WO2017195506A1 - 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 - Google Patents

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 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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Prior art keywords
organic
film
adhesive layer
display device
sensitive adhesive
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PCT/JP2017/014222
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English (en)
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 KR1020187030433A priority Critical patent/KR102339860B1/ko
Priority to CN201780025832.0A priority patent/CN109121431B/zh
Priority to SG11201809771SA priority patent/SG11201809771SA/en
Publication of WO2017195506A1 publication Critical patent/WO2017195506A1/ja

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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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PCT/JP2017/014222 2016-05-10 2017-04-05 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 WO2017195506A1 (ja)

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KR1020187030433A KR102339860B1 (ko) 2016-05-10 2017-04-05 유기 el 표시 장치용 광학 필름, 유기 el 표시 장치용 편광 필름, 유기 el 표시 장치용 점착제층 구비 편광 필름, 및 유기 el 표시 장치
CN201780025832.0A CN109121431B (zh) 2016-05-10 2017-04-05 用于有机电致发光显示装置的光学膜、偏振膜、带粘合剂层的偏振膜、以及有机电致发光显示装置
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

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