised from the layer 2. FIG. Moreover, when using as the double-sided protective polarizing film 5B containing the polarizer 5a, as shown in FIG.3 (b), as shown in FIG.3 (b), protective film 5b / polarizer 5a / protective film 5b / adhesive layer or adhesive layer 4 / phase difference It can be set as the polarizing film comprised from the film 3a / adhesive layer 2.
　前記構成（位相差フィルム３ａのみを用いる場合）において、偏光子５ａの吸収軸と位相差フィルム３ａの遅相軸とのなす角度は、３５°～５５°であることが好ましく、３８°～５２°がより好ましく、４０°～５０°がさらに好ましく、４２°～４８°がさらに好ましく、４４°～４６°が特に好ましい。当該角度がこのような範囲であれば、所望の円偏光機能が実現され得るため好ましい。なお、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及び反時計回りの両方の方向の角度を包含する。 In the above configuration (when only the retardation film 3a is used), the angle formed between the absorption axis of the polarizer 5a and the slow axis of the retardation film 3a is preferably 35 ° to 55 °, and preferably 38 ° to 52 °. Is more preferable, 40 ° to 50 ° is more preferable, 42 ° to 48 ° is further preferable, and 44 ° to 46 ° is particularly preferable. If the said angle is such a range, since a desired circular polarization function can be implement | achieved, it is preferable. Note that when an angle is referred to in this specification, the angle includes both clockwise and counterclockwise directions unless otherwise specified.
　前記構成においては、位相差フィルムは、第１の位相差フィルム３ａのみを用いた場合を例示しているが、前述の通り、第２の位相差フィルム３ｂを用いる構成であっても良い。その場合、上記それぞれの構成は、保護フィルム５ｂ／偏光子５ａ／接着剤層又は粘着剤層４／位相差フィルム３ａ／接着剤層又は粘着剤層４／位相差フィルム３ｂ／粘接着剤層２、保護フィルム５ｂ／偏光子５ａ／保護フィルム５ｂ／接着剤層又は粘着剤層４／位相差フィルム３ａ／接着剤層又は粘着剤層４／位相差フィルム３ｂ／粘接着剤層２となる。 In the above configuration, the case where only the first retardation film 3a is used as the retardation film is illustrated, but as described above, the configuration using the second retardation film 3b may be used. In that case, each said structure is protective film 5b / polarizer 5a / adhesive layer or adhesive layer 4 / retardation film 3a / adhesive layer or adhesive layer 4 / retardation film 3b / adhesive layer 2. Protective film 5b / polarizer 5a / protective film 5b / adhesive layer or adhesive layer 4 / retardation film 3a / adhesive layer or adhesive layer 4 / retardation film 3b / adhesive layer 2 .
　前記構成（位相差フィルム３ａと３ｂを用いる場合）において、偏光子５ａの吸収軸と第１の位相差フィルム３ａの遅相軸とのなす角度は、６５°～８５°が好ましく、７２°～７８°がより好ましく、７４°～７６°がさらに好ましい。また、偏光子５ａの吸収軸と第２の位相差フィルム３ｂの遅相軸とのなす角度は、１０°～２０°が好ましく、１３°～１７°がより好ましく、１４°～１６°がさらに好ましい。２つの位相差フィルムを上記のような軸角度で配置することにより、広帯域において非常に優れた円偏光特性（結果として、非常に優れた反射防止特性）を有する円偏光板が得られるため、好ましい。 In the above configuration (when the retardation films 3a and 3b are used), the angle between the absorption axis of the polarizer 5a and the slow axis of the first retardation film 3a is preferably 65 ° to 85 °, preferably 72 ° to 78 ° is more preferable, and 74 ° to 76 ° is even more preferable. Further, the angle formed by the absorption axis of the polarizer 5a and the slow axis of the second retardation film 3b is preferably 10 ° to 20 °, more preferably 13 ° to 17 °, and further preferably 14 ° to 16 °. preferable. Arranging the two retardation films at the axial angles as described above is preferable because a circularly polarizing plate having very excellent circular polarization characteristics (as a result, very excellent antireflection characteristics) in a wide band can be obtained. .
　以下、本発明の有機ＥＬ表示装置用偏光フィルムに用いる各構成要素について説明する。 Hereinafter, each component used for the polarizing film for organic EL display devices of the present invention will be described.
　（有機ＥＬ表示装置用光学フィルム）
　有機ＥＬ表示装置用光学フィルムは、前述のものを挙げることができる。 (Optical film for organic EL display)
The above-mentioned thing can be mentioned for the optical film for organic EL display apparatuses.
　（偏光子）
　偏光子は、特に限定されず、各種のものを使用できる。偏光子としては、例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、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の二色性物質を吸着させて一軸延伸したもの、ポリビニルアルコール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。これらの中でも、ポリビニルアルコール系フィルムとヨウ素等の二色性物質からなる偏光子が好適である。これらの偏光子の厚さは特に制限されないが、一般的に５～８０μｍ程度である。 (Polarizer)
The polarizer is not particularly limited, and various types can be used. Examples of polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films. Examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 μm.
　ポリビニルアルコール系フィルムをヨウ素で染色し一軸延伸した偏光子は、例えば、ポリビニルアルコールをヨウ素の水溶液に浸漬することによって染色し、元長の３～７倍に延伸することで作製することができる。必要に応じてホウ酸や硫酸亜鉛、塩化亜鉛等を含んでいても良いヨウ化カリウム等の水溶液に浸漬することもできる。さらに必要に応じて染色前にポリビニルアルコール系フィルムを水に浸漬して水洗してもよい。ポリビニルアルコール系フィルムを水洗することでポリビニルアルコール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ほかに、ポリビニルアルコール系フィルムを膨潤させることで染色のムラ等の不均一を防止する効果もある。延伸はヨウ素で染色した後に行っても良いし、染色しながら延伸しても良いし、また延伸してからヨウ素で染色しても良い。ホウ酸やヨウ化カリウム等の水溶液や水浴中でも延伸することができる。 A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with stains and antiblocking agents by washing the polyvinyl alcohol film with water, the polyvinyl alcohol film is also swollen to prevent unevenness such as uneven coloring. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even in an aqueous solution of boric acid or potassium iodide or in a water bath.
　また、薄膜化の観点から、厚みが１５μｍ以下の薄型偏光子を用いることが好ましく、１０μｍ以下の薄型偏光子を用いることがより好ましい。薄型化の観点から言えば当該厚みは、１～７μｍであるのが好ましい。このような薄型の偏光子は、厚みムラが少なく、視認性が優れており、また寸法変化が少ないため耐久性に優れ、さらには偏光フィルムとしての厚みも薄型化が図れる点が好ましい。 Further, from the viewpoint of thinning, it is preferable to use a thin polarizer having a thickness of 15 μm or less, and more preferable to use a thin polarizer having a thickness of 10 μm or less. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.
　薄型の偏光子としては、代表的には、特開昭５１－０６９６４４号公報や特開２０００－３３８３２９号公報や、国際公開第２０１０／１００９１７号パンフレット、又は特開２０１４－５９３２８号公報や特開２０１２－７３５６３号公報に記載されている薄型偏光膜を挙げることができる。これら薄型偏光膜は、ポリビニルアルコール系樹脂（以下、ＰＶＡ系樹脂ともいう）層と延伸用樹脂基材を積層体の状態で延伸する工程と染色する工程を含む製法により得ることができる。この製法であれば、ＰＶＡ系樹脂層が薄くても、延伸用樹脂基材に支持されていることにより延伸による破断等の不具合なく延伸することが可能となる。 As the thin polarizer, typically, Japanese Patent Application Laid-Open No. 51-069644, Japanese Patent Application Laid-Open No. 2000-338329, International Publication No. 2010/100917 pamphlet, Japanese Patent Application Laid-Open No. 2014-59328, and Japanese Patent Application Laid-Open No. 2014-59328 are disclosed. The thin polarizing film described in 2012-73563 gazette can be mentioned. These thin polarizing films can be obtained by a production method including a step of stretching and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin substrate in the state of a laminate. With this production method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.
　前記薄型偏光膜としては、積層体の状態で延伸する工程と染色する工程を含む製法の中でも、高倍率に延伸できて偏光性能を向上させることのできる点で、国際公開第２０１０／１００９１７号パンフレット、又は特開２０１４－０５９３２８号公報や特開２０１２－０７３５６３号公報に記載のあるようなホウ酸水溶液中で延伸する工程を含む製法で得られるものが好ましく、特に特開２０１４－０５９３２８号公報や特開２０１２－０７３５６３号公報に記載のあるホウ酸水溶液中で延伸する前に補助的に空中延伸する工程を含む製法により得られるものが好ましい。 As the thin polarizing film, International Publication No. 2010/100917 pamphlet in that it can be stretched at a high magnification and the polarization performance can be improved among the production methods including the step of stretching in the state of a laminate and the step of dyeing. Or obtained by a production method including a step of stretching in a boric acid aqueous solution as described in Japanese Patent Application Laid-Open No. 2014-059328 and Japanese Patent Application Laid-Open No. 2012-0753563. What is obtained by the manufacturing method including the process of extending | stretching in the air auxiliary before extending | stretching in the boric-acid aqueous solution described in Unexamined-Japanese-Patent No. 2012-0753563 is preferable.
　（保護フィルム）
　前記偏光子の片面又は両面に設けられる保護フィルムを形成する材料としては、透明性、機械的強度、熱安定性、水分遮断性、等方性等に優れるものが好ましい。例えば、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル系ポリマー、ジアセチルセルロースやトリアセチルセルロース等のセルロース系ポリマー、ポリメチルメタクリレート等のアクリル系ポリマー、ポリスチレンやアクリロニトリル・スチレン共重合体（ＡＳ樹脂）等のスチレン系ポリマー、ポリカーボネート系ポリマー等が挙げられる。また、ポリエチレン、ポリプロピレン、シクロ系ないしはノルボルネン構造を有するポリオレフィン、エチレン・プロピレン共重合体等のポリオレフィン系ポリマー、塩化ビニル系ポリマー、ナイロンや芳香族ポリアミド等のアミド系ポリマー、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマー、又は、前記ポリマーのブレンド物等も前記保護フィルムを形成するポリマーの例として挙げられる。保護フィルムは、アクリル系、ウレタン系、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、紫外線硬化型の樹脂の硬化層として形成することもできる。偏光子の両側に保護フィルムを設ける場合、その表裏で同じポリマー材料からなる保護フィルムを用いても良く、異なるポリマー材料等からなる保護フィルムを用いても良い。 (Protective film)
As a material for forming a protective film provided on one side or both sides of the polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) And polymers based on polycarbonate and polycarbonate. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the protective film include blends of the polymer. The protective film can also be formed as a cured layer of an acrylic, urethane, acrylic urethane, epoxy, silicone, or other thermosetting or ultraviolet curable resin. When providing a protective film on both sides of the polarizer, a protective film made of the same polymer material may be used on the front and back, or a protective film made of a different polymer material or the like may be used.
　保護フィルムの厚みは、適宜に決定しうるが、一般には強度や取扱性等の作業性、薄膜性等の点より１～５００μｍ程度である。 The thickness of the protective film can be determined as appropriate, but is generally about 1 to 500 μm from the viewpoints of workability such as strength and handleability, and thin film properties.
　前記偏光子と保護フィルムとは通常、水系接着剤等を介して密着している。水系接着剤としては、イソシアネート系接着剤、ポリビニルアルコール系接着剤、ゼラチン系接着剤、ビニル系ラテックス系、水系ポリウレタン、水系ポリエステル等を例示できる。上記の他、偏光子と保護フィルムとの接着剤としては、紫外硬化型接着剤、電子線硬化型接着剤等が挙げられる。電子線硬化型偏光フィルム用接着剤は、上記各種の保護フィルムに対して、好適な接着性を示す。また本発明で用いる接着剤には、金属化合物フィラーを含有させることができる。 The polarizer and the protective film are usually in close contact with each other through an aqueous adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester. In addition to the above, examples of the adhesive between the polarizer and the protective film include an ultraviolet curable adhesive and an electron beam curable adhesive. The electron beam curable polarizing film adhesive exhibits suitable adhesion to the various protective films. The adhesive used in the present invention can contain a metal compound filler.
　前記保護フィルムの偏光子を接着させない面には、ハードコート層や反射防止処理、スティッキング防止や、拡散ないしアンチグレアを目的とした処理を施したものであっても良い。 The surface of the protective film to which the polarizer is not adhered may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.
　（接着剤層又は粘着剤層）
　偏光フィルム５と位相差フィルム３ａの接着や、位相差フィルム３ａと位相差フィルム３ｂの接着に用いられる接着剤層又は粘着剤層４としては、特に限定されるものではなく、本明細書中に記載のものを好適に使用することができる。具体的には、位相差フィルム３ａと位相差フィルム３ｂの接着には、例えば、（メタ）アクリル系ポリマーをベースポリマーとするアクリル系粘着剤が、光学的透明性に優れ、適度な濡れ性と凝集性と接着性の粘着特性を示して、耐候性や耐熱性等に優れているため、好ましい。偏光フィルム５と位相差フィルム３ａの接着は、偏光子と保護フィルムとの接着に用いられる前記水系接着剤等を挙げることができ、具体的には、ポリビニルアルコール系接着剤が好ましい。 (Adhesive layer or adhesive layer)
The adhesive layer or the pressure-sensitive adhesive layer 4 used for adhesion between the polarizing film 5 and the retardation film 3a, or adhesion between the retardation film 3a and the retardation film 3b is not particularly limited. Those described can be preferably used. Specifically, for adhesion between the retardation film 3a and the retardation film 3b, for example, an acrylic pressure-sensitive adhesive having a (meth) acrylic polymer as a base polymer is excellent in optical transparency and has an appropriate wettability. It is preferable because it exhibits cohesive and adhesive adhesive properties and is excellent in weather resistance, heat resistance, and the like. Examples of the adhesion between the polarizing film 5 and the retardation film 3a include the water-based adhesive used for the adhesion between the polarizer and the protective film. Specifically, a polyvinyl alcohol-based adhesive is preferable.
　（その他の層）
　本発明の有機ＥＬ表示装置用偏光フィルムには、前記以外の接着剤層や粘着剤層、下塗り層（プライマー層）等の介在層や、易接着層を含んでいてもよい。介在層や易接着剤層は、前述のものを挙げることができる。 (Other layers)
The polarizing film for an organic EL display device of the present invention may contain an intervening layer such as an adhesive layer, a pressure-sensitive adhesive layer, and an undercoat layer (primer layer) other than those described above, and an easily adhesive layer. Examples of the intervening layer and the easy-adhesive layer may include those described above.
　また、本発明の有機ＥＬ表示装置用偏光フィルムには、機能層を設けることができる。機能層を設けることで、偏光子に生じる貫通クラック及びナノスリット等の欠陥の発生を抑制することができるため、好ましい。機能層は、各種の形成材から形成することができる。機能層は、例えば、樹脂材料を偏光子に塗布することにより形成することができる。 Moreover, a functional layer can be provided in the polarizing film for organic EL display devices of the present invention. Providing the functional layer is preferable because generation of defects such as through cracks and nano slits generated in the polarizer can be suppressed. The functional layer can be formed from various forming materials. The functional layer can be formed, for example, by applying a resin material to the polarizer.
　前記機能層を形成する樹脂材料としては、例えば、ポリエステル系樹脂、ポリエーテル系樹脂、ポリカーボネート系樹脂、ポリウレタン系樹脂、シリコーン系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ＰＶＡ系樹脂、アクリル系樹脂等を挙げることができる。これら樹脂材料は１種を単独で又は２種以上を組み合わせて用いることができるが、これらの中でも、ポリウレタン系樹脂、ポリビニルアルコール（ＰＶＡ）系樹脂からなる群から選択される１種以上が好ましく、ＰＶＡ系樹脂がより好ましい。また、前記樹脂の形態は、水系、溶剤系のいずれでもよい。前記樹脂の形態は、水系樹脂が好ましく、ＰＶＡ系樹脂が好ましい。また、水系樹脂としては、アクリル樹脂水溶液やウレタン樹脂水溶液を用いることができる。 Examples of the resin material forming the functional layer include polyester resins, polyether resins, polycarbonate resins, polyurethane resins, silicone resins, polyamide resins, polyimide resins, PVA resins, acrylic resins, and the like. Can be mentioned. These resin materials can be used alone or in combination of two or more, but among these, one or more selected from the group consisting of polyurethane-based resins and polyvinyl alcohol (PVA) -based resins are preferable, PVA resin is more preferable. The form of the resin may be either water-based or solvent-based. The resin is preferably a water-based resin, and is preferably a PVA-based resin. As the water-based resin, an acrylic resin aqueous solution or a urethane resin aqueous solution can be used.
　前記機能層は、厚くなりすぎると光学信頼性と耐水性が低下するため、機能層の厚みは１５μｍ以下であるのが好ましく、１０μｍ以下であるのがより好ましく、８μｍ以下がさらに好ましく、６μｍ以下がさらに好ましく、５μｍ以下がさらに好ましく、３μｍ以下が特に好ましい。一方、機能層の厚みは０．２μｍ以上であることが好ましく、０．５μｍ以上であるのがより好ましく、０．７μｍ以上であるのがさらに好ましい。当該厚みの機能層により、クラックの発生を抑制することができるため、好ましい。 If the functional layer becomes too thick, the optical reliability and water resistance are lowered. Therefore, the thickness of the functional layer is preferably 15 μm or less, more preferably 10 μm or less, further preferably 8 μm or less, and 6 μm or less. Is more preferably 5 μm or less, and particularly preferably 3 μm or less. On the other hand, the thickness of the functional layer is preferably 0.2 μm or more, more preferably 0.5 μm or more, and further preferably 0.7 μm or more. Since the generation of cracks can be suppressed by the functional layer having the thickness, it is preferable.
　前記偏光フィルムの総厚（偏光子、透明保護フィルムの他に、介在層、機能層を含む）は、薄型化の観点から、３～１１５μｍが好ましく、４３～６０μｍがより好ましく、１４～４８μｍがさらに好ましい。 The total thickness of the polarizing film (including the polarizer and the transparent protective film as well as the intervening layer and the functional layer) is preferably 3 to 115 μm, more preferably 43 to 60 μm, and more preferably 14 to 48 μm from the viewpoint of thinning. Further preferred.
　本発明の有機ＥＬ表示装置用偏光フィルムは、前記有機ＥＬ表示装置用光学フィルムを用いているため、優れた低透湿性を有するものである。本発明の有機ＥＬ表示装置用偏光フィルムを、前記粘接着剤層２を介して有機ＥＬ素子に貼り合わせるため、前記粘接着剤層２が、有機ＥＬ素子近くに配置され、有機ＥＬ素子への水分等の移行を十分に抑制することができるものである。 The polarizing film for an organic EL display device of the present invention has excellent low moisture permeability because the optical film for an organic EL display device is used. In order to bond the polarizing film for an organic EL display device of the present invention to an organic EL element via the adhesive layer 2, the adhesive layer 2 is disposed near the organic EL element, and the organic EL element It is possible to sufficiently suppress the transfer of moisture and the like.
　３．有機ＥＬ表示装置用粘着剤層付き偏光フィルム
　本発明の粘着剤層付き偏光フィルムは、前記有機ＥＬ表示装置用偏光フィルムの偏光子側に、さらに粘着剤層を有することを特徴とする。 3. Polarizing film with pressure-sensitive adhesive layer for organic EL display device The polarizing film with a pressure-sensitive adhesive layer of the present invention further comprises a pressure-sensitive adhesive layer on the polarizer side of the polarizing film for organic EL display device.
　本発明の有機ＥＬ表示装置用粘着剤層付き偏光フィルム８は、図４に示すように、本発明の有機ＥＬ表示装置用偏光フィルム６の偏光フィルム５側に粘着剤層７を有するものである。 The polarizing film 8 with an adhesive layer for organic EL display devices of the present invention has an adhesive layer 7 on the polarizing film 5 side of the polarizing film 6 for organic EL display devices of the present invention, as shown in FIG. .
　有機ＥＬ表示装置用偏光フィルムとしては、前述のものを挙げることができる。 Examples of the polarizing film for organic EL display devices include those mentioned above.
　前記粘着剤層７としては、特に限定されるものではなく、公知のものを用いることができる。また、前記粘着剤層として、前述の低透湿の粘着剤層も用いることもできる。このような粘着剤層としては、具体的には、例えば、（メタ）アクリル系ポリマー、シリコーン系ポマー、ポリエステル、ポリウレタン、ポリアミド、ポリエーテル、フッ素系やゴム系等のポリマーをベースポリマーとするものを適宜に選択して用いることができる。これらの中でも、（メタ）アクリル系ポリマーをベースポリマーとするアクリル系粘着剤が、光学的透明性に優れ、適度な濡れ性と凝集性と接着性の粘着特性を示して、耐候性や耐熱性等に優れているため、好ましい。 The pressure-sensitive adhesive layer 7 is not particularly limited, and a known layer can be used. Moreover, the above-mentioned low moisture-permeable pressure-sensitive adhesive layer can also be used as the pressure-sensitive adhesive layer. As such an adhesive layer, specifically, for example, a (meth) acrylic polymer, a silicone-based polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine-based or rubber-based polymer is used as a base polymer. Can be appropriately selected and used. Among these, acrylic pressure-sensitive adhesives based on (meth) acrylic polymers are excellent in optical transparency, exhibiting moderate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, weather resistance and heat resistance. Etc. are preferable.
　前記（メタ）アクリル系ポリマーとしては、特に限定されるものではないが、炭素数４～２４のアルキル基をエステル基の末端に有するアルキル（メタ）アクリレートを含むモノマー成分を重合することにより得られたものを挙げることができる。なお、アルキル（メタ）アクリレートは、アルキルアクリレート及び／又はアルキルメタクリレートをいい、本発明の（メタ）とは同様の意味である。 The (meth) acrylic polymer is not particularly limited, and can be obtained by polymerizing a monomer component containing an alkyl (meth) acrylate having an alkyl group having 4 to 24 carbon atoms at the terminal of the ester group. Can be mentioned. Alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.
　アルキル（メタ）アクリレートとしては、直鎖状又は分岐鎖状の炭素数４～２４のアルキル基を有すものを例示でき、直鎖状又は分岐鎖状の炭素数４～９のアルキル基を有するアルキル（メタ）アクリレートが、粘着特性のバランスがとりやすい点で好ましい。これらのアルキル（メタ）アクリレートは１種を単独で又は２種以上を組み合わせて用いることができる。 Examples of the alkyl (meth) acrylate include those having a linear or branched alkyl group having 4 to 24 carbon atoms, and having a linear or branched alkyl group having 4 to 9 carbon atoms. Alkyl (meth) acrylates are preferred because they are easy to balance the adhesive properties. These alkyl (meth) acrylates can be used alone or in combination of two or more.
　（メタ）アクリル系ポリマーを形成するモノマー成分には、単官能性モノマー成分として、前記アルキル（メタ）アクリレート以外の共重合モノマーを含有することができる。このような共重合モノマーとしては、例えば、環状窒素含有モノマー、ヒドロキシル基含有モノマー、カルボキシル基含有モノマー、環状エーテル基を有するモノマー等が挙げられる。 The monomer component forming the (meth) acrylic polymer can contain a copolymerizable monomer other than the alkyl (meth) acrylate as a monofunctional monomer component. Examples of such copolymerizable monomers include cyclic nitrogen-containing monomers, hydroxyl group-containing monomers, carboxyl group-containing monomers, and monomers having a cyclic ether group.
　また、（メタ）アクリル系ポリマーを形成するモノマー成分には、前記単官能性モノマーの他に、粘着剤の凝集力を調整するために、必要に応じて多官能性モノマーを含有することができる。前記多官能性モノマーは、（メタ）アクリロイル基又はビニル基等の不飽和二重結合を有する重合性の官能基を少なくとも２つ有するモノマーであり、例えば、ジペンタエリスリトールヘキサ（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、トリメチロールプロパントリ（メタ）アクリレートが挙げられる。多官能性モノマーは、１種を単独で又は２種以上を組み合わせて使用することができる。 In addition to the monofunctional monomer, the monomer component forming the (meth) acrylic polymer can contain a polyfunctional monomer as necessary in order to adjust the cohesive force of the pressure-sensitive adhesive. . The polyfunctional monomer is a monomer having at least two polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, such as dipentaerythritol hexa (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate. A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.
　このような（メタ）アクリル系ポリマーの製造は、溶液重合、紫外線重合等の放射線重合、塊状重合、乳化重合等の各種ラジカル重合等の公知の製造方法を適宜選択できる。また、得られる（メタ）アクリル系ポリマーは、ランダム共重合体、ブロック共重合体、グラフト共重合体等いずれでもよい。 The production of such a (meth) acrylic polymer can be appropriately selected from known production methods such as radiation polymerization such as solution polymerization and ultraviolet polymerization, various radical polymerizations such as bulk polymerization and emulsion polymerization. Further, the (meth) acrylic polymer obtained may be a random copolymer, a block copolymer, a graft copolymer or the like.
　ラジカル重合に用いられる重合開始剤、連鎖移動剤、乳化剤等は特に限定されず、本分野において通常用いられる公知のものを適宜選択して使用することができる。また、（メタ）アクリル系ポリマーの重量平均分子量は、重合開始剤、連鎖移動剤の使用量、反応条件により制御可能であり、これらの種類に応じて適宜のその使用量が調整される。 The polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited, and known ones commonly used in this field can be appropriately selected and used. In addition, the weight average molecular weight of the (meth) acrylic polymer can be controlled by the amount of polymerization initiator, the amount of chain transfer agent used, and the reaction conditions, and the amount used is appropriately adjusted according to these types.
　本発明で用いる（メタ）アクリル系ポリマーの重量平均分子量は４０万～４００万であるのが好ましい。重量平均分子量を４０万より大きくすることで、粘着剤層の耐久性を満足させたり、粘着剤層の凝集力が小さくなって糊残りが生じるのを抑えることができる。一方、重量平均分子量が４００万よりも大きくなると貼り合せ性が低下する傾向がある。さらに、粘着剤が溶液系において、粘度が高くなりすぎ、塗工が困難になる場合がある。なお、重量平均分子量は、ＧＰＣ（ゲルパーミネーション・クロマトグラフィー）により測定し、ポリスチレン換算により算出された値をいう。なお、放射線重合で得られた（メタ）アクリル系ポリマーについては、分子量測定は困難である。 The weight average molecular weight of the (meth) acrylic polymer used in the present invention is preferably 400,000 to 4,000,000. By making the weight average molecular weight larger than 400,000, it is possible to satisfy the durability of the pressure-sensitive adhesive layer, or to suppress the occurrence of adhesive residue due to the reduced cohesive force of the pressure-sensitive adhesive layer. On the other hand, when the weight average molecular weight is larger than 4 million, the bonding property tends to be lowered. Furthermore, in the solution system, the viscosity becomes too high, and coating may be difficult. The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene. In addition, it is difficult to measure the molecular weight of the (meth) acrylic polymer obtained by radiation polymerization.
　本発明で用いる粘着剤組成物には、架橋剤を含有することができる。架橋剤としては、イソシアネート系架橋剤、エポキシ系架橋剤、シリコーン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、シラン系架橋剤、アルキルエーテル化メラミン系架橋剤、金属キレート系架橋剤、過酸化物等の架橋剤を挙げることができ、これらを1種単独で又は２種以上を組み合わせて用いることができる。前記架橋剤としては、イソシアネート系架橋剤、エポキシ系架橋剤が好ましく用いられる。 The pressure-sensitive adhesive composition used in the present invention can contain a crosslinking agent. Examples of crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyletherified melamine crosslinking agents, metal chelate crosslinking agents, Examples of the crosslinking agent include oxides, and these can be used alone or in combination of two or more. As said crosslinking agent, an isocyanate type crosslinking agent and an epoxy-type crosslinking agent are used preferably.
　上記架橋剤は１種を単独で使用してもよく、また２種以上を混合して使用してもよいが、全体としての含有量は、前記（メタ）アクリル系ポリマー１００重量部に対し、前記架橋剤を０．０１～１０重量部の範囲で含有することが好ましい。 The crosslinking agent may be used alone or in combination of two or more, but the total content is based on 100 parts by weight of the (meth) acrylic polymer. The crosslinking agent is preferably contained in the range of 0.01 to 10 parts by weight.
　本発明において用いる粘着剤組成物には、接着力を向上させるために、（メタ）アクリル系オリゴマーを含有させることができる。さらに、本発明において用いる粘着剤組成物には、粘着剤層のガラス等の親水性被着体に適用する場合における界面での耐水性を上げるためにシランカップリング剤を含有することができる。 In the pressure-sensitive adhesive composition used in the present invention, a (meth) acrylic oligomer can be contained in order to improve the adhesive force. Furthermore, the pressure-sensitive adhesive composition used in the present invention may contain a silane coupling agent in order to increase the water resistance at the interface when applied to a hydrophilic adherend such as glass of the pressure-sensitive adhesive layer.
　さらに本発明で用いる粘着剤組成物には、その他の公知の添加剤を含有していてもよく、例えば、ポリプロピレングリコール等のポリアルキレングリコールのポリエーテル化合物、着色剤、顔料等の粉体、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、無機又は有機の充填剤、金属粉、粒子状、箔状物等を使用する用途に応じて適宜添加することができる。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。 Furthermore, the pressure-sensitive adhesive composition used in the present invention may contain other known additives, such as polyether compounds of polyalkylene glycols such as polypropylene glycol, powders of colorants and pigments, dyes, and the like. , Surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, UV absorbers, polymerization inhibitors, inorganic or organic fillers, It can be added as appropriate depending on the application in which metal powder, particles, foil, etc. are used. Moreover, you may employ | adopt the redox system which added a reducing agent within the controllable range.
　粘着剤層７の形成方法は、公知の方法により行うことができる。 The formation method of the adhesive layer 7 can be performed by a well-known method.
　４．有機ＥＬ表示装置
　本発明の有機ＥＬ表示装置は、前記有機ＥＬ表示装置用偏光板又は前記粘着剤層付き偏光板を有することを特徴とする。 4). Organic EL Display Device The organic EL display device of the present invention is characterized by having the polarizing plate for an organic EL display device or the polarizing plate with an adhesive layer.
　本発明の有機ＥＬ表示装置は、本発明の有機ＥＬ表示装置用偏光板又は粘着剤層付き偏光板を含むものであって、前記粘接着剤層２を介して有機ＥＬ素子に貼り合わすことができる。本発明の有機ＥＬ表示装置のその他の構成については、従来の有機ＥＬ表示装置と同様のものを挙げることができる。 The organic EL display device of the present invention includes the polarizing plate for an organic EL display device of the present invention or a polarizing plate with an adhesive layer, and is bonded to the organic EL element via the adhesive layer 2. Can do. About the other structure of the organic electroluminescence display of this invention, the thing similar to the conventional organic electroluminescence display can be mentioned.
　本発明の有機ＥＬ表示装置は、前記有機ＥＬ表示装置用偏光板又は前記粘着剤層付き偏光板を含むため、高い光学信頼性を有するものである。 Since the organic EL display device of the present invention includes the polarizing plate for an organic EL display device or the polarizing plate with an adhesive layer, the organic EL display device has high optical reliability.
　以下に、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、各例中の部及び％はいずれも重量基準である。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, all the parts and% in each example are based on weight.
　製造例１（第１の位相差フィルムの作製）
　イソソルビド（ＩＳＢ）３７．５質量部、９，９－ビス［４－（２－ヒドロキシエトキシ）フェニル］フルオレン（ＢＨＥＰＦ）９１．５質量部、平均分子量４００のポリエチレングリコール（ＰＥＧ）８．４質量部、ジフェニルカーボネート（ＤＰＣ）１０５．７質量部、及び、触媒として炭酸セシウム（０．２質量％水溶液）０．５９４質量部をそれぞれ反応容器に投入し、窒素雰囲気下にて、反応の第１段目の工程として、反応容器の熱媒温度を１５０℃にし、必要に応じて攪拌しながら、原料を溶解させた（約１５分）。 Production Example 1 (Production of first retardation film)
Isosorbide (ISB) 37.5 parts by mass, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BHEPF) 91.5 parts by mass, polyethylene glycol (PEG) 8.4 parts by mass with an average molecular weight of 400 , 105.7 parts by weight of diphenyl carbonate (DPC) and 0.594 parts by weight of cesium carbonate (0.2% by weight aqueous solution) as a catalyst were put in a reaction vessel, respectively, and the first stage of the reaction in a nitrogen atmosphere. As an eye process, the temperature of the heat medium in the reaction vessel was set to 150 ° C., and the raw materials were dissolved while stirring as necessary (about 15 minutes).
　次いで、反応容器内の圧力を常圧から１３．３ｋＰａにし、反応容器の熱媒温度を１９０℃まで１時間で上昇させながら、発生するフェノールを反応容器外へ抜き出した。反応容器内温度を１９０℃で１５分保持した後、第２段目の工程として、反応容器内の圧力を６．６７ｋＰａとし、反応容器の熱媒温度を２３０℃まで、１５分で上昇させ、発生するフェノールを反応容器外へ抜き出した。攪拌機の攪拌トルクが上昇してくるので、８分で２５０℃まで昇温し、さらに発生するフェノールを取り除くため、反応容器内の圧力を０．２００ｋＰａ以下に減圧した。所定の攪拌トルクに到達後、反応を終了し、生成した反応物を水中に押し出した後に、ペレット化を行い、ＢＨＥＰＦ／ＩＳＢ／ＰＥＧ＝４２．９モル％／５２．８モル％／４．３モル％の割合でジヒドロキシ化合物に由来する構造単位を含むポリカーボネート樹脂Ａを得た。得られたポリカーボネート樹脂Ａのガラス転移温度は１２６℃であり、還元粘度は０．３７２ｄＬ／ｇであった。得られたポリカーボネート樹脂Ａを８０℃で５時間真空乾燥した後、単軸押出機（スクリュー径：２５ｍｍ、シリンダー設定温度：２２０℃、いすず化工機（株）製）、Ｔダイ（幅：３００ｍｍ、設定温度：２２０℃）、チルロール（設定温度：１２０～１３０℃）及び巻取機を備えたフィルム製膜装置を用いて、長さ３ｍ、幅３００ｍｍ、厚み１２０μｍのポリカーボネート樹脂フィルムを作製した。得られたポリカーボネート樹脂フィルムの吸水率は、１．２％であった。 Then, the pressure in the reaction vessel was changed from normal pressure to 13.3 kPa, and the generated phenol was extracted out of the reaction vessel while raising the temperature of the heat medium in the reaction vessel to 190 ° C. over 1 hour. After holding the reaction vessel temperature at 190 ° C. for 15 minutes, as a second step, the pressure in the reaction vessel is set to 6.67 kPa, and the heat medium temperature of the reaction vessel is increased to 230 ° C. in 15 minutes. The generated phenol was extracted out of the reaction vessel. Since the stirring torque of the stirrer increased, the temperature was raised to 250 ° C. in 8 minutes, and the pressure in the reaction vessel was reduced to 0.200 kPa or less in order to remove the generated phenol. After reaching a predetermined stirring torque, the reaction was terminated, and the formed reaction product was extruded into water, and then pelletized to obtain BHEPF / ISB / PEG = 42.9 mol% / 52.8 mol% / 4.3. A polycarbonate resin A containing a structural unit derived from a dihydroxy compound at a mol% ratio was obtained. The obtained polycarbonate resin A had a glass transition temperature of 126 ° C. and a reduced viscosity of 0.372 dL / g. The obtained polycarbonate resin A was vacuum dried at 80 ° C. for 5 hours, and then a single screw extruder (screw diameter: 25 mm, cylinder set temperature: 220 ° C., manufactured by Isuzu Chemical Industries Ltd.), T die (width: 300 mm, A polycarbonate resin film having a length of 3 m, a width of 300 mm, and a thickness of 120 μm was prepared using a film forming apparatus equipped with a setting temperature: 220 ° C., a chill roll (setting temperature: 120 to 130 ° C.) and a winder. The water absorption of the obtained polycarbonate resin film was 1.2%.
　得られたポリカーボネート樹脂フィルムを、長さ３００ｍｍ、幅３００ｍｍに切り出し、ラボストレッチャーＫＡＲＯ　ＩＶ（Ｂｒｕｃｋｎｅｒ社製）を用いて、温度１３６℃、倍率２倍で縦延伸を行い、位相差フィルムを得た。得られた位相差フィルムのＲｅ（５５０）は１４１ｎｍ、Ｒｔｈ（５５０）は１４１ｎｍであり（ｎｘ：１．５９６９、ｎｙ：１．５９４２、ｎｚ：１．５９４２）、ｎｘ＞ｎｙ＝ｎｚの屈折率特性を示した。また、得られた位相差フィルムのＲｅ（４５０）／Ｒｅ（５５０）は０．８９であった（さらに、環境試験による位相差変動は５ｎｍであった）。 The obtained polycarbonate resin film was cut into a length of 300 mm and a width of 300 mm, and longitudinally stretched at a temperature of 136 ° C. and a magnification of 2 times using a lab stretcher KARO IV (manufactured by Bruckner) to obtain a retardation film. . Re (550) of the obtained retardation film is 141 nm, Rth (550) is 141 nm (nx: 1.5969, ny: 1.5942, nz: 1.5942), and refractive index of nx> ny = nz. The characteristics are shown. In addition, Re (450) / Re (550) of the obtained retardation film was 0.89 (further, the retardation fluctuation due to the environmental test was 5 nm).
　製造例２（第２の位相差層（第２の位相差フィルム）の作製）
　下記化学式（Ｉ）（式中の数字６５及び３５はモノマーユニットのモル％を示し、便宜的にブロックポリマー体で表している、重量平均分子量：５０００）で示される側鎖型液晶ポリマー２０重量部、ネマチック液晶相を示す重合性液晶（商品名：ＰａｌｉｏｃｏｌｏｒＬＣ２４２、ＢＡＳＦ社製）８０重量部及び光重合開始剤（商品名：イルガキュア９０７、チバスペシャリティーケミカルズ社製）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。そして、基材フィルム（ノルボルネン系樹脂フィルム、商品名：ゼオネックス、：日本ゼオン（株）製）に当該塗工液をバーコーターにより塗工した後、８０℃で４分間加熱乾燥することによって液晶を配向させた。この液晶層に紫外線を照射し、液晶層を硬化させることにより、基材上に第２の位相差層となる液晶固化層（厚み：０．５８μｍ）を形成した。この層のＲｅ（５５０）は０ｎｍ、Ｒｔｈ（５５０）は－７１ｎｍであり（ｎｘ：１．５３２６、ｎｙ：１．５３２６、ｎｚ：１．６５５０）、ｎｚ＞ｎｘ＝ｎｙの屈折率特性を示した。 Production Example 2 (Production of second retardation layer (second retardation film))
20 parts by weight of a side chain type liquid crystal polymer represented by the following chemical formula (I) (numbers 65 and 35 in the formula indicate mol% of the monomer unit and are represented by a block polymer for convenience) 80 parts by weight of a polymerizable liquid crystal exhibiting a nematic liquid crystal phase (trade name: Paliocolor LC242, manufactured by BASF) and 5 parts by weight of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) are added to 200 parts by weight of cyclopentanone. A liquid crystal coating solution was prepared by dissolving in the part. And after apply | coating the said coating liquid to a base film (norbornene-type resin film, brand name: ZEONEX, KK: Nippon Zeon Co., Ltd.) with a bar coater, the liquid crystal is dried by heating at 80 ° C. for 4 minutes. Oriented. The liquid crystal layer was irradiated with ultraviolet rays to cure the liquid crystal layer, thereby forming a liquid crystal solidified layer (thickness: 0.58 μm) serving as the second retardation layer on the substrate. This layer has Re (550) of 0 nm and Rth (550) of -71 nm (nx: 1.5326, ny: 1.5326, nz: 1.6550), and exhibits a refractive index characteristic of nz> nx = ny. It was.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　製造例３（位相差フィルムＡの作製）
　製造例１で得られた第１の位相差フィルムに、アクリル系粘着剤を介して、製造例２で得られた第２の位相差層（液晶固化層）を貼り合わせた後、上記基材フィルムを除去して、第１の位相差フィルムに液晶固化層が転写された積層体（位相差フィルムＡ）を得た。得られた位相差フィルムＡは、第１の位相差フィルム／アクリル系粘着剤層／第２の位相差層から構成されていた。得られた位相差フィルムＡのＲｅ（５５０）は１４１ｎｍであり、Ｒｔｈ（５５０）は７０ｎｍであった。 Production Example 3 (Production of retardation film A)
After bonding the second retardation layer (liquid crystal solidified layer) obtained in Production Example 2 to the first retardation film obtained in Production Example 1 via an acrylic pressure-sensitive adhesive, the substrate The film was removed to obtain a laminate (retardation film A) in which the liquid crystal solidified layer was transferred to the first retardation film. The obtained retardation film A was composed of a first retardation film / acrylic pressure-sensitive adhesive layer / second retardation layer. Re (550) of the obtained retardation film A was 141 nm, and Rth (550) was 70 nm.
　製造例４（位相差フィルムＢの作製）
　長尺状のノルボルネン系樹脂フィルム（商品名：ゼオノア、厚さ：５０μｍ、日本ゼオン社製）を１．５２倍に延伸することによって、Ｒｅ（５５０）が１４０ｎｍの位相差フィルムＢ（厚さ：３５μｍ）を得た。 Production Example 4 (Production of retardation film B)
A long norbornene-based resin film (trade name: ZEONOR, thickness: 50 μm, manufactured by Nippon Zeon Co., Ltd.) is stretched 1.52 times, whereby Re (550) is a retardation film B (thickness: 140 nm). 35 μm) was obtained.
　製造例５（位相差フィルムＣの作製）
　位相差フィルムＡを基材として、Ａｌ、ＳｉＯ２及びＺｎＯを含むスパッタリングターゲットを用いて、ＤＣマグネトロンスパッタリング法により前記基材の第１の位相差フィルム上に第１の酸化物層（厚み：３０ｎｍ）を形成した。次に、Ｓｉターゲットを用いて、基材／第１の酸化物層の積層体の第１の酸化物層上に第２の酸化物層（厚み：５０ｎｍ）を形成した。このようにして、第２の位相差層／アクリル系粘着剤層／第１の位相差フィルム／第１の酸化物層（ＡＺＯ）／第２の酸化物層（ＳｉＯ２）の構成を有する位相差フィルムＣを作製した。 Production Example 5 (Production of retardation film C)
Using the retardation film A as a base material, a first oxide layer (thickness: 30 nm) is formed on the first retardation film of the base material by a DC magnetron sputtering method using a sputtering target containing Al, SiO 2 and ZnO. ) Was formed. Next, a second oxide layer (thickness: 50 nm) was formed on the first oxide layer of the base material / first oxide layer stack using a Si target. Thus, the position having the configuration of the second retardation layer / acrylic pressure-sensitive adhesive layer / first retardation film / first oxide layer (AZO) / second oxide layer (SiO 2 ). Phase difference film C was produced.
　製造例６（光学フィルム積層体の作製）
　非晶性ポリエチレンテレフタレート（ＰＥＴ）基材に、９μｍ厚のポリビニルアルコール（ＰＶＡ）層が製膜された積層体を、延伸温度１３０℃の空中補助延伸によって延伸積層体を生成した。次に、延伸積層体を染色によって着色積層体を生成し、さらに着色積層体を延伸温度６５℃のホウ酸水中延伸によって総延伸倍率が５．９４倍になるように非晶性ＰＥＴ基材と一体に延伸された５μｍ厚のＰＶＡ層を含む光学フィルム積層体を生成した。このような２段延伸によって非晶性ＰＥＴ基材に製膜されたＰＶＡ層のＰＶＡ分子が高次に配向され、染色によって吸着されたヨウ素がポリヨウ素イオン錯体として一方向に高次に配向された高機能偏光膜（偏光子）を構成する、厚さ５μｍのＰＶＡ層を含む光学フィルム積層体を生成した。 Production Example 6 (Production of optical film laminate)
A stretched laminate was produced by air-assisted stretching at a stretching temperature of 130 ° C. from a laminate in which a 9 μm-thick polyvinyl alcohol (PVA) layer was formed on an amorphous polyethylene terephthalate (PET) substrate. Next, a colored laminate is produced by dyeing the stretched laminate, and the colored laminate is further stretched in boric acid in water at a stretching temperature of 65 ° C. so that the total stretch ratio becomes 5.94 times. An optical film laminate comprising a 5 μm thick PVA layer stretched together was produced. The PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex. Thus, an optical film laminate including a PVA layer having a thickness of 5 μm constituting a highly functional polarizing film (polarizer) was produced.
　製造例７（ゴム系粘着剤組成物の作製）
　ポリイソブチレン（商品名：ＯＰＰＡＮＯＬ　Ｂ８０、Ｍｗ：約７５万、ＢＡＳＦ社製）１００重量部と、多官能ラジカル重合性化合物としてのトリシクロデカンジメタノールジアクリレート（商品名：ＮＫエステルＡ－ＤＣＰ、２官能アクリレート、分子量：３０４、新中村化学工業（株）製）５重量部、水素引抜型光重合開始剤であるベンゾフェノン（和光純薬工業（株）製）０．５部、完全水添テルペンフェノール１０重量部を配合したトルエン溶液（粘着剤溶液）を固形分が１５重量％になるように調整し、ゴム系粘着剤組成物（溶液）を調製した。 Production Example 7 (Production of rubber-based pressure-sensitive adhesive composition)
100 parts by weight of polyisobutylene (trade name: OPPANOL B80, Mw: about 750,000, manufactured by BASF) and tricyclodecane dimethanol diacrylate (trade name: NK ester A-DCP, 2) as a polyfunctional radical polymerizable compound Functional acrylate, molecular weight: 304, 5 parts by weight, Shin-Nakamura Chemical Co., Ltd.), 0.5 parts of benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.), a hydrogen abstraction photopolymerization initiator, fully hydrogenated terpene phenol A toluene solution (adhesive solution) containing 10 parts by weight was adjusted to a solid content of 15% by weight to prepare a rubber-based adhesive composition (solution).
　製造例８（ゴム系粘着剤組成物の作製）
　ポリイソブチレン（商品名：ＯＰＰＡＮＯＬ　Ｂ８０、Ｍｗ：約７５万、ＢＡＳＦ社製）１００重量部と、多官能ラジカル重合性化合物としてのトリシクロデカンジメタノールジアクリレート（商品名：ＮＫエステルＡ－ＤＣＰ、２官能アクリレート、分子量：３０４、新中村化学工業（株）製）１０重量部、水素引抜型光重合開始剤であるベンゾフェノン（和光純薬工業（株）製）０．５部、完全水添テルペンフェノール１０重量部を配合したトルエン溶液（粘着剤溶液）を固形分が１５重量％になるように調整し、ゴム系粘着剤組成物（溶液）を調製した。 Production Example 8 (Production of rubber-based pressure-sensitive adhesive composition)
100 parts by weight of polyisobutylene (trade name: OPPANOL B80, Mw: about 750,000, manufactured by BASF) and tricyclodecane dimethanol diacrylate (trade name: NK ester A-DCP, 2) as a polyfunctional radical polymerizable compound Functional acrylate, molecular weight: 304, manufactured by Shin-Nakamura Chemical Co., Ltd.) 10 parts by weight, benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.) 0.5 parts hydrogenated photopolymerization initiator, fully hydrogenated terpene phenol A toluene solution (adhesive solution) containing 10 parts by weight was adjusted to a solid content of 15% by weight to prepare a rubber-based adhesive composition (solution).
　製造例９
　（アクリル系粘着剤組成物の作製）
　温度計、攪拌機、還流冷却管及び窒素ガス導入管を備えたセパラブルフラスコに、モノマー成分として、ブチルアクリレート（ＢＡ）９９重量部、４－ヒドロキシブチルアクリレート（４ＨＢＡ）１重量部、重合開始剤としてアゾビスイソブチロニトリル０．２重量部及び重合溶媒として酢酸エチルを固形分が２０％になるように投入した後、窒素ガスを流し、攪拌しながら約１時間窒素置換を行った。その後、６０℃にフラスコを加熱し、７時間反応させて重量平均分子量（Ｍｗ）１１０万のアクリル系ポリマーを得た。上記アクリル系ポリマー溶液（固形分１００重量部）に、イソシアネート系架橋剤と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（商品名：コロネートＬ、日本ポリウレタン工業（株）製）０．８重量部、シランカップリング剤（商品名：ＫＢＭ－４０３、信越化学（株）製）０．１重量部を加えてアクリル系粘着剤組成物を調製した。 Production Example 9
(Preparation of acrylic pressure-sensitive adhesive composition)
In a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, 99 parts by weight of butyl acrylate (BA), 1 part by weight of 4-hydroxybutyl acrylate (4HBA) as a monomer component, and a polymerization initiator After 0.2 parts by weight of azobisisobutyronitrile and ethyl acetate as a polymerization solvent were added so as to have a solid content of 20%, nitrogen substitution was performed for about 1 hour while flowing nitrogen gas and stirring. Thereafter, the flask was heated to 60 ° C. and reacted for 7 hours to obtain an acrylic polymer having a weight average molecular weight (Mw) of 1.1 million. To the acrylic polymer solution (solid content: 100 parts by weight), 0.8 parts by weight of trimethylolpropane tolylene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) as an isocyanate-based crosslinking agent, silane coupling agent An acrylic pressure-sensitive adhesive composition was prepared by adding 0.1 parts by weight (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).
　（アクリル系粘着剤層の作製）
　前記得られたアクリル系粘着剤組成物を、片面をシリコーンで剥離処理した厚み３８μｍのポリエステルフィルム（商品名：ダイアホイルＭＲＦ、三菱樹脂（株）製）の剥離処理面に塗布して塗布層を形成した。次いで、塗布層を１２０℃で３分乾燥させて、粘着剤層を形成し、粘着剤層の厚みが５０μｍの粘着シートを作製した。また、粘着シートの粘着面には、前記片面をシリコーンで剥離処理した厚み３８μｍのポリエステルフィルム（商品名：ダイアホイルＭＲＦ、三菱樹脂（株）製）を、剥離処理面と前記粘着剤層が接するように貼り合せて、アクリル系粘着シートを得た。粘着剤層の両面に被覆されたポリエステルフィルムは、剥離ライナー（セパレーター）として機能する。 (Production of acrylic adhesive layer)
The obtained acrylic pressure-sensitive adhesive composition was applied to the release-treated surface of a 38 μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone. Formed. Next, the coating layer was dried at 120 ° C. for 3 minutes to form a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet having a thickness of 50 μm was prepared. Also, the adhesive surface of the pressure-sensitive adhesive sheet is a 38 μm thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone, and the peel-treated surface and the pressure-sensitive adhesive layer are in contact with each other. Thus, an acrylic pressure-sensitive adhesive sheet was obtained. The polyester film coated on both sides of the pressure-sensitive adhesive layer functions as a release liner (separator).
　実施例１
　（粘着シートの作製）
　製造例７で得られたゴム系粘着剤組成物（溶液）を、片面をシリコーンで剥離処理した厚み３８μｍのポリエステルフィルム（商品名：ダイアホイルＭＲＦ、三菱樹脂（株）製）の剥離処理面に塗布して塗布層を形成した。次いで、塗布層を８０℃で３分乾燥させて、粘着剤層を形成し、粘着剤層の厚みが５０μｍの粘着シートを作製した。また、粘着シートの粘着面には、前記片面をシリコーンで剥離処理した厚み３８μｍのポリエステルフィルム（商品名：ダイアホイルＭＲＦ、三菱樹脂（株）製）を、剥離処理面と前記粘着剤層が接するように貼り合せた。粘着剤層の両面に被覆されたポリエステルフィルムは、剥離ライナー（セパレーター）として機能する。 Example 1
(Preparation of adhesive sheet)
The rubber-based pressure-sensitive adhesive composition (solution) obtained in Production Example 7 was applied to the release-treated surface of a 38 μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) whose one side was peel-treated with silicone. The coating layer was formed by coating. Subsequently, the coating layer was dried at 80 ° C. for 3 minutes to form a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet having a thickness of 50 μm was prepared. Also, the adhesive surface of the pressure-sensitive adhesive sheet is a 38 μm thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone, and the peel-treated surface and the pressure-sensitive adhesive layer are in contact with each other. Were pasted together. The polyester film coated on both sides of the pressure-sensitive adhesive layer functions as a release liner (separator).
　一方のセパレーターを剥離し、セパレーターを剥離した側から、室温で紫外線を照射し、ゴム系粘着剤層／セパレーターからなる粘着シートを得た。前記紫外線照射は、ＵＶＡ領域にて、光量１０００ｍＪ／ｃｍ２であった。 One separator was peeled off, and ultraviolet rays were irradiated at room temperature from the side where the separator was peeled off to obtain a pressure-sensitive adhesive sheet comprising a rubber-based pressure-sensitive adhesive layer / separator. In the UVA region, the UV irradiation was a light amount of 1000 mJ / cm 2 .
　（粘着剤層付き位相差フィルムの作製）
　製造例３で得られた位相差フィルムＡの第２の位相差層に、前記得られたゴム系粘着シートを貼り合せて、位相差フィルムＡ／ゴム系粘着剤層／セパレーターからなる積層体を得た。 (Preparation of retardation film with adhesive layer)
A laminate comprising the retardation film A / rubber pressure-sensitive adhesive layer / separator is bonded to the second retardation layer of the retardation film A obtained in Production Example 3 by bonding the obtained rubber-based pressure-sensitive adhesive sheet. Obtained.
　（偏光フィルムの作製方法）
　製造例６で得られた光学フィルム積層体の偏光膜（偏光子、厚み：５μｍ）の表面に、接着剤層の厚さが０．１μｍになるようにポリビニルアルコール系接着剤を塗布しながら、保護フィルム（トリアセチルセルロース（ＴＡＣ）フィルム（商品名：ＫＣ４ＵＹＷ、厚み：４０μｍ、コニカミノルタ社製）を貼合せたのち、５０℃で５分間の乾燥を行った。次いで、非晶性ＰＥＴ基材を剥離して、薄型偏光子を用いた片保護偏光フィルムを作製した。得られた片保護偏光フィルムの偏光膜側に、ポリビニルアルコール系接着剤を介して、前記積層体の位相差フィルムＡを貼り合わせた。ここで、位相差フィルムＡの遅相軸が偏光子の吸収軸に対して反時計回りに４５°となるように貼り合わせた。得られた偏光フィルムは、ＴＡＣフィルム／接着剤層／偏光子／接着剤層／位相差フィルムＡ／ゴム系粘着剤層／セパレーターからなる構造を有していた。 (Preparation method of polarizing film)
While applying a polyvinyl alcohol-based adhesive on the surface of the polarizing film (polarizer, thickness: 5 μm) of the optical film laminate obtained in Production Example 6 so that the thickness of the adhesive layer is 0.1 μm, After a protective film (triacetyl cellulose (TAC) film (trade name: KC4UYW, thickness: 40 μm, manufactured by Konica Minolta)) was laminated, drying was performed for 5 minutes at 50 ° C. Next, an amorphous PET substrate A piece protective polarizing film using a thin polarizer was prepared, and the retardation film A of the laminate was placed on the polarizing film side of the obtained piece protective polarizing film via a polyvinyl alcohol-based adhesive. Here, the retardation film A was laminated so that the slow axis of the retardation film A was 45 ° counterclockwise with respect to the absorption axis of the polarizer. It had a structure consisting of adhesive layer / polarizer / adhesive layer / retardation film A / rubber-based pressure-sensitive adhesive layer / separator.
　実施例２
　（粘着剤層付き位相差フィルムの作製）
　位相差フィルムとして、製造例４で得られた位相差フィルムＢを使用した以外は、実施例１と同様にして、位相差フィルムＢ／ゴム系粘着剤層／セパレータからなる積層体を得た。 Example 2
(Preparation of retardation film with adhesive layer)
A laminate comprising retardation film B / rubber-based adhesive layer / separator was obtained in the same manner as in Example 1 except that the retardation film B obtained in Production Example 4 was used as the retardation film.
　（偏光フィルムの作製方法）
　前記得られた積層体を用いた以外は実施例１と同様にして偏光フィルムを作製した。得られた偏光フィルムは、ＴＡＣフィルム／接着剤層／偏光子／接着剤層／位相差フィルムＢ／ゴム系粘着剤層／セパレーターからなる構造を有していた。 (Preparation method of polarizing film)
A polarizing film was produced in the same manner as in Example 1 except that the obtained laminate was used. The obtained polarizing film had a structure consisting of TAC film / adhesive layer / polarizer / adhesive layer / retardation film B / rubber pressure-sensitive adhesive layer / separator.
　比較例１
　（粘着剤層付き位相差フィルムの作製）
　ゴム系粘着剤層の代わりに、製造例９で得られたアクリル系粘着剤層を用いた以外は、実施例１と同様にして、位相差フィルムＡ／アクリル系粘着剤層／セパレーターからなる積層体を得た。 Comparative Example 1
(Preparation of retardation film with adhesive layer)
Laminated film composed of retardation film A / acrylic pressure-sensitive adhesive layer / separator in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive layer obtained in Production Example 9 was used instead of the rubber-based pressure-sensitive adhesive layer. Got the body.
　（偏光フィルムの作製方法）
　前記得られた積層体を用いた以外は実施例１と同様にして偏光フィルムを作製した。得られた偏光フィルムは、ＴＡＣフィルム／接着剤層／偏光子／接着剤層／位相差フィルムＡ／アクリル系粘着剤層／セパレーターからなる構造を有していた。 (Preparation method of polarizing film)
A polarizing film was produced in the same manner as in Example 1 except that the obtained laminate was used. The obtained polarizing film had a structure consisting of TAC film / adhesive layer / polarizer / adhesive layer / retardation film A / acrylic pressure-sensitive adhesive layer / separator.
　実施例及び比較例で得られた粘着剤組成物、積層体、又は偏光フィルムを用いて、以下の測定を行った。評価結果を表１に示す。 The following measurements were performed using the pressure-sensitive adhesive compositions, laminates, and polarizing films obtained in Examples and Comparative Examples. The evaluation results are shown in Table 1.
　＜粘着剤層の透湿度の測定＞
　実施例、比較例で得られた粘着シート（粘着剤層の厚み：５０μｍ）の粘着面に、トリアセチルセルロースフィルム（ＴＡＣフィルム、厚み：２５μｍ、コニカミノルタ（株）製）に貼り合わせた。その後、粘着シートの剥離ライナーを剥がして、測定用サンプルを得た。次に、この測定用サンプルを用いて、下記条件で、透湿度試験方法（カップ法、ＪＩＳ　Ｚ　０２０８に準じる）により、透湿度（水蒸気透過率）を測定した。
　　測定温度：４０℃
　　相対湿度：９２％
　　測定時間：２４時間
　　測定の際には、恒温恒湿槽を使用した。 <Measurement of moisture permeability of pressure-sensitive adhesive layer>
The triacetylcellulose film (TAC film, thickness: 25 μm, manufactured by Konica Minolta Co., Ltd.) was bonded to the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer thickness: 50 μm) obtained in Examples and Comparative Examples. Thereafter, the release liner of the pressure-sensitive adhesive sheet was peeled off to obtain a measurement sample. Next, using this measurement sample, moisture permeability (water vapor permeability) was measured by the moisture permeability test method (cup method, conforming to JIS Z 0208) under the following conditions.
Measurement temperature: 40 ° C
Relative humidity: 92%
Measurement time: 24 hours A constant temperature and humidity chamber was used for measurement.
　＜粘着剤層付き位相差フィルムの透湿度の測定＞
　実施例、比較例１で得られた積層体からセパレーターを剥離し、粘着面を露出させ、測定用サンプルとした。次に、この測定用サンプルを用いて、下記条件で、透湿度試験方法（カップ法、ＪＩＳ　Ｚ　０２０８に準じる）により、透湿度（水蒸気透過率）を測定した。
　　測定温度：４０℃
　　相対湿度：９２％
　　測定時間：２４時間
　　測定の際には、恒温恒湿槽を使用した。 <Measurement of moisture permeability of retardation film with adhesive layer>
The separator was peeled from the laminate obtained in Example and Comparative Example 1, and the adhesive surface was exposed to obtain a measurement sample. Next, using this measurement sample, moisture permeability (water vapor permeability) was measured by the moisture permeability test method (cup method, conforming to JIS Z 0208) under the following conditions.
Measurement temperature: 40 ° C
Relative humidity: 92%
Measurement time: 24 hours A constant temperature and humidity chamber was used for measurement.
　＜耐久性＞
　実施例及び比較例で得られた粘着剤層付き偏光フィルムのセパレーターを剥がし、試験片をガラス板に貼り合わせ、これを８５℃の環境下に３００時間投入後の状態を目視又はルーペ（２０倍）を用いて観察した。以下の評価基準により評価した。
　◎：ルーペで確認しても、不具合（発泡、剥がれ等）の発生がなかった。
　○：目視では不具合が確認できなかったが、ルーペで確認すると使用に問題ない程度の多少の不具合が生じていた。
　×：目視で不具合が確認できた。 <Durability>
The separator of the polarizing film with a pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off, the test piece was bonded to a glass plate, and the state after being put in an environment of 85 ° C. for 300 hours was visually or magnified (20 times). ). Evaluation was performed according to the following evaluation criteria.
A: Even when confirmed with a loupe, no defects (foaming, peeling, etc.) occurred.
○: Although no defects could be confirmed by visual observation, some defects occurred to the extent that they were not problematic for use when confirmed with a magnifying glass.
X: Defects could be confirmed visually.
　＜視野角特性＞
　実施例及び比較例で得られた偏光フィルムを寸法５０ｍｍ×５０ｍｍに切り出した。有機ＥＬディスプレイ（製品名：１５ＥＬ９５００、ＬＧ社製）から有機ＥＬパネルを取り出し、この有機ＥＬパネルに貼り付けられている偏光フィルムを剥がし取り、代わりに切り出した偏光フィルムを貼り合わせて有機ＥＬパネルを得た。この有機ＥＬパネルの反射色相の測定結果を表に示す。なお、「視野角特性」は、ＣＩＥ表色系のｘｙ色度図上における、正面方向の反射色相と斜め方向の反射色相（極角４５°における最大値又は最小値）との２点間距離Δｘｙを示す。
　得られた有機ＥＬパネルに黒画像を表示させ、Ａｕｏｒｏｎｉｃ－ＭＥＲＣＨＥＲＳ社製の視野角測定評価装置コノスコープを用いて反射色相を測定した。
　○：０．０７以下であり、反射特性が良好であり、有機ＥＬデバイスとして用いることができる。
　×：０．０７未満で反射特性が良くなく、有機ＥＬデバイスとして用いることができない。 <Viewing angle characteristics>
The polarizing films obtained in the examples and comparative examples were cut into dimensions of 50 mm × 50 mm. The organic EL panel is taken out from the organic EL display (product name: 15EL9500, manufactured by LG), the polarizing film attached to the organic EL panel is peeled off, and the cut out polarizing film is pasted in place to attach the organic EL panel. Obtained. The measurement results of the reflection hue of this organic EL panel are shown in the table. The “viewing angle characteristic” is the distance between two points of the reflected hue in the front direction and the reflected hue in the oblique direction (maximum value or minimum value at 45 ° polar angle) on the xy chromaticity diagram of the CIE color system. Δxy is shown.
A black image was displayed on the obtained organic EL panel, and the reflection hue was measured using a viewing angle measurement evaluation apparatus conoscope manufactured by Auoronic-MERCHERS.
A: 0.07 or less, good reflection characteristics, and can be used as an organic EL device.
X: Less than 0.07, the reflection characteristics are not good, and the organic EL device cannot be used.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
　表１中の表記は以下の通りである。
　＜ゴム系ポリマー＞
　ＯＰＰＡＮＯＬ　Ｂ８０：ポリイソブチレン（Ｍｗ：約７５万、ＢＡＳＦ社製）
　＜アクリル系ポリマー＞
　製造例９で得られたアクリル系粘着剤組成物
　＜多官能ラジカル重合性化合物＞
　Ａ－ＤＣＰ：トリシクロデカンジメタノールジアクリレート（商品名：ＮＫエステルＡ－ＤＣＰ、２官能アクリレート、分子量：３０４、新中村化学工業（株）製）
　＜光重合開始剤＞
　ベンゾフェノン：水素引抜型光重合開始剤
　＜粘着付与剤＞
　完全水添テルペンフェノール：軟化点が１６０℃、水酸基価が６０である完全水添テルペンフェノール The notations in Table 1 are as follows.
<Rubber polymer>
OPPANOL B80: Polyisobutylene (Mw: approx. 750,000, manufactured by BASF)
<Acrylic polymer>
Acrylic pressure-sensitive adhesive composition obtained in Production Example 9 <Polyfunctional radical polymerizable compound>
A-DCP: Tricyclodecane dimethanol diacrylate (trade name: NK ester A-DCP, bifunctional acrylate, molecular weight: 304, manufactured by Shin-Nakamura Chemical Co., Ltd.)
<Photopolymerization initiator>
Benzophenone: Hydrogen abstraction type photopolymerization initiator <Tackifier>
Completely hydrogenated terpene phenol: fully hydrogenated terpene phenol having a softening point of 160 ° C. and a hydroxyl value of 60
　１　　有機ＥＬ表示装置用光学フィルム
　２　　粘接着剤層
　３ａ　λ／４板として機能する位相差フィルム（第１の位相差フィルム）
　３ｂ　λ／２板として機能する位相差フィルム（第２の位相差フィルム）
　４　　接着剤層又は粘着剤層
　５Ａ　　片面保護偏光フィルム
　５Ｂ　　両面保護偏光フィルム
　５ａ　偏光子
　５ｂ　保護フィルム
　６　　有機ＥＬ表示装置用偏光フィルム
　７　　粘着剤層
　８　　有機ＥＬ表示装置用粘着剤層付き偏光フィルム DESCRIPTION OF SYMBOLS 1 Optical film for organic EL display apparatuses 2 Adhesive layer 3a Retardation film (1st retardation film) which functions as (lambda) / 4 board
3b Retardation film functioning as a λ / 2 plate (second retardation film)
DESCRIPTION OF SYMBOLS 4 Adhesive layer or adhesive layer 5A Single-sided protective polarizing film 5B Double-sided protective polarizing film 5a Polarizer 5b Protective film 6 Polarizing film for organic EL display devices 7 Adhesive layer 8 Polarizing film with an adhesive layer for organic EL display devices

Claims (8)

  1. 　λ／４板として機能する位相差フィルムと、４０℃、９２％Ｒ．Ｈ．における透湿度が５０ｇ／（ｍ２・ｄａｙ）以下の粘接着剤層とを備えることを特徴とする有機ＥＬ表示装置用光学フィルム。 a retardation film functioning as a λ / 4 plate, 40 ° C., 92% R.D. H. An optical film for an organic EL display device comprising: an adhesive layer having a moisture permeability of 50 g / (m 2 · day) or less.
  2. 　前記粘接着剤層が、ポリイソブチレン、及び水素引抜型光重合開始剤を含むゴム系粘着剤組成物から形成された粘着剤層であることを特徴とする請求項１に記載の有機ＥＬ表示装置用光学フィルム。 2. The organic EL display according to claim 1, wherein the adhesive layer is a pressure-sensitive adhesive layer formed from a rubber-based pressure-sensitive adhesive composition containing polyisobutylene and a hydrogen abstraction type photopolymerization initiator. Optical film for equipment.
  3. 　偏光子と、請求項１又は２に記載の有機ＥＬ表示装置用光学フィルムを含むことを特徴とする有機ＥＬ表示装置用偏光フィルム。 A polarizing film for an organic EL display device comprising a polarizer and the optical film for an organic EL display device according to claim 1.
  4. 　前記偏光子の厚みが、１５μｍ以下であることを特徴とする請求項３に記載の有機ＥＬ表示装置用偏光フィルム。 The polarizing film for an organic EL display device according to claim 3, wherein the polarizer has a thickness of 15 μm or less.
  5. 　前記偏光子と、λ／４板として機能する位相差フィルムと、４０℃、９２％Ｒ．Ｈ．における透湿度が５０ｇ／（ｍ２・ｄａｙ）以下の粘接着剤層とをこの順に備えることを特徴とする請求項３又は４に記載の有機ＥＬ表示装置用偏光フィルム。 The polarizer, a retardation film functioning as a λ / 4 plate, 40 ° C., 92% R.D. H. The polarizing film for an organic EL display device according to claim 3, further comprising an adhesive layer having a moisture permeability of 50 g / (m 2 · day) or less in this order.
  6. 　前記偏光子と、４０℃、９２％Ｒ．Ｈ．における透湿度が５０ｇ／（ｍ２・ｄａｙ）以下の粘接着剤層と、λ／４板として機能する位相差フィルムとを、この順に備えることを特徴とする請求項３又は４に記載の有機ＥＬ表示装置用偏光フィルム。 The polarizer and 40 ° C., 92% R.D. H. The water vapor transmission rate is 50 g / (m 2 · day) or less, and an adhesive layer and a retardation film functioning as a λ / 4 plate are provided in this order. Polarizing film for organic EL display devices.
  7. 　請求項３～６のいずれかに記載の有機ＥＬ表示装置用偏光フィルムの偏光子側に、さらに粘着剤層を有することを特徴とする有機ＥＬ表示装置用粘着剤層付き偏光フィルム。 A polarizing film with an adhesive layer for an organic EL display device, further comprising an adhesive layer on the polarizer side of the polarizing film for an organic EL display device according to any one of claims 3 to 6.
  8. 　請求項３～６のいずれかに記載の有機ＥＬ表示装置用偏光フィルム、又は請求項７に記載の有機ＥＬ表示装置用粘着剤層付き偏光フィルムを有することを特徴とする有機ＥＬ表示装置。 An organic EL display device comprising the polarizing film for an organic EL display device according to any one of claims 3 to 6 or the polarizing film with an adhesive layer for an organic EL display device according to claim 7.
PCT/JP2017/014222 2016-05-10 2017-04-05 Optical film for organic el display devices, polarizing film for organic el display devices, polarizing film with adhesive layer for organic el display devices, and organic el display device WO2017195506A1 (en)

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CN201780025832.0A CN109121431B (en) 2016-05-10 2017-04-05 Optical film for organic electroluminescent display device, polarizing film with adhesive layer, and organic electroluminescent display device
SG11201809771SA SG11201809771SA (en) 2016-05-10 2017-04-05 Optical film for organic el display devices, polarizing film for organic el display devices, pressure-sensitive-adhesive layer attached polarizing film for organic el display devices, and organic el display device
KR1020187030433A KR102339860B1 (en) 2016-05-10 2017-04-05 Optical film for organic EL display devices, polarizing film for organic EL display devices, polarizing film with adhesive layer for organic EL display devices, and organic EL display device

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