WO2017145469A1 - Laminate, polarizing plate and image display device - Google Patents

Laminate, polarizing plate and image display device Download PDF

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Publication number
WO2017145469A1
WO2017145469A1 PCT/JP2016/084796 JP2016084796W WO2017145469A1 WO 2017145469 A1 WO2017145469 A1 WO 2017145469A1 JP 2016084796 W JP2016084796 W JP 2016084796W WO 2017145469 A1 WO2017145469 A1 WO 2017145469A1
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group
general formula
repeating unit
polymer
laminate
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PCT/JP2016/084796
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French (fr)
Japanese (ja)
Inventor
考浩 加藤
佑起 中沢
遊 内藤
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富士フイルム株式会社
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Priority to JP2018500993A priority Critical patent/JP6713529B2/en
Publication of WO2017145469A1 publication Critical patent/WO2017145469A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

Definitions

  • the present invention relates to a laminate, a polarizing plate using the laminate, and an image display device using the polarizing plate.
  • Image display devices represented by electroluminescence displays (ELD), liquid crystal display devices (LCD), and the like are increasingly demanded for thinning.
  • ELD electroluminescence displays
  • LCD liquid crystal display devices
  • image display devices have the ability to stably maintain good image quality even in harsh environments (high durability). Is now required.
  • the decrease in image quality in the image display device is partly caused by water entering the polarizing plate and degrading the polarizer.
  • the polarizer is protected by laminating a protective film (optical film) on the surface, and the protective film is also required to be thin. When the protective film is thinned, water is more likely to come into contact with the polarizer, and the image quality is likely to deteriorate.
  • the protective film tends to deteriorate in optical characteristics when used in the harsh environment described above (particularly in a high temperature environment). Examples of such deterioration of optical characteristics include an increase in haze value and film coloring.
  • cellulose ester resins, acrylic resins, and the like are widely used from the viewpoints of versatility and processability. It is also known to form a protective film using a blend resin in which a cellulose ester and an acrylic resin are mixed in order to obtain a desired protective film exhibiting desired optical properties and moisture permeability (for example, Patent Documents 1 and 2).
  • the present invention is a laminate comprising a cellulose ester resin layer, which has excellent interlayer adhesion, and suppresses deterioration of the polarizer over time even when it is thinned and used as a protective film for a polarizer.
  • a laminate that suppresses the increase in haze value over time even in a high-temperature environment and can maintain good display performance for a long time when incorporated in an image display device, and uses this laminate. It is an object of the present invention to provide a polarizing plate and an image display device using the polarizing plate.
  • the present inventors directly provided a layer containing a polymer having a repeating unit having a specific structure and having a glass transition temperature equal to or higher than a specific temperature on the cellulose ester resin layer.
  • the laminate is excellent in adhesion between layers, can suppress the increase in haze value over time even in a high temperature environment, and when used as a protective film for a polarizer, It was found that deterioration can be suppressed.
  • the present invention has been further studied based on these findings and has been completed.
  • R a represents a hydrogen atom, an alkyl group, or an alkoxycarbonyl group.
  • R b and R c represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
  • R 2 represents an alkyl group, a cycloalkyl group or an aryl group.
  • L 1 represents a divalent linking group formed by combining two or more divalent groups selected from an alkylene group, an arylene group, —C ( ⁇ O) —, —O—, and —NR 3 —. However, L 1 includes a group represented by —C ( ⁇ O) NR 3 —. R 3 represents a hydrogen atom or a substituent.
  • R 1a represents a hydrogen atom or methyl.
  • R 2 has the same meaning as R 2 in the general formula (1).
  • L 2 represents an alkylene group, an alkyleneoxy group or a polyalkyleneoxy group.
  • R 3 has the same meaning as R 3 in the general formula (1).
  • R 1a and R 2 are the same meanings as R 1a and R 2 in the general formula (2).
  • R 3a represents a hydrogen atom or an alkyl group.
  • R 1a and R 2 are the same meanings as R 1a and R 2 in the general formula (3).
  • the polymer having a repeating unit represented by the general formula (1) has a repeating unit represented by the general formula (1) and a repeating unit represented by the following general formula (5).
  • R 4 and R 5 represent a hydrogen atom, an alkyl group, an aryl group, or an alkoxycarbonyl group.
  • R 6 represents a hydrogen atom or an alkyl group.
  • L 3 is a single bond, a divalent group selected from an alkylene group, an arylene group, —C ( ⁇ O) —, —O— and —N (R 3A ) —, or two of these groups A divalent linking group formed by combining the above is shown.
  • R 3A represents a hydrogen atom or a substituent.
  • substituents, etc. when there are a plurality of substituents, linking groups, etc. (hereinafter referred to as substituents, etc.) indicated by specific symbols, or when a plurality of substituents etc. are specified simultaneously or alternatively, It means that a substituent etc. may mutually be same or different. The same applies to the definition of the number of substituents and the like. Further, when a plurality of substituents and the like are close (especially adjacent), they may be connected to each other or condensed to form a ring.
  • the display of a compound uses in the meaning containing its salt and its ion besides the compound itself.
  • the salt of the compound include, for example, an acid addition salt of the compound formed with the compound and an inorganic acid or an organic acid, or a base addition salt of the compound formed with the compound and an inorganic base or an organic base.
  • the ion of the compound include an ion including a skeleton of the compound formed by dissociating the salt of the above-described compound.
  • a substituent that does not specify substitution or non-substitution means that the group may have an arbitrary substituent as long as a desired effect is achieved. . This is also the same for compounds that do not specify substitution or non-substitution.
  • substituted includes groups selected from the following substituent group T unless otherwise specified.
  • substituent group T when only a substituent having a specific range is described (for example, when only described as “alkyl group”), a corresponding group of the following substituent group T (in the above case, an alkyl group) The preferred range in FIG.
  • this number of carbons means the total number of carbon atoms in the group. That is, when this group is a form further having a substituent, it means the total number of carbon atoms including this substituent.
  • Substituent group T An alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an n-octyl group, n-decyl group, n-hexadecyl group, etc.), cycloalkyl group (preferably having 3 to 20, more preferably 3 to 12, particularly preferably 3 to 8 carbon atoms, cyclopropyl group) , A cyclopentyl group, a cyclohexyl group, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms such as vinyl group, allyl group, 2- Butenyl group, 3-pentenyl group, etc.), alkynyl group (preferably having 2 to 20
  • 6 to 12 for example, phenyloxy group, 2-naphthyloxy group, etc.
  • acyl group preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms.
  • 12 such as an acetyl group, a benzoyl group, a formyl group, and a pivaloyl group
  • an alkoxycarbonyl group preferably having 2 to 20, more preferably 2 to 16, and particularly preferably 2 to 12 carbon atoms).
  • methoxycarbonyl group, ethoxycarbonyl group, etc. aryloxycarbonyl group (preferably having 7 to 20, more preferably 7 to 16, particularly preferably 7 to 10 carbon atoms such as phenyloxy A carbonyl group, etc.), an acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16, particularly preferably 2 to 10, and examples thereof include an acetoxy group and a benzoyloxy group.
  • An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 and particularly preferably 2 to 10 such as acetylamino group and benzoylamino group), alkoxycarbonylamino group ( Preferably it has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group, and an aryloxycarbonylamino group (preferably 7 to 7 carbon atoms).
  • Examples thereof include a phenyloxycarbonylamino group), a sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms). And particularly preferably 1 to 12, for example, methanesulfonylamino group, benzenesulfonate Amino groups, etc.), sulfamoyl groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms such as sulfamoyl group, methylsulfamoyl group, dimethylsulfayl group).
  • a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as a carbamoyl group and a methylcarbamoyl group).
  • alkylthio group preferably having 1 to 20, more preferably 1 to 16, particularly preferably 1 to 12 carbon atoms, such as methylthio group and ethylthio group
  • Arylthio group preferably having 6 to 20 carbon atoms, More preferably, it is 6 to 16, particularly preferably 6 to 12, and examples thereof include a phenylthio group.
  • a sulfonyl group preferably having 1 to 20 carbon atoms, more preferably 1 to 16, and particularly preferably 1 to 1).
  • a mesyl group and a tosyl group such as a mesyl group and a tosyl group
  • a sulfinyl group preferably having 1 to 20 carbon atoms, more preferably 1 to 16 and particularly preferably 1 to 12, such as a methanesulfinyl group, Benzenesulfinyl group, etc.
  • urethane group preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, such as ureido group, methylureido group, phenyl group) Ureido groups, etc.
  • phosphoric acid amide groups preferably having 1-20 carbon atoms, more preferably 1-16, 1 to 12 is preferable, and examples thereof include diethyl phosphoric acid amide and phenyl phosphoric acid amide.
  • Heterocyclic group preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, an imidazolyl group, a pyridyl group, a quinolyl group , A furyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, a benzimidazolyl group, a benzthiazolyl group, and the like, and a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to
  • the laminate of the present invention has excellent adhesion between layers in the laminate and can suppress deterioration of the polarizer over time under high-temperature and high-humidity conditions by forming a thin film and overlapping the polarizer. Moreover, the laminated body of this invention can suppress the raise over time of a haze value also in a high temperature environment.
  • the polarizing plate and the image display device of the present invention have the laminate of the present invention that exhibits the above effects, and the deterioration of the polarizer can be effectively suppressed even under high temperature and high humidity conditions.
  • the degree of suppressing the deterioration of the polarizer under high temperature and high humidity conditions is also referred to as “polarizer durability” or “polarizing plate durability”.
  • FIG. 1 is a cross-sectional view showing an embodiment of the laminate of the present invention.
  • FIG. 2 is a schematic diagram showing an outline of an embodiment of a liquid crystal display device including a polarizing plate incorporating the polarizing plate protective film of the present invention.
  • the laminate of the present invention has a cellulose ester resin layer 11 and a repeating unit that is directly provided on the cellulose ester resin layer 11 and represented by the following general formula (1).
  • a layer 12 containing a polymer having a glass transition temperature higher than a specific temperature (hereinafter also simply referred to as “polymer layer”) is included. Details of the cellulose ester resin layer 11 and the polymer layer 12 will be described later.
  • the polymer layer may be provided on one side of the cellulose ester resin layer 11 as shown in FIG. 1, or the polymer layer may be provided on both sides of the cellulose ester resin layer 11. There may be.
  • the laminate of the present invention has a form in which the polymer layer is provided on one side of the cellulose ester resin layer 11. Two or more polymer layers having different compositions may be provided on the cellulose ester resin layer. When two or more polymer layers are formed, two or more polymer layers may be provided on one side of the cellulose ester resin layer, and two or more polymer layers may be provided on both sides of the cellulose ester resin layer. .
  • the laminate of the present invention may have various functional layers (not shown) specialized for specific functions in addition to the cellulose ester resin layer 11 and the polymer layer 12.
  • a functional layer include a hard coat layer, an antireflection layer, a light scattering layer, an antifouling layer, and an antistatic layer.
  • the “polymer layer” refers to a polymer having a repeating unit of the general formula (1) described later and having a glass transition temperature of 50 ° C. or higher (hereinafter referred to as “polymer (S)”.
  • the term “polymer” refers to a polymer (S) or a polymer corresponding thereto (for example, a polymer to be compared with the polymer (S), and not a cellulose ester resin) unless otherwise specified. It means a layer containing 50% by mass or more.
  • the content of the polymer (S) in the polymer layer is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 85% by mass or more.
  • the content of the polymer (S) in the polymer layer may be 100% by mass, and is usually 99% by mass or less.
  • the balance can contain various conventional additives or resins. Examples of such additives include plasticizers, organic acids, dyes, polymers, retardation modifiers, ultraviolet absorbers, antioxidants, matting agents, and the like.
  • the polymer (S) constituting the polymer layer has a repeating unit represented by the following general formula (1).
  • R a represents a hydrogen atom, an alkyl group or an alkoxycarbonyl group.
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 1 to 4.
  • Preferable specific examples of this alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, s-butyl and isobutyl.
  • R a is an alkoxycarbonyl group
  • the alkoxycarbonyl group may be linear or branched.
  • the alkoxycarbonyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, further preferably 2 to 8 carbon atoms, and further preferably 2 to 4 carbon atoms.
  • Preferable specific examples of this alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl and the like.
  • R a is more preferably a hydrogen atom or methyl.
  • R b and R c represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, more preferably 1 to 3, more preferably methyl or ethyl, and still more preferably methyl.
  • R b and R c are an aryl group
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, particularly preferably 6 to 12 carbon atoms, and particularly preferably phenyl.
  • R b and R c are alkoxycarbonyl groups
  • the alkoxycarbonyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and still more preferably methoxycarbonyl or ethoxycarbonyl.
  • R b and R c are more preferably a hydrogen atom.
  • L 1 represents a divalent linking group formed by combining two or more divalent groups selected from an alkylene group, an arylene group, —C ( ⁇ O) —, —O—, and —NR 3 —.
  • L 1 includes a group represented by —C ( ⁇ O) NR 3 — in its structure.
  • the number of —C ( ⁇ O) NR 3 — in L 1 is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.
  • the number of NR 3 ⁇ is one.
  • L 1 includes a group represented by —C ( ⁇ O) NR 3 —
  • L 1 includes a group represented by —C ( ⁇ O) NR 3 —
  • the form in which the C ( ⁇ O) side of —C ( ⁇ O) NR 3 — is bonded to the R 2 side In addition, both forms in which the NR 3 side of —C ( ⁇ O) NR 3 — is bonded to the R 2 side are included.
  • R 3 represents a hydrogen atom or a substituent.
  • substituents include a group selected from the substituent group T described above, and an alkyl group is particularly preferable.
  • the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably methyl or ethyl.
  • R 3 is preferably a group bonded to a nitrogen atom in —C ( ⁇ O) NR 3 — by a carbonyl group.
  • R 3 preferably takes a form in which R 3 is bonded to the substituent of R 2 .
  • R 2 is preferably an aryl group (preferably a phenyl group). Of these, R 3 is preferably a hydrogen atom.
  • the alkylene group that can constitute L 1 may be linear or branched.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.
  • the arylene group that can constitute L 1 preferably has 6 to 20 carbon atoms, and more preferably 6 to 15 carbon atoms. 6 to 12 are more preferable, and a phenylene group is more preferable.
  • L 1 is preferably a divalent linking group formed by combining two or more divalent groups selected from an alkylene group, —C ( ⁇ O) —, —O—, and —NR 3 —.
  • L 1 has a molecular weight of preferably 12 to 240, more preferably 44 to 150.
  • R 2 represents an alkyl group, a cycloalkyl group or an aryl group.
  • the structure of R 2 does not include any of —C ( ⁇ O) —, an oxygen atom, and a nitrogen atom. That is, when R 2 is an alkyl group, a cycloalkyl group, or an aryl group, when these alkyl group, cycloalkyl group, and aryl group are in a form having a substituent, the substituent includes a carbonyl group, an oxygen atom And nitrogen atoms are not included.
  • R 2 when R 2 is an alkyl group, the alkyl group is interpreted to be as long as possible a long-chain alkyl group (an alkyl group having the largest number of carbon atoms).
  • L 1 does not have an alkylene group at the R 2 side end and R 2 is ethyl
  • this form is, in a different way, L 1 has methylene at the R 2 side end and R 2 Can also be interpreted as the form in which is methyl.
  • this form is interpreted as R 2 is ethyl.
  • R 2 when R 2 is an aryl group, the aryl group should be interpreted as an aryl group having a molecular weight as large as possible.
  • L 1 is as free an arylene group R 2 side end, and a phenylene when R 2 is a phenyl group having a phenyl as a substituent, if this form another point of view, L 1 is the R 2 side end And R 2 is phenyl.
  • this form is interpreted as a phenyl group in which R 2 has phenyl as a substituent.
  • R 2 is an alkyl group
  • the alkyl group may be linear or branched. Further, it may be unsubstituted or may have a substituent.
  • the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and further preferably 1 to 4.
  • L 1 has a form having —NR 3 — at the R 2 side terminal
  • the alkyl group R 2 may be linked to R 3 to form a ring. Examples of such a ring structure include a morpholine ring, a pyrrolidone ring, an imidazolidone ring, and a succinimide ring, and a morpholine ring is preferred.
  • R 2 is a cycloalkyl group
  • the cycloalkyl group may be unsubstituted or may have a substituent.
  • the cycloalkyl preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, still more preferably 6 to 12 carbon atoms, and even more preferably a cyclopentyl group or a cyclohexyl group.
  • R 2 is an aryl group
  • the aryl group may be unsubstituted or may have a substituent.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, still more preferably 6 to 12 carbon atoms, and particularly preferably a phenyl group.
  • the repeating unit represented by the general formula (1) is preferably a repeating unit represented by the following general formula (2) or (3).
  • R 1a represents a hydrogen atom or methyl.
  • R 2 has the same meaning as R 2 in the general formula (1), and the preferred form is also the same.
  • L 2 represents an alkylene group, an alkyleneoxy group or a polyalkyleneoxy group.
  • the alkylene group may be linear or branched, and is preferably linear.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably ethylene.
  • L 2 is an alkyleneoxy group
  • the alkyleneoxy group may be linear or branched, and is preferably linear.
  • the alkyleneoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3.
  • the alkyleneoxy group constituting the polyalkyleneoxy group may be linear or branched, and is preferably linear.
  • the alkyleneoxy group constituting the polyalkyleneoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3.
  • the total number of carbon atoms of the polyalkyleneoxy group is preferably 1 to 10, more preferably 1 to 6.
  • the oxygen number of the polyalkyleneoxy group is preferably 1 to 4, more preferably 1 to 3, and particularly preferably 1 to 2.
  • L 2 is a polyalkyleneoxy group
  • the alkyleneoxy groups constituting the polyalkyleneoxy group may be the same or different.
  • L 2 is particularly preferably an ethyleneoxy group.
  • an oxygen atom in the alkyleneoxy group or polyalkyleneoxy group is linked to A.
  • A represents —C ( ⁇ O) NR 3 — or —NR 3 —C ( ⁇ O) —NR 3 —.
  • R 3 has the same meaning as R 3 described in the general formula (1), and the preferred form is also the same.
  • R 1a and R 2 each have the same meaning as R 1a and R 2 in the general formula (2), a preferred form also the same.
  • R 3a represents a hydrogen atom or an alkyl group.
  • the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably methyl or ethyl.
  • R 2 and R 3a are both alkyl groups, they may be linked to each other to form a ring.
  • the ring atoms of this ring structure may contain heteroatoms other than nitrogen atoms. Specific examples of this ring structure include a morpholine ring, a pyrrolidone ring, an imidazolidone ring, and a succinimide ring, and a morpholine ring is preferred.
  • the repeating unit represented by the general formula (1) is more preferably a repeating unit represented by the following general formula (4).
  • R 1a and R 2 each have the same meaning as R 1a and R 2 in the general formula (3), a preferred form also the same.
  • the polymer (S) may consist of only the repeating unit represented by the general formula (1) or may have a repeating unit other than the repeating unit represented by the general formula (1). .
  • the content of the repeating unit represented by the general formula (1) in the polymer (S) is preferably 10 to 100% by mass, and more preferably 20 to 100% by mass.
  • the polymer (S) has physical properties that are easily dissolved in a coating solvent used when forming the cellulose ester resin layer, and is excellent in recyclability.
  • the obtained laminate is cut into a desired size and shipped. It is assumed that the cut unnecessary pieces are mixed and recycled within a range that is allowed in the material forming the cellulose ester resin layer (within a range that does not impair desired optical properties and the like). In that case, the polymer (S) is sufficiently dissolved in the coating solvent used to form the cellulose ester resin layer, and the polymer (S) and the cellulose ester resin are homogeneously mixed in the coating solvent.
  • the polymer (S) is excellent in solubility in such a solvent and excellent in recyclability.
  • the polymer (S) also preferably has a repeating unit represented by the following general formula (5). By having a repeating unit represented by the following general formula (5), the solubility in the coating solvent can be further increased, and the recyclability described above can be further improved.
  • R 6 represents a hydrogen atom or an alkyl group.
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms.
  • R 6 is more preferably methyl or ethyl, and even more preferably methyl.
  • R 6 is more preferably a hydrogen atom or methyl.
  • R 4 and R 5 represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, more preferably 1 to 3, more preferably methyl or ethyl, and still more preferably methyl.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, particularly preferably 6 to 12 carbon atoms, and particularly preferably phenyl.
  • R 4 and R 5 are alkoxycarbonyl groups
  • the alkoxycarbonyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and still more preferably methoxycarbonyl or ethoxycarbonyl.
  • R 4 and R 5 are more preferably a hydrogen atom.
  • L 3 is a single bond, or a divalent group selected from an alkylene group, an arylene group, —C ( ⁇ O) —, —O— and —NR 3A —, or a combination of two or more of these groups And a divalent linking group.
  • R 3A represents a hydrogen atom or a substituent.
  • examples of the substituent include a group selected from the substituent group T described above, and an alkyl group is particularly preferable.
  • the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably methyl or ethyl.
  • the number of the linking groups to be combined is not particularly limited, but is preferably 2 to 9, and more preferably 2 or 3.
  • the combination of the linking groups is not particularly limited.
  • a combination of —C ( ⁇ O) —, —O— and an alkylene group is more preferred.
  • L 3 is a linking group containing —C ( ⁇ O) —, and —C ( ⁇ O) — is bonded to the main chain (the carbon atom to which R 6 is bonded).
  • the alkylene group L 3 or the alkylene group incorporated in L 3 is preferably linear.
  • the alkylene group preferably has 1 to 5 carbon atoms, more preferably 1 to 4, more preferably 1 to 3, and particularly preferably 2.
  • the arylene group L 3 or the arylene group incorporated in L 3 preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, particularly preferably 6 to 12 carbon atoms, and particularly preferably phenylene.
  • the content of the repeating unit represented by the general formula (5) in the polymer (S) is 5 to 30% by mass. 10 to 20% by mass is more preferable.
  • the polymer (S) contains a repeating unit other than the repeating unit represented by the general formula (1) together with the repeating unit represented by the general formula (1),
  • the remainder excluding the repeating unit represented by the general formula (1) is not included in the repeating unit represented by the general formula (5) and / or the repeating unit represented by the general formula (1).
  • repeating Unit (R) a repeating unit derived from a (meth) acrylic acid ester not included in the repeating unit represented by the general formula (1) and not included in the repeating unit represented by the general formula (5) is referred to as “repeating Unit (R) ”.
  • the repeating unit derived from (meth) acrylic-acid alkylester is more preferable.
  • the repeating unit (R) include, for example, a repeating unit derived from benzyl (meth) acrylate, a repeating unit derived from methyl (meth) acrylate, a repeating unit derived from ethyl (meth) acrylate, and phenoxyethyl (meth) acrylate.
  • the general formula (1) in the polymer (S), in the total molar amount of the repeating unit represented by the general formula (1), the repeating unit represented by the general formula (5), and the repeating unit (R), the general formula
  • the molar amount of the repeating unit represented by (1) is preferably 10 to 100 mol%, more preferably 15 to 100 mol%, and further preferably 20 to 95 mol%.
  • the said polymer (S) has the said repeating unit (R), in the said polymer (S), it represents with the repeating unit represented by the said General formula (1), and the said General formula (5).
  • the molar amount of the repeating unit (R) is preferably 10 to 95 mol%, more preferably 10 to 90 mol%, and further preferably 20 to 90 mol%.
  • the polymer (S) has a glass transition temperature (Tg) of 50 ° C. or higher.
  • Tg of the polymer (S) is preferably 70 ° C or higher, more preferably 80 ° C or higher, further preferably 90 ° C or higher, and further preferably 95 ° C or higher.
  • Tg glass transition temperature
  • Tg is measured using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the methods described in Examples described later can be used.
  • the measurement sample in addition to the polymer powder itself, a powder obtained by scraping the polymer layer from the laminate may be used.
  • the lower limit value of the weight average molecular weight of the polymer (S) is preferably 10,000 or more, more preferably 20,000 or more, and further preferably 30,000, from the viewpoint of film planarity. preferable.
  • the upper limit of the weight average molecular weight of the polymer (S) is preferably 500,000 or less, more preferably 300,000 or less, and 200,000 or less, from the viewpoint of film forming properties. More preferably, it is more preferably 150,000 or less.
  • the weight average molecular weight can be measured by the method described in Examples described later.
  • the polymer (S) can be obtained by polymerizing a monomer that leads each of the above repeating units by a conventional method.
  • it can be obtained by polymerizing a monomer by heat treatment and / or light irradiation in the presence of a thermal polymerization initiator and / or a photopolymerization initiator.
  • the film thickness of the polymer layer is not particularly limited, preferably 1 to 25 ⁇ m, more preferably 2 to 20 ⁇ m, particularly preferably 1 to 15 ⁇ m.
  • the film thickness of the polymer layer is preferably 2 to 15 ⁇ m, preferably 3 to 15 ⁇ m, and preferably 5 to 15 ⁇ m.
  • the cellulose ester resin layer which comprises the laminated body of this invention is a layer which contains 50 mass% or more of cellulose esters in a layer. 60 mass% or more is preferable, as for content of the cellulose ester in a cellulose-ester resin layer, 70 mass% or more is more preferable, 80 mass% or more is further more preferable, and 85 mass% or more is further more preferable.
  • the upper limit of the content of the cellulose ester in the cellulose ester resin layer is usually 96% by mass or less, preferably 95% by mass or less, and more preferably 92% by mass or less. In this case, the remainder excluding the cellulose ester includes, for example, additives described later.
  • the cellulose ester used as a raw material in the production of the cellulose ester resin layer of the present invention will be described.
  • the cellulose ester raw material cellulose used in the present invention includes cotton linter, wood pulp (hardwood pulp, softwood pulp), etc., and any cellulose obtained from any raw material cellulose can be used. May be.
  • the raw material cellulose is, for example, Marusawa, Uda, “Plastic Materials Course (17) Fibrous Resin”, Nikkan Kogyo Shimbun (published in 1970), or Japan Institute of Invention and Technology Publication No. 2001-1745 (page 7). To page 8) can be used.
  • As a cellulose ester the well-known cellulose ester used for manufacture of a cellulose-ester film can be used without a restriction
  • Cellulose acylate As the cellulose acylate used in the present invention, a known cellulose acylate used for producing a cellulose acylate film can be used without any limitation.
  • the ⁇ -1,4-bonded glucose unit constituting cellulose has free hydroxy groups at the 2nd, 3rd and 6th positions.
  • Cellulose acylate is a polymer obtained by acylating a part of these hydroxy groups with an acyl group.
  • the degree of acyl substitution (hereinafter sometimes simply referred to as “degree of substitution”) indicates the degree of acylation of the hydroxy group of cellulose located at the 2-position, 3-position and 6-position, and is 2 for all glucose units.
  • the total degree of acyl substitution is 3.
  • the total acyl substitution degree is 1 when all of any one of the 6-position and 2-position is acylated in each glucose unit in all hydroxy groups of all glucose. That is, the degree of substitution indicates the degree of acylation, assuming that 3 is when all the hydroxy groups in the glucose molecule are all acylated.
  • the degree of substitution of cellulose acylate is described in Tezuka et al., Carbohydrate. Res. , 273, 83-91 (1995), or according to the method prescribed in ASTM-D817-96.
  • the total acyl substitution degree of the cellulose acylate used in the present invention is preferably 1.50 or more and 3.00 or less, more preferably 2.00 to 2.97, from the viewpoint of moisture permeability, and 2.30 or more. More preferably, it is less than 2.97, and particularly preferably 2.30 to 2.95.
  • the acyl group of the cellulose acylate used in the present invention is not particularly limited, and may be a form having one kind of acyl group or a form having two or more kinds of acyl groups.
  • the cellulose acylate that can be used in the present invention preferably has an acyl group having 2 or more carbon atoms as a substituent.
  • the acyl group having 2 or more carbon atoms is not particularly limited, and may be an aliphatic acyl group or an aromatic acyl group.
  • acyl group having 2 or more carbon atoms include acetyl, propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, isobutanoyl, tert-butanoyl, cyclohexanecarbonyl Oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like.
  • acetyl, propionyl, butanoyl, dodecanoyl, octadecanoyl, tert-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, and cinnamoyl are preferable, and acetyl, propionyl, and butanoyl are more preferable.
  • Cellulose acetate using only an acetyl group as the acyl group of cellulose acylate can be preferably used in the present invention.
  • the total acyl substitution degree of this cellulose acetate is 2.00 to 3 from the viewpoint of moisture permeability and optical properties. Is preferably 0.000, more preferably 2.20 to 3.00, still more preferably 2.30 to 3.00, still more preferably 2.30 to 2.97, Particularly preferred is 2.30 to 2.95.
  • a mixed fatty acid ester having two or more kinds of acyl groups can also be preferably used as the cellulose acylate in the present invention.
  • mixed acid esters having fatty acid acyl groups and substituted or unsubstituted aromatic acyl groups described in paragraphs 0023 to 0038 of JP-A-2008-20896 can be preferably used.
  • the acyl group of the mixed fatty acid ester preferably includes an acetyl group and an acyl group having 3 to 4 carbon atoms.
  • the degree of acetyl substitution is preferably less than 2.5 and more preferably less than 1.9.
  • the degree of substitution of the acyl group having 3 to 4 carbon atoms is preferably 0.1 to 1.5, and preferably 0.2 to 1.2. Is more preferable, and 0.5 to 1.1 is particularly preferable.
  • the cellulose ester resin layer used in the present invention it is also preferable to employ a resin layer composed of a plurality of layers composed of different cellulose acylates by a co-casting method described later.
  • the cellulose ester or cellulose acylate used in the present invention preferably has a degree of polymerization of 250 to 800, more preferably 300 to 600.
  • the number average molecular weight of the cellulose ester or cellulose acylate used in the present invention is preferably 40000 to 230,000, more preferably 60000 to 230,000, and most preferably 75,000 to 200000.
  • the degree of polymerization can be determined by dividing the number average molecular weight measured in terms of polystyrene by gel permeation chromatography (GPC) by the molecular weight of the glucopyranose unit of cellulose ester or cellulose acylate.
  • the cellulose ester used in the present invention can be synthesized by a conventional method.
  • cellulose acylate can be synthesized using an acid anhydride, acid chloride, or the like as an acylating agent.
  • an organic acid for example, acetic acid
  • a protic catalyst such as sulfuric acid can be used as the catalyst.
  • the acylating agent is an acid chloride
  • a basic compound can be used as a catalyst.
  • cellulose acylate In general industrial production of cellulose acylate, an organic acid (acetic acid, propionic acid, butyric acid, etc.) corresponding to the desired acyl group or an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride, etc.) of cellulose is used. Is used to esterify the hydroxy group. For example, a cellulose derived from cotton linter or wood pulp is used as a raw material, and this is activated with an organic acid such as acetic acid and then esterified with an organic acid having a desired structure in the presence of a sulfuric acid catalyst. Acylate can be obtained.
  • an organic acid acetic acid, propionic acid, butyric acid, etc.
  • an acid anhydride acetic anhydride, propionic anhydride, butyric anhydride, etc.
  • cellulose is generally esterified using an excess amount of the organic acid anhydride relative to the amount of hydroxy groups present in the cellulose.
  • Cellulose acylate can also be synthesized, for example, by the method described in JP-A-10-45804.
  • the cellulose ester resin layer of the present invention other resins (for example, (meth) acrylic resin etc.) can be used in combination with the cellulose ester within a range not impairing the effects of the present invention.
  • the content of the other resin in the cellulose ester film is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and further preferably 15% by mass or less in the cellulose ester film. 10 mass% or less is still more preferable.
  • the formation of the cellulose ester resin layer is not particularly limited.
  • the cellulose ester resin layer is preferably formed by a melt film formation method or a solution film formation method (solvent casting method). More preferably, it is formed by a film forming method (solvent casting method). Examples of film production using the solvent cast method are described in U.S. Pat. Nos. 2,336,310, 2,367,603, 2,492,078, 2,492,977, Nos. 2,492,978, 2,607,704, 2,739,069 and 2,739,070, British Patent Nos. 640731 and 736892 And the Japanese Patent Publications Nos.
  • the said cellulose-ester resin layer may be extended
  • JP-A-62-115035, JP-A-4-152125, 4-284221, 4-298310, and 11-48271. can do.
  • a method of casting the solution As a method of casting the solution, a method of uniformly extruding the prepared dope from a pressure die onto a metal support, a doctor blade for adjusting the film thickness with a blade of the dope once cast on a support of metal or the like And a method using a reverse roll coater that adjusts with a reversely rotating roll, and a method using a pressure die is preferred.
  • the pressure die includes a coat hanger type and a T die type, and any of them can be preferably used. In addition to the methods listed here, it can be carried out by various known methods for casting a cellulose ester solution, and each condition is set in consideration of differences in the boiling point of the solvent used. can do.
  • the cellulose ester resin layer may be a single layer or multiple layers, and in the case of multiple layers, it is preferable to use a lamination casting method such as a co-casting method, a sequential casting method, or a coating method.
  • a lamination casting method such as a co-casting method, a sequential casting method, or a coating method.
  • the simultaneous co-casting (also referred to as simultaneous multi-layer co-casting) method is particularly preferable from the viewpoint of stable production and production cost reduction.
  • a casting dope for each layer (which may be three layers or more) is simultaneously applied from a separate slit or the like on a casting support (band or drum).
  • the dope is extruded using a casting die that can be extruded, and the layers are cast simultaneously. It is a casting method in which after casting, the film is peeled off from the support after an appropriate time and dried to form a film.
  • a co-casting die for example, a total of three layers: a surface layer two layers formed from a surface layer dope on a casting support, and a core layer composed of a core layer dope sandwiched between these surface layers. It can be extruded and cast simultaneously on a support.
  • the casting dope for the first layer is first extruded from the casting die on the casting support, cast, and dried on the second layer without drying or drying.
  • the dope for casting is extruded from the casting die, and if necessary, the dope is cast and laminated sequentially up to the third layer or more, and peeled off from the support after a suitable time and dried.
  • a cellulose ester resin layer is formed.
  • the coating method generally, a core layer is formed into a film by a solution casting method, and a coating solution that is a target cellulose ester solution is applied to the surface layer, followed by drying to form a cellulose ester having a laminated structure. A resin layer is formed.
  • the cellulose ester resin layer is preferably stretched after casting and drying.
  • the stretching direction of the cellulose ester resin layer may be either the film transport direction (MD (Machine Direction) direction) or the direction orthogonal to the transport direction (TD (Transverse Direction) direction). Considering the subsequent polarizing plate processing process, the TD direction is preferable.
  • the stretching process may be performed a plurality of times in two or more stages.
  • the film can be stretched by conveying the film while holding the film with a tenter and gradually widening the width of the tenter. Further, after the film is dried, it can be stretched using a stretching machine (preferably uniaxial stretching using a long stretching machine). In the case of stretching in the MD direction, for example, it can be performed by adjusting the speed of the film transport roller to make the winding speed faster than the film peeling speed.
  • the transmission axis of the polarizer and the cellulose ester An embodiment in which slow axes in the plane of the resin layer are arranged in parallel is preferable. Since the transmission axis of the roll film-like polarizer produced continuously is generally parallel to the width direction of the roll film, it is composed of the roll film-like polarizer and the roll film-like cellulose ester resin layer.
  • the in-plane slow axis of the roll film-shaped protective film needs to be parallel to the width direction of the cellulose ester resin layer. Therefore, it is preferable to stretch more in the TD direction.
  • the stretching process may be performed in the middle of the film forming process, or the original fabric that has been formed and wound may be stretched.
  • the stretching in the TD direction is preferably 5 to 100%, more preferably 5 to 80%, and particularly preferably 5 to 40%. In the case of unstretched, the stretching is 0%.
  • the cellulose ester resin layer may contain an additive as long as the effects of the present invention are not impaired.
  • the additive include known plasticizers, organic acids, dyes, polymers, retardation adjusting agents, ultraviolet absorbers, antioxidants, matting agents, and the like. Regarding these, the description of paragraph numbers 0062 to 0097 of JP2012-155287A can be referred to, and the contents thereof are incorporated in the present specification.
  • the additive include a peeling accelerator, an organic acid, and a polyvalent carboxylic acid derivative. With respect to these, the description of WO2015 / 005398, paragraphs 0212 to 0219 can be referred to, and the contents thereof are incorporated in the present specification.
  • examples of the additive include a radical scavenger, a deterioration inhibitor, and a barbituric acid compound, which will be described later.
  • the content of the additive is preferably 50 parts by mass or less with respect to 100 parts by mass of the cellulose ester. 30 parts by mass or less, more preferably 5 to 30 parts by mass.
  • Plasticizer One preferred additive is a plasticizer.
  • a plasticizer By adding a plasticizer to the cellulose ester resin layer, the hydrophobicity of the cellulose ester resin layer can be increased. This point is preferable from the viewpoint of reducing the water content of the cellulose ester resin layer.
  • the use of such a plasticizer can reduce the occurrence of display unevenness of the image display device due to humidity when the laminate having a cellulose ester resin layer is used as a polarizing plate protective film. preferable.
  • the molecular weight of the plasticizer is preferably 3000 or less, more preferably 1500 or less, and still more preferably 1000 or less, from the viewpoint of obtaining the above-described effect by adding it satisfactorily.
  • the molecular weight of the plasticizer is, for example, 300 or more, preferably 350 or more, from the viewpoint of low volatility. In the case of multimeric plasticizers, the molecular weight is the number average molecular weight.
  • a polyhydric ester compound of polyhydric alcohol hereinafter also referred to as “polyhydric alcohol ester plasticizer”
  • a polycondensed ester compound hereinafter also referred to as “polycondensed ester plasticizer”
  • carbohydrate compounds hereinafter also referred to as “carbohydrate derivative plasticizers”.
  • polyhydric alcohol ester plasticizers WO2015 / 005398 paragraphs 0081 to 0098, for polycondensed ester plasticizers, paragraphs 00099 to 0122, and for carbohydrate derivative plasticizers, paragraphs 0123 to 0140. The contents of which are hereby incorporated by reference.
  • the content of these plasticizers is 1 to 20 parts by mass with respect to 100 parts by mass of the resin (cellulose ester) of the layer to which the plasticizer is added from the viewpoint of achieving both the effect of adding the plasticizer and suppressing the precipitation of the plasticizer.
  • the content is 2 to 15 parts by mass, more preferably 5 to 15 parts by mass.
  • Two or more kinds of these plasticizers may be added. Also when adding 2 or more types, the specific example and preferable range of addition amount are the same as the above.
  • One preferable additive may include an antioxidant.
  • the description of WO 2015/005398, paragraphs 0143 to 0165 can be referred to, and the contents thereof are incorporated in the present specification.
  • radical scavenger One preferred additive may include a radical scavenger.
  • a radical scavenger reference can be made to the description of WO 2015/005398, paragraphs 0166 to 0199, the contents of which are incorporated herein.
  • a deterioration preventing agent As one of preferable additives, a deterioration preventing agent can be mentioned. Regarding the deterioration preventing agent, the description in WO2015 / 005398 paragraphs 0205 to 0206 can be referred to, and the contents thereof are incorporated in the present specification.
  • the cellulose ester resin layer can also contain a compound having a barbituric acid structure (barbituric acid compound).
  • a barbituric acid compound is a compound which can express various functions in a cellulose-ester resin layer by adding this compound.
  • the barbituric acid compound is effective for improving the hardness of the cellulose ester resin layer.
  • the barbituric acid compound is also effective in improving the durability against light, heat, humidity and the like of a polarizing plate provided with a cellulose ester resin layer containing this compound.
  • the cellulose ester resin layer can be improved in adhesion to a polarizer material such as polyvinyl alcohol by alkali saponification treatment.
  • a polarizer material such as polyvinyl alcohol
  • the saponification method the method described in paragraph No. 0211 and paragraph No. 0212 of JP-A-2007-86748 can be used.
  • the alkali saponification treatment for the cellulose ester resin layer is preferably performed in a cycle in which the film surface is immersed in an alkali solution, neutralized with an acidic solution, washed with water and dried.
  • the alkaline solution include potassium hydroxide solution and sodium hydroxide solution.
  • the concentration of hydroxide ions is preferably in the range of 0.1 to 5.0 mol / L, more preferably in the range of 0.5 to 4.0 mol / L.
  • the alkaline solution temperature is preferably in the range of room temperature to 90 ° C, more preferably in the range of 40 to 70 ° C.
  • the film thickness of the cellulose ester resin layer is preferably 1 to 80 ⁇ m, more preferably 1 to 60 ⁇ m, and further preferably 3 to 60 ⁇ m.
  • the film thickness of the cellulose ester resin layer is preferably 10 to 60 ⁇ m, more preferably 20 to 60 ⁇ m, and also preferably 20 to 50 ⁇ m.
  • the manufacturing method of the laminated body of this invention is demonstrated.
  • the manufacturing method of the laminated body of this invention is not specifically limited, A well-known method is employable.
  • a layer containing the polymer (S) is formed by various known coating methods, and this is dried to obtain a laminate.
  • coating method A micro gravure coating system can be used preferably. In any case, any coating method may be used as long as the monomer is dissolved in an appropriate solvent at an appropriate concentration. There is no particular limitation.
  • the film can be formed by a melt film forming method or a solution film forming method (solvent casting method).
  • a melt film forming method it is preferable to use a manufacturing method such as a T-die method, and it is particularly preferable to use a simultaneous coextrusion method.
  • a solution casting method it is preferable to use a lamination casting method such as the above-mentioned co-casting method, sequential casting method, coating method or the like, and particularly a simultaneous co-casting method (also referred to as simultaneous multi-layer co-casting) method is used. Is particularly preferable from the viewpoints of stable production and production cost reduction.
  • the content of the polymer (S) in the laminate is preferably 1 to 30% by mass, more preferably 5 to 28% by mass, and further preferably 8 to 25% by mass.
  • the laminate of the present invention preferably has a total haze value of 2.00% or less.
  • the total haze value is more preferably 1.00% or less, further preferably 0.50% or less, particularly preferably 0.30% or less, and most preferably 0.20% or less.
  • the internal haze value of the laminate of the present invention is preferably 1.00% or less.
  • the contrast ratio of the liquid crystal display device can be improved and excellent display characteristics can be realized.
  • the internal haze value is more preferably 0.50% or less, further preferably 0.20% or less, particularly preferably 0.10% or less, and most preferably 0.05% or less. From the viewpoint of raw material selection, production control, etc., 0.01% or more is preferable.
  • the laminate of the present invention preferably has a total haze value of 0.30% or less and an internal haze value of 0.10% or less.
  • Total haze value and internal haze value are the type of film material, amount added, selection of additives (particularly, particle size, refractive index, amount added), and film production conditions (stretching temperature and stretching) The magnification can be adjusted.
  • the haze value can be measured on a film sample of 40 mm ⁇ 80 mm at 25 ° C. and a relative humidity of 60% with a haze meter (HGM-2DP, Suga Test Machine) according to JIS K-7136 (2000).
  • the film thickness of the laminate of the present invention can be appropriately determined according to the application, but can be set to, for example, 5 to 100 ⁇ m. When the thickness is 5 ⁇ m or more, the handling property when producing a web-like film is improved, which is preferable. Moreover, by setting it as 100 micrometers or less, it becomes easy to respond to a humidity change and it becomes easy to maintain an optical characteristic.
  • the film thickness of the laminate is more preferably 8 to 80 ⁇ m, still more preferably 10 to 70 ⁇ m.
  • the moisture permeability of the laminate is measured under the conditions of 40 ° C. and relative humidity 90% based on JIS Z-0208.
  • the moisture permeability of the laminate of the present invention is preferably 1600 g / m 2 / day (24 hours) or less, more preferably 1000 g / m 2 / day or less, and 600 g / m 2 / day or less. More preferably, it is particularly preferably 200 g / m 2 / day or less.
  • the moisture content of the laminate is 25 ° C., regardless of the film thickness, so as not to impair the adhesion with a hydrophilic thermoplastic resin such as polyvinyl alcohol when used as a protective film for a polarizing plate.
  • the water content at a relative humidity of 80% is preferably 0 to 4.0% by mass.
  • the content is more preferably 0 to 2.5% by mass, and still more preferably 0 to 1.5% by mass. If the equilibrium moisture content is 4.0% by mass or less, the dependence of retardation on humidity changes does not become too large, and the display unevenness of the liquid crystal display device during black display after aging at room temperature, high humidity, and high temperature and high humidity.
  • the moisture content is measured by measuring the film sample 7 mm x 35 mm by the Karl Fischer method using a moisture meter and sample drying devices “CA-03” and “VA-05” (both manufactured by Mitsubishi Chemical Corporation). Can do.
  • the moisture content can be calculated by dividing the moisture content (g) by the sample mass (g).
  • the polarizing plate of the present invention includes a polarizer and at least one laminate of the present invention as a protective film for the polarizer.
  • the polarizer for example, a film obtained by immersing and stretching a polyvinyl alcohol film in an iodine solution can be used.
  • a polarizer obtained by immersing and stretching a polyvinyl alcohol film in an iodine solution for example, the saponification surface of the cellulose ester resin layer in the laminate is bonded to at least one surface of the polarizer using an adhesive.
  • the adhesive include an aqueous solution of polyvinyl alcohol or polyvinyl acetal (for example, polyvinyl butyral), a latex of a vinyl-based polymer (for example, polybutyl acrylate), and an ultraviolet curable adhesive.
  • Particularly preferred adhesives are UV curable adhesives or aqueous solutions of fully saponified polyvinyl alcohol.
  • the production method of the polarizing plate of the present invention is not particularly limited, and can be produced according to a general method.
  • alkali treatment easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed. Further, the surface treatment as described above may be performed.
  • the laminate surface of the laminate with the polarizer may be on the polymer layer side or on the cellulose ester resin layer side. But it ’s okay.
  • the polymer layer side is preferably bonded to the polarizer.
  • the lamination of the laminate of the present invention is preferably bonded to the polarizer so that the transmission axis of the polarizer and the slow axis of the laminate of the present invention are parallel, orthogonal or 45 °.
  • the slow axis can be measured by various known methods, for example, using a birefringence meter (KOBRADH, manufactured by Oji Scientific Instruments).
  • parallel, orthogonal, or 45 ° includes a range of errors allowed in the technical field to which the present invention belongs.
  • the parallel of the transmission axis of the polarizer and the slow axis of the laminate of the present invention means that the direction of the main refractive index nx of the laminate of the present invention and the direction of the transmission axis of the polarizer intersect at an angle of ⁇ 10 °.
  • This angle is preferably within a range of ⁇ 5 °, more preferably within a range of ⁇ 3 °, further preferably within a range of ⁇ 1 °, and most preferably within a range of ⁇ 0.5 °.
  • the orthogonality of the transmission axis of the polarizer and the slow axis of the laminate of the present invention means that the direction of the main refractive index nx of the laminate of the present invention and the direction of the transmission axis of the polarizer are 90 ° ⁇ 10 °. It means that they intersect at an angle within the range of.
  • This angle is preferably in the range of 90 ° ⁇ 5 °, more preferably in the range of 90 ° ⁇ 3 °, even more preferably in the range of 90 ° ⁇ 1 °, most preferably 90 ° ⁇ 0.1 °. Within range. If it is the above ranges, the fall of the polarization degree performance under polarizing plate cross Nicol will be suppressed, and light omission is reduced and it is preferable.
  • the polarizing plate is composed of a polarizer and protective films protecting both surfaces thereof, and at least one of the protective films is preferably a laminate of the present invention. Further, usually, a protective film is bonded to one surface of the polarizing plate, and a separate film is bonded to the other surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the adhesive layer bonded to a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal plate.
  • the degree of polarization is preferably 95.0% or more, more preferably 98.0% or more, and most preferably 99.5% or more.
  • the degree of polarization of the polarizing plate can be measured using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation. More specifically, the polarization degree spectrum is calculated from the orthogonal transmittance and the parallel transmittance measured at wavelengths of 380 nm to 700 nm by the following formula, and the weighted average of the light source (auxiliary illuminant C) and the CIE visibility (Y) is calculated. Can be obtained.
  • Polarization degree (%) ⁇ (Parallel transmittance ⁇ orthogonal transmittance) / (parallel transmittance + orthogonal transmittance) ⁇ 1/2 ⁇ 100
  • the polarizing plate of the present invention is excellent in durability under wet heat aging conditions. For this reason, the amount of change in the degree of polarization before and after the polarizing plate durability test described later is small.
  • the polarizing plate of the present invention was measured for orthogonal transmittance and parallel transmittance using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation, and the degree of polarization was calculated by the above formula. It is preferable that the amount of change in polarization degree is less than 5% when stored in an environment of 85% humidity for 500 hours.
  • the polarizing plate of the present invention is preferably used for an image display device.
  • Examples of such an image display device include a liquid crystal display device and an organic electroluminescence display device.
  • the polarizing plate of this invention is used suitably for a liquid crystal display device.
  • the liquid crystal display device which is one embodiment as the image display device of the present invention includes a liquid crystal cell and the polarizing plate of the present invention disposed in at least one of the liquid crystal cells.
  • FIG. 2 is a schematic view showing an embodiment of the liquid crystal display device.
  • the liquid crystal display device 20 includes a liquid crystal cell having a liquid crystal layer 24 and a liquid crystal cell upper electrode substrate 23 and a liquid crystal cell lower electrode substrate 25 disposed above and below, and upper polarizing plates disposed on both sides of the liquid crystal cell. 21 and the lower polarizing plate 26.
  • a color filter may be disposed between the liquid crystal cell and each polarizing plate.
  • liquid crystal display device 20 When the liquid crystal display device 20 is used as a transmission type, a cold cathode or hot cathode fluorescent tube, or a backlight having a light emitting diode, field emission element, or electroluminescent element as a light source is disposed on the back surface.
  • the substrate of the liquid crystal cell generally has a thickness of 50 ⁇ m to 2 mm.
  • the upper polarizing plate 21 and the lower polarizing plate 26 usually have a configuration in which a polarizer is sandwiched between two polarizing plate protective films.
  • at least one polarizing plate is the polarizing plate of the present invention.
  • the polarizing plates 21 and 26 included in the liquid crystal display device 20 of the present invention are the laminate of the present invention as a polarizing plate protective film, a polarizer, and a general transparent protective film in order from the outside of the device (the side far from the liquid crystal cell).
  • a form in which each layer is laminated in order is preferable.
  • it replaces with the said general transparent protective film, and the form which used the laminated board of this invention as a phase difference film is also preferable.
  • the substrate of the liquid crystal cell generally has a thickness of 50 ⁇ m to 2 mm.
  • the cellulose ester film of the present invention can be used for liquid crystal cells in various display modes.
  • TN Transmission Nematic
  • IPS In-Plane Switching
  • FLC Fluoroelectric Liquid Crystal
  • AFLC Anti-Frequency Liquid Crystal
  • OCB Optically Charged Compensated.
  • Various display modes have been proposed, such as Electrically Controlled Birefringence (HAN) and Hybrid Aligned Nematic (HAN).
  • HAN Electrically Controlled Birefringence
  • HAN Hybrid Aligned Nematic
  • HAN Hybrid Aligned Nematic
  • the cellulose ester of the present invention can be suitably used for a liquid crystal display device in any display mode. Further, it can be suitably used for any liquid crystal display device of a transmissive type, a reflective type, and a transflective type.
  • Comparative Synthesis Examples 1 and 2 Synthesis of Comparative Polymers HP-1 and HP-2> Comparative Polymers HP-1 and HP-2 were obtained in the same manner as in Synthesis Example 1 except that the monomer type and charge ratio used in Synthesis Example 1 were changed as shown in Table 1 below.
  • Table 1 below A-2, A-4, A-5, A-6, A-7, A-9, A-10, and A-11 correspond to the repeating units exemplified above.
  • Table 1 below shows the weight average molecular weights of the polymers obtained in the above synthesis examples and comparative synthesis examples.
  • a weight average molecular weight measured in terms of polystyrene by gel permeation chromatography (GPC) was adopted. Specific measurement conditions are shown below.
  • GPC equipment GPC equipment manufactured by Tosoh Corporation (HLC-8320GPC, Ecosec) Column: TSK gel SuperHZM-H, TSK gel SuperHZ4000, TSK gel SuperHZ2000 combined use (Tosoh, 4.6 mm ID (inner diameter) x 15.0 cm)
  • Eluent Tetrahydrofuran (THF)
  • Tg Measurement of glass transition temperature Tg
  • X-DSC7000 produced by IT Measurement Control Co., Ltd.
  • 20 mg of a polymer sample is placed in a measurement pan, and this is heated from 30 ° C. to 120 ° C. at a rate of 10 ° C./min in a nitrogen stream.
  • the temperature was raised and held for 15 minutes, and then cooled to 30 ° C. at ⁇ 20 ° C./min. Thereafter, the temperature was raised again from 30 ° C. to 250 ° C., and the temperature at which the baseline began to change from the low temperature side was defined as the glass transition temperature Tg.
  • the prepared dope was uniformly cast from a casting die onto a stainless steel endless band (casting support) having a width of 2000 mm.
  • a stainless steel endless band casting support
  • the amount of residual solvent in the dope reaches 40% by mass, it is peeled off from the casting support as a polymer film, conveyed without being actively stretched by a tenter, and dried at 130 ° C. in a drying zone. It was.
  • the thickness of the obtained cellulose ester resin layer (cellulose ester film) CA-1 was 55 ⁇ m.
  • the prepared dope was uniformly cast from a casting die onto a stainless steel endless band (casting support) having a width of 2000 mm.
  • the residual solvent amount in the dope A reaches 40% by mass
  • the polymer film is peeled from the casting support, and the rotational speed of the downstream roller is made higher than the rotational speed of the upstream roller at the transition portion.
  • drying was performed at 130 ° C. in the drying zone.
  • the film thickness of the obtained cellulose ester resin layer (cellulose ester film) CA-2 was 40 ⁇ m.
  • the polymer P-1 was mixed with methyl ethyl ketone so as to have a solid content of 15%, charged into a glass separable flask equipped with a stirrer, stirred at room temperature for 5 hours, and filtered through a polypropylene depth filter having a pore size of 5 ⁇ m.
  • a composition for forming a polymer layer was obtained.
  • the composition for forming a polymer layer was applied on the cellulose ester resin layer CA-1 prepared above using a gravure coater. Subsequently, it was dried at 25 ° C. for 1 minute and further dried at 120 ° C. for about 5 minutes to obtain a laminate S-1 having a thickness of 60 ⁇ m.
  • Polarization degree (%) [(parallel transmittance ⁇ orthogonal transmittance) / (orthogonal transmittance + parallel transmittance)] 1/2 ⁇ 100
  • the degree of polarization was measured in the range of 380 nm to 780 nm using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation, and the measured value at a wavelength of 410 nm at which the degree of deterioration is more noticeable than other wavelengths was adopted. . Thereafter, it was stored for 500 hours in an environment of a temperature of 85 ° C. and a relative humidity of 85%. Subsequently, the polarization degree was measured about two samples like the above, the measured value of two samples was arithmetically averaged, and it was set as the polarization degree of the polarizing plate after a preservation
  • Polarization degree change (%) [Polarization degree before storage (%) ⁇ Polarization degree after storage (%)]
  • the polarizing plates PL-1 to PL-3 of the present invention using the laminate of the present invention as a protective film can be stored for a long time under severe conditions of high temperature and high humidity.
  • the change in the degree of polarization could be kept as low as less than 3.0%, and excellent polarizer durability was exhibited. That is, by incorporating a polarizing plate using the laminate of the present invention as a protective film for a polarizer into an image display device, deterioration in image quality can be effectively suppressed even when used for a long time under high temperature and high humidity conditions. Recognize.

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Abstract

A laminate which comprises a cellulose ester resin layer and a layer that is provided directly on the cellulose ester resin layer and contains a polymer having a repeating unit represented by general formula (1), and wherein the polymer has a glass transition temperature of 50°C or higher; a polarizing plate which uses this laminate; and an image display device which uses this polarizing plate. In general formula (1), Ra represents a hydrogen atom, an alkyl group or an alkoxycarbonyl group; each of Rb and Rc represents a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group; and R2 represents an alkyl group, a cycloalkyl group or an aryl group.

Description

積層体、偏光板及び画像表示装置Laminated body, polarizing plate, and image display device
　本発明は、積層体、この積層体を用いた偏光板、並びに、この偏光板を用いた画像表示装置に関する。 The present invention relates to a laminate, a polarizing plate using the laminate, and an image display device using the polarizing plate.
　エレクトロルミネッセンスディスプレイ（ＥＬＤ）、液晶表示装置（ＬＣＤ）等に代表される画像表示装置には、その薄型化への要求が益々高まっている。また、屋外用途をはじめとして画像表示装置の使用環境は多様化しており、画像表示装置には従来に比べて過酷な環境下でも良好な画像品質を安定して維持できる性能（高度な耐久性）が求められるようになっている。
　画像表示装置における画像品質の低下は、水が偏光板内部へと進入し、偏光子を劣化させることが一因とされる。偏光子はその表面に保護フィルム（光学フィルム）が積層されて保護されているが、この保護フィルムにも薄膜化が求められている。保護フィルムを薄膜化すると水が偏光子とより接触しやすくなり、画像品質が低下しやすくなる。また、かかる画像品質の低下は、屋外用途等の過酷な環境下での使用においてより顕在化する。
　また、実用的な保護フィルムとするためには、保護フィルムの光学特性の経時に伴う変動を極力抑えることも重要となる。しかし、一般的に、保護フィルムは上述した過酷な環境下（特に高温環境下）での使用において光学特性の劣化が進行しやすい。このような光学特性の劣化としては、ヘイズ値の上昇やフィルムの着色が例として挙げられる。 Image display devices represented by electroluminescence displays (ELD), liquid crystal display devices (LCD), and the like are increasingly demanded for thinning. In addition, the usage environment of image display devices has been diversified, including outdoor applications, and image display devices have the ability to stably maintain good image quality even in harsh environments (high durability). Is now required.
The decrease in image quality in the image display device is partly caused by water entering the polarizing plate and degrading the polarizer. The polarizer is protected by laminating a protective film (optical film) on the surface, and the protective film is also required to be thin. When the protective film is thinned, water is more likely to come into contact with the polarizer, and the image quality is likely to deteriorate. Further, such a decrease in image quality becomes more apparent when used under harsh environments such as outdoor applications.
Moreover, in order to obtain a practical protective film, it is also important to suppress fluctuations with time of optical characteristics of the protective film as much as possible. However, in general, the protective film tends to deteriorate in optical characteristics when used in the harsh environment described above (particularly in a high temperature environment). Examples of such deterioration of optical characteristics include an increase in haze value and film coloring.
　上記保護フィルムとしては、汎用性、加工性等の観点からセルロースエステル樹脂、アクリル樹脂等が広く用いられている。また、所望の光学特性を発現し、且つ透湿度を抑えた保護フィルムとするために、セルロースエステルとアクリル樹脂とを混合したブレンド樹脂を用いて保護フィルムを形成することも知られている（例えば特許文献１及び２）。 As the protective film, cellulose ester resins, acrylic resins, and the like are widely used from the viewpoints of versatility and processability. It is also known to form a protective film using a blend resin in which a cellulose ester and an acrylic resin are mixed in order to obtain a desired protective film exhibiting desired optical properties and moisture permeability (for example, Patent Documents 1 and 2).
特開２０１０－２４３９３５号公報JP 2010-243935 A 特開２０１３－２４９６３号公報JP 2013-24963 A
　本発明者らは、上記特許文献１及び２記載のフィルムをはじめ、従来の保護フィルムを検討した結果、これらの保護フィルムは、特に上述した要求水準まで高度に薄膜化した際には偏光子の劣化の問題に十分に対応できないことが困難であることが明らかとなってきた。
　また、これらの保護フィルムを高温環境下で保存した場合に、ヘイズ値が上昇しやすい傾向にあり、これらの保護フィルムを画像表示装置に組み込んだ際に表示性能を良好に維持することが困難であることも明らかとなってきた。
　本発明は、セルロースエステル樹脂層を備えた積層体であって、層間の密着性に優れ、薄膜化して偏光子の保護フィルムとして用いた際にも偏光子の経時的な劣化を抑制することができ、さらに高温環境下においてもヘイズ値の経時的な上昇が抑制され、画像表示装置に組み込んだ際に表示性能を長期に亘り良好に維持することを可能とする積層体、この積層体を用いた偏光板、並びにこの偏光板を用いた画像表示装置を提供することを課題とする。 As a result of studying the conventional protective films including the films described in Patent Documents 1 and 2, the present inventors have found that these protective films are particularly suitable for polarizers when they are highly thinned to the above-mentioned required levels. It has become clear that it is difficult to adequately address the problem of degradation.
In addition, when these protective films are stored in a high temperature environment, the haze value tends to increase, and it is difficult to maintain good display performance when these protective films are incorporated into an image display device. It has also become clear.
The present invention is a laminate comprising a cellulose ester resin layer, which has excellent interlayer adhesion, and suppresses deterioration of the polarizer over time even when it is thinned and used as a protective film for a polarizer. In addition, a laminate that suppresses the increase in haze value over time even in a high-temperature environment and can maintain good display performance for a long time when incorporated in an image display device, and uses this laminate. It is an object of the present invention to provide a polarizing plate and an image display device using the polarizing plate.
　本発明者らは上記課題に鑑み鋭意検討を重ねた結果、特定構造の繰り返し単位を有し、且つ特定温度以上のガラス転移温度を有するポリマーを含有する層をセルロースエステル樹脂層上に直接設けた積層体が、層間の密着性に優れること、高温環境下においてもヘイズ値の経時的な上昇が抑制できること、偏光子の保護フィルムとして用いた場合に高温高湿条件下でも偏光子の経時的な劣化を抑えることができることを見出した。
　本発明はこれらの知見に基づきさらに検討を重ね、完成されるに至ったものである。 As a result of intensive studies in view of the above problems, the present inventors directly provided a layer containing a polymer having a repeating unit having a specific structure and having a glass transition temperature equal to or higher than a specific temperature on the cellulose ester resin layer. The laminate is excellent in adhesion between layers, can suppress the increase in haze value over time even in a high temperature environment, and when used as a protective film for a polarizer, It was found that deterioration can be suppressed.
The present invention has been further studied based on these findings and has been completed.
　本発明の上記課題は下記の手段により解決された。
〔１〕
　セルロースエステル樹脂層と、このセルロースエステル樹脂層上に直接設けた、下記一般式（１）で表される繰り返し単位を有するポリマーを含有する層とを有し、このポリマーのガラス転移温度が５０℃以上である、積層体。
Figure JPOXMLDOC01-appb-C000006
 　一般式（１）中、Ｒａは水素原子、アルキル基又はアルコキシカルボニル基を示す。
　Ｒｂ及びＲｃは水素原子、アルキル基、アリール基又はアルコキシカルボニル基を示す。
　Ｒ２はアルキル基、シクロアルキル基又はアリール基を示す。
　Ｌ１はアルキレン基、アリーレン基、－Ｃ（＝Ｏ）－、－Ｏ－及び－ＮＲ３－から選ばれる２価の基を２種以上組み合わせてなる２価の連結基を示す。但し、Ｌ１は－Ｃ（＝Ｏ）ＮＲ３－で表される基を含む。
　Ｒ３は水素原子又は置換基を示す。
〔２〕
　上記一般式（１）で表される繰り返し単位が下記一般式（２）又は（３）で表される繰り返し単位である、〔１〕記載の積層体。
Figure JPOXMLDOC01-appb-C000007
 　一般式（２）中、Ｒ１ａは水素原子又はメチルを示す。
　Ｒ２は一般式（１）におけるＲ２と同義である。
　Ｌ２はアルキレン基、アルキレンオキシ基又はポリアルキレンオキシ基を示す。
　Ａは－Ｃ（＝Ｏ）ＮＲ３－又は－ＮＲ３－Ｃ（＝Ｏ）－ＮＲ３－を示す。Ｒ３は上記一般式（１）におけるＲ３と同義である。
Figure JPOXMLDOC01-appb-C000008
 　一般式（３）中、Ｒ１ａ及びＲ２は、それぞれ上記一般式（２）におけるＲ１ａ及びＲ２と同義である。
　Ｒ３ａは水素原子又はアルキル基を示す。
〔３〕
　上記一般式（３）で表される繰り返し単位が下記一般式（４）で表される繰り返し単位である、〔２〕記載の積層体。
Figure JPOXMLDOC01-appb-C000009
 　一般式（４）中、Ｒ１ａ及びＲ２は、それぞれ上記一般式（３）におけるＲ１ａ及びＲ２と同義である。
〔４〕
　上記一般式（１）で表される繰り返し単位を有する上記ポリマーが、上記一般式（１）で表される繰り返し単位と、下記一般式（５）で表される繰り返し単位とを有する、〔１〕～〔３〕のいずれか記載の積層体。
Figure JPOXMLDOC01-appb-C000010
 　一般式（５）中、Ｒ４及びＲ５は水素原子、アルキル基、アリール基又はアルコキシカルボニル基を示す。
　Ｒ６は水素原子又はアルキル基を示す。
　Ｌ３は単結合であるか、又は、アルキレン基、アリーレン基、－Ｃ（＝Ｏ）－、－Ｏ－及び－Ｎ（Ｒ３Ａ）－から選ばれる２価の基もしくはこれらの基の２種以上を組合せてなる２価の連結基を示す。
　Ｒ３Ａは水素原子又は置換基を示す。
〔５〕
　上記積層体中、上記一般式（１）で表される繰り返し単位を有するポリマーの含有量が１～３０質量％である、〔１〕～〔４〕のいずれか記載の積層体。
〔６〕
　〔１〕～〔５〕のいずれか記載の積層体と、偏光子とを有する偏光板。
〔７〕
　〔６〕に記載の偏光板を有する画像表示装置。 The above-described problems of the present invention have been solved by the following means.
[1]
It has a cellulose ester resin layer and a layer containing a polymer having a repeating unit represented by the following general formula (1) provided directly on the cellulose ester resin layer, and the glass transition temperature of this polymer is 50 ° C. That is the laminate.
Figure JPOXMLDOC01-appb-C000006
 In General Formula (1), R a represents a hydrogen atom, an alkyl group, or an alkoxycarbonyl group.
R b and R c represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
R 2 represents an alkyl group, a cycloalkyl group or an aryl group.
L 1 represents a divalent linking group formed by combining two or more divalent groups selected from an alkylene group, an arylene group, —C (═O) —, —O—, and —NR 3 —. However, L 1 includes a group represented by —C (═O) NR 3 —.
R 3 represents a hydrogen atom or a substituent.
[2]
The laminate according to [1], wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (2) or (3).
Figure JPOXMLDOC01-appb-C000007
 In general formula (2), R 1a represents a hydrogen atom or methyl.
R 2 has the same meaning as R 2 in the general formula (1).
L 2 represents an alkylene group, an alkyleneoxy group or a polyalkyleneoxy group.
A represents —C (═O) NR 3 — or —NR 3 —C (═O) —NR 3 —. R 3 has the same meaning as R 3 in the general formula (1).
Figure JPOXMLDOC01-appb-C000008
 In the general formula (3), R 1a and R 2 are the same meanings as R 1a and R 2 in the general formula (2).
R 3a represents a hydrogen atom or an alkyl group.
[3]
The laminate according to [2], wherein the repeating unit represented by the general formula (3) is a repeating unit represented by the following general formula (4).
Figure JPOXMLDOC01-appb-C000009
 In the general formula (4), R 1a and R 2 are the same meanings as R 1a and R 2 in the general formula (3).
[4]
The polymer having a repeating unit represented by the general formula (1) has a repeating unit represented by the general formula (1) and a repeating unit represented by the following general formula (5). ] To [3].
Figure JPOXMLDOC01-appb-C000010
 In General Formula (5), R 4 and R 5 represent a hydrogen atom, an alkyl group, an aryl group, or an alkoxycarbonyl group.
R 6 represents a hydrogen atom or an alkyl group.
L 3 is a single bond, a divalent group selected from an alkylene group, an arylene group, —C (═O) —, —O— and —N (R 3A ) —, or two of these groups A divalent linking group formed by combining the above is shown.
R 3A represents a hydrogen atom or a substituent.
[5]
The laminate according to any one of [1] to [4], wherein the content of the polymer having the repeating unit represented by the general formula (1) is 1 to 30% by mass in the laminate.
[6]
[1] A polarizing plate comprising the laminate according to any one of [5] and a polarizer.
[7]
The image display apparatus which has a polarizing plate as described in [6].
　本明細書において「～」で表される数値範囲は、その前後に記載される数値を下限値及び上限値として含む意味である。 In the present specification, the numerical range represented by “to” means that the numerical values described before and after it are included as the lower limit value and the upper limit value.
　本明細書において、特定の符号で表示された置換基、連結基等（以下、置換基等という）が複数あるとき、あるいは複数の置換基等を同時もしくは択一的に規定するときには、それぞれの置換基等は互いに同一でも異なっていてもよいことを意味する。このことは、置換基等の数の規定についても同様である。また、複数の置換基等が近接（特に隣接）するときにはそれらが互いに連結したり縮環したりして環を形成していてもよい意味である。 In the present specification, when there are a plurality of substituents, linking groups, etc. (hereinafter referred to as substituents, etc.) indicated by specific symbols, or when a plurality of substituents etc. are specified simultaneously or alternatively, It means that a substituent etc. may mutually be same or different. The same applies to the definition of the number of substituents and the like. Further, when a plurality of substituents and the like are close (especially adjacent), they may be connected to each other or condensed to form a ring.
　本明細書において化合物の表示については、化合物そのもののほか、その塩、そのイオンを含む意味に用いる。また、目的の効果を奏する範囲で、構造の一部を変化させたものを含む意味である。
　なお、化合物の塩としては、例えば、化合物と無機酸もしくは有機酸とで形成された、化合物の酸付加塩、又は、化合物と無機塩基もしくは有機塩基とで形成された、化合物の塩基付加塩等が挙げられる。また、化合物のイオンとしては、例えば、上述の化合物の塩が乖離してなる、化合物の骨格を含むイオンが挙げられる。
　本明細書において置換、無置換を明記していない置換基（連結基についても同様）については、所望の効果を奏する範囲で、その基に任意の置換基を有していてもよい意味である。これは置換、無置換を明記していない化合物についても同義である。
　また本明細書において単に「置換基」という場合、特段の断りが無い限り、下記置換基群Ｔから選択される基が挙げられる。また、特定の範囲を有する置換基が記載されているだけの場合（例えば「アルキル基」と記載されているだけの場合）は、下記置換基群Ｔの対応する基（上記の場合はアルキル基）における好ましい範囲、具体例が適用される。
　本明細書において、ある基の炭素数を規定する場合、この炭素数は、基全体の炭素数を意味する。つまり、この基がさらに置換基を有する形態である場合、この置換基を含めた全体の炭素数を意味する。 In this specification, about the display of a compound, it uses in the meaning containing its salt and its ion besides the compound itself. In addition, it means that a part of the structure is changed as long as the desired effect is achieved.
Examples of the salt of the compound include, for example, an acid addition salt of the compound formed with the compound and an inorganic acid or an organic acid, or a base addition salt of the compound formed with the compound and an inorganic base or an organic base. Is mentioned. In addition, examples of the ion of the compound include an ion including a skeleton of the compound formed by dissociating the salt of the above-described compound.
In the present specification, a substituent that does not specify substitution or non-substitution (the same applies to a linking group) means that the group may have an arbitrary substituent as long as a desired effect is achieved. . This is also the same for compounds that do not specify substitution or non-substitution.
In the present specification, the term “substituent” includes groups selected from the following substituent group T unless otherwise specified. In addition, when only a substituent having a specific range is described (for example, when only described as “alkyl group”), a corresponding group of the following substituent group T (in the above case, an alkyl group) The preferred range in FIG.
In the present specification, when the number of carbon atoms of a certain group is defined, this number of carbons means the total number of carbon atoms in the group. That is, when this group is a form further having a substituent, it means the total number of carbon atoms including this substituent.
置換基群Ｔ：
　アルキル基（好ましくは炭素原子数１～２０、より好ましくは１～１２、特に好ましくは１～８のものであり、例えばメチル基、エチル基、イソプロピル基、ｔｅｒｔ－ブチル基、ｎ－オクチル基、ｎ－デシル基、ｎ－ヘキサデシル基などが挙げられる。）、シクロアルキル基（好ましくは炭素原子数３～２０、より好ましくは３～１２、特に好ましくは３～８のものであり、シクロプロピル基、シクロペンチル基、シクロヘキシル基などが挙げられる。）、アルケニル基（好ましくは炭素原子数２～２０、より好ましくは２～１２、特に好ましくは２～８であり、例えばビニル基、アリル基、２－ブテニル基、３－ペンテニル基などが挙げられる。）、アルキニル基（好ましくは炭素原子数２～２０、より好ましくは２～１２、特に好ましくは２～８であり、例えばプロパルギル基、３－ペンチニル基などが挙げられる。）、アリール基（好ましくは炭素原子数６～３０、より好ましくは６～２０、特に好ましくは６～１２であり、例えばフェニル基、ビフェニル基、ナフチル基などが挙げられる。）、アミノ基（好ましくは炭素原子数０～２０、より好ましくは０～１０、特に好ましくは０～６であり、例えばアミノ基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジベンジルアミノ基などが挙げられる。）、アルコキシ基（好ましくは炭素原子数１～２０、より好ましくは１～１２、特に好ましくは１～８であり、例えばメトキシ基、エトキシ基、ブトキシ基などが挙げられる。）、アリールオキシ基（好ましくは炭素原子数６～２０、より好ましくは６～１６、特に好ましくは６～１２であり、例えばフェニルオキシ基、２－ナフチルオキシ基などが挙げられる。）、アシル基（好ましくは炭素原子数１～２０、より好ましくは１～１６、特に好ましくは１～１２であり、例えばアセチル基、ベンゾイル基、ホルミル基、ピバロイル基などが挙げられる。）、アルコキシカルボニル基（好ましくは炭素原子数２～２０、より好ましくは２～１６、特に好ましくは２～１２であり、例えばメトキシカルボニル基、エトキシカルボニル基などが挙げられる。）、アリールオキシカルボニル基（好ましくは炭素原子数７～２０、より好ましくは７～１６、特に好ましくは７～１０であり、例えばフェニルオキシカルボニル基などが挙げられる。）、アシルオキシ基（好ましくは炭素原子数２～２０、より好ましくは２～１６、特に好ましくは２～１０であり、例えばアセトキシ基、ベンゾイルオキシ基などが挙げられる。）、アシルアミノ基（好ましくは炭素原子数２～２０、より好ましくは２～１６、特に好ましくは２～１０であり、例えばアセチルアミノ基、ベンゾイルアミノ基などが挙げられる。）、アルコキシカルボニルアミノ基（好ましくは炭素原子数２～２０、より好ましくは２～１６、特に好ましくは２～１２であり、例えばメトキシカルボニルアミノ基などが挙げられる。）、アリールオキシカルボニルアミノ基（好ましくは炭素原子数７～２０、より好ましくは７～１６、特に好ましくは７～１２であり、例えばフェニルオキシカルボニルアミノ基などが挙げられる。）、スルホニルアミノ基（好ましくは炭素原子数１～２０、より好ましくは１～１６、特に好ましくは１～１２であり、例えばメタンスルホニルアミノ基、ベンゼンスルホニルアミノ基などが挙げられる。）、スルファモイル基（好ましくは炭素原子数０～２０、より好ましくは０～１６、特に好ましくは０～１２であり、例えばスルファモイル基、メチルスルファモイル基、ジメチルスルファモイル基、フェニルスルファモイル基などが挙げられる。）、カルバモイル基（好ましくは炭素原子数１～２０、より好ましくは１～１６、特に好ましくは１～１２であり、例えばカルバモイル基、メチルカルバモイル基、ジエチルカルバモイル基、フェニルカルバモイル基などが挙げられる。）、アルキルチオ基（好ましくは炭素原子数１～２０、より好ましくは１～１６、特に好ましくは１～１２であり、例えばメチルチオ基、エチルチオ基などが挙げられる。）、アリールチオ基（好ましくは炭素原子数６～２０、より好ましくは６～１６、特に好ましくは６～１２であり、例えばフェニルチオ基などが挙げられる。）、スルホニル基（好ましくは炭素原子数１～２０、より好ましくは１～１６、特に好ましくは１～１２であり、例えばメシル基、トシル基などが挙げられる。）、スルフィニル基（好ましくは炭素原子数１～２０、より好ましくは１～１６、特に好ましくは１～１２であり、例えばメタンスルフィニル基、ベンゼンスルフィニル基などが挙げられる。）、ウレタン基、ウレイド基（好ましくは炭素原子数１～２０、より好ましくは１～１６、特に好ましくは１～１２であり、例えばウレイド基、メチルウレイド基、フェニルウレイド基などが挙げられる。）、リン酸アミド基（好ましくは炭素原子数１～２０、より好ましくは１～１６、特に好ましくは１～１２であり、例えばジエチルリン酸アミド、フェニルリン酸アミドなどが挙げられる。）、ヒドロキシ基、メルカプト基、ハロゲン原子（例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子）、シアノ基、スルホ基、カルボキシル基、ニトロ基、ヒドロキサム酸基、スルフィノ基、ヒドラジノ基、イミノ基、ヘテロ環基（好ましくは炭素原子数１～３０、より好ましくは１～１２であり、ヘテロ原子としては、例えば窒素原子、酸素原子、硫黄原子、具体的には例えばイミダゾリル基、ピリジル基、キノリル基、フリル基、ピペリジル基、モルホリノ基、ベンゾオキサゾリル基、ベンズイミダゾリル基、ベンズチアゾリル基などが挙げられる。）、及びシリル基（好ましくは、炭素原子数３～４０、より好ましくは３～３０、特に好ましくは３～２４であり、例えば、トリメチルシリル基、トリフェニルシリル基などが挙げられる）。
　これらの置換基は更に置換基を有してもよい。また、置換基が２つ以上ある場合は、同じでも異なってもよい。また、隣接する置換基は互いに連結して環を形成してもよい。 Substituent group T:
An alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an n-octyl group, n-decyl group, n-hexadecyl group, etc.), cycloalkyl group (preferably having 3 to 20, more preferably 3 to 12, particularly preferably 3 to 8 carbon atoms, cyclopropyl group) , A cyclopentyl group, a cyclohexyl group, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms such as vinyl group, allyl group, 2- Butenyl group, 3-pentenyl group, etc.), alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferred) 2-8, for example, propargyl group, 3-pentynyl group, etc.), aryl group (preferably 6-30 carbon atoms, more preferably 6-20, particularly preferably 6-12, For example, a phenyl group, a biphenyl group, a naphthyl group, etc.), an amino group (preferably having a carbon number of 0 to 20, more preferably 0 to 10, particularly preferably 0 to 6, such as an amino group, methylamino Group, dimethylamino group, diethylamino group, dibenzylamino group, etc.), alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 8, such as methoxy Group, ethoxy group, butoxy group, etc.), aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms). Particularly preferred is 6 to 12, for example, phenyloxy group, 2-naphthyloxy group, etc.), acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms). 12 such as an acetyl group, a benzoyl group, a formyl group, and a pivaloyl group), an alkoxycarbonyl group (preferably having 2 to 20, more preferably 2 to 16, and particularly preferably 2 to 12 carbon atoms). For example, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (preferably having 7 to 20, more preferably 7 to 16, particularly preferably 7 to 10 carbon atoms such as phenyloxy A carbonyl group, etc.), an acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16, particularly preferably 2 to 10, and examples thereof include an acetoxy group and a benzoyloxy group. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 and particularly preferably 2 to 10 such as acetylamino group and benzoylamino group), alkoxycarbonylamino group ( Preferably it has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group, and an aryloxycarbonylamino group (preferably 7 to 7 carbon atoms). 20, more preferably 7 to 16, particularly preferably 7 to 12, and examples thereof include a phenyloxycarbonylamino group), a sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms). And particularly preferably 1 to 12, for example, methanesulfonylamino group, benzenesulfonate Amino groups, etc.), sulfamoyl groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms such as sulfamoyl group, methylsulfamoyl group, dimethylsulfayl group). And a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as a carbamoyl group and a methylcarbamoyl group). , Diethylcarbamoyl group, phenylcarbamoyl group, etc.), alkylthio group (preferably having 1 to 20, more preferably 1 to 16, particularly preferably 1 to 12 carbon atoms, such as methylthio group and ethylthio group) Arylthio group (preferably having 6 to 20 carbon atoms, More preferably, it is 6 to 16, particularly preferably 6 to 12, and examples thereof include a phenylthio group.), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, and particularly preferably 1 to 1). 12 such as a mesyl group and a tosyl group), a sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 and particularly preferably 1 to 12, such as a methanesulfinyl group, Benzenesulfinyl group, etc.), urethane group, ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, such as ureido group, methylureido group, phenyl group) Ureido groups, etc.), phosphoric acid amide groups (preferably having 1-20 carbon atoms, more preferably 1-16, 1 to 12 is preferable, and examples thereof include diethyl phosphoric acid amide and phenyl phosphoric acid amide. ), Hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, an imidazolyl group, a pyridyl group, a quinolyl group , A furyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, a benzimidazolyl group, a benzthiazolyl group, and the like, and a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, Particularly preferred is 3 to 24, and examples thereof include a trimethylsilyl group and a triphenylsilyl group. That).
These substituents may further have a substituent. Moreover, when there are two or more substituents, they may be the same or different. Further, adjacent substituents may be connected to each other to form a ring.
　本発明の積層体は、積層体における層間の密着性に優れ、薄膜化して偏光子と重ね合わせることにより、高温高湿条件下での偏光子の経時的な劣化を抑制することができる。また本発明の積層体は、高温環境下においてもヘイズ値の経時的な上昇を抑制できる。本発明の偏光板及び画像表示装置は上記効果を奏する本発明の積層体を有し、高温高湿条件下においても偏光子の劣化が効果的に抑えられる。
　なお、本明細書において、高温高湿条件下における偏光子の劣化を抑制する程度を「偏光子耐久性」または「偏光板耐久性」とも言う。
　本発明の上記及び他の特徴及び利点は、適宜添付の図面を参照して、下記の記載からより明らかになるであろう。 The laminate of the present invention has excellent adhesion between layers in the laminate and can suppress deterioration of the polarizer over time under high-temperature and high-humidity conditions by forming a thin film and overlapping the polarizer. Moreover, the laminated body of this invention can suppress the raise over time of a haze value also in a high temperature environment. The polarizing plate and the image display device of the present invention have the laminate of the present invention that exhibits the above effects, and the deterioration of the polarizer can be effectively suppressed even under high temperature and high humidity conditions.
In the present specification, the degree of suppressing the deterioration of the polarizer under high temperature and high humidity conditions is also referred to as “polarizer durability” or “polarizing plate durability”.
The above and other features and advantages of the present invention will become more apparent from the following description, with reference where appropriate to the accompanying drawings.
図１は、本発明の積層体の一実施形態を示す断面図である。FIG. 1 is a cross-sectional view showing an embodiment of the laminate of the present invention. 図２は、本発明の偏光板保護フィルムを組み込んだ偏光板を備えた液晶表示装置の一実施形態について、その概略を示す模式図である。FIG. 2 is a schematic diagram showing an outline of an embodiment of a liquid crystal display device including a polarizing plate incorporating the polarizing plate protective film of the present invention.
　本発明の好ましい実施形態について以下に説明する。
［積層体］
　本発明の積層体は、図１に示すように、セルロースエステル樹脂層１１と、このセルロースエステル樹脂層１１上に直接設けられた、後述する一般式（１）で表される繰り返し単位を有し且つ特定温度以上のガラス転移温度を有するポリマーを含有する層１２（以下、単に「ポリマー層」ともいう。）を有する。セルロースエステル樹脂層１１とポリマー層１２の詳細については後述する。本発明の積層体は、図１に示すようにセルロースエステル樹脂層１１の片面に上記ポリマー層が設けられていてもよいし、セルロースエステル樹脂層１１の両面に上記ポリマー層が設けられた形態であってもよい。より好ましくは、本発明の積層体はセルロースエステル樹脂層１１の片面に上記ポリマー層が設けられた形態である。
　なお、組成が異なる２層以上のポリマー層をセルロースエステル樹脂層上に設けてもよい。２層以上のポリマー層を形成する場合は、セルロースエステル樹脂層の片面に２層以上のポリマー層を設けてもよく、セルロースエステル樹脂層の両面にそれぞれ２層以上のポリマー層を設けてもよい。 Preferred embodiments of the present invention are described below.
[Laminate]
As shown in FIG. 1, the laminate of the present invention has a cellulose ester resin layer 11 and a repeating unit that is directly provided on the cellulose ester resin layer 11 and represented by the following general formula (1). In addition, a layer 12 containing a polymer having a glass transition temperature higher than a specific temperature (hereinafter also simply referred to as “polymer layer”) is included. Details of the cellulose ester resin layer 11 and the polymer layer 12 will be described later. In the laminate of the present invention, the polymer layer may be provided on one side of the cellulose ester resin layer 11 as shown in FIG. 1, or the polymer layer may be provided on both sides of the cellulose ester resin layer 11. There may be. More preferably, the laminate of the present invention has a form in which the polymer layer is provided on one side of the cellulose ester resin layer 11.
Two or more polymer layers having different compositions may be provided on the cellulose ester resin layer. When two or more polymer layers are formed, two or more polymer layers may be provided on one side of the cellulose ester resin layer, and two or more polymer layers may be provided on both sides of the cellulose ester resin layer. .
　また、本発明の積層体は、セルロースエステル樹脂層１１とポリマー層１２の他、特定の機能に特化した各種機能層（図示していない）を有していてもよい。かかる機能層として、例えばハードコート層、反射防止層、光散乱層、防汚層、帯電防止層、等が挙げられる。 Moreover, the laminate of the present invention may have various functional layers (not shown) specialized for specific functions in addition to the cellulose ester resin layer 11 and the polymer layer 12. Examples of such a functional layer include a hard coat layer, an antireflection layer, a light scattering layer, an antifouling layer, and an antistatic layer.
＜ポリマー層＞
　本発明の積層体を構成するポリマー層について説明する。 <Polymer layer>
The polymer layer which comprises the laminated body of this invention is demonstrated.
　本発明において「ポリマー層」とは、後述する一般式（１）の繰り返し単位を有し且つガラス転移温度が５０℃以上のポリマー（以下、「ポリマー（Ｓ）」という。本明細書において単に「ポリマー」という場合、特に断りの無い限りポリマー（Ｓ）あるいはこれに対応するポリマー（例えばポリマー（Ｓ）と比較対象となるポリマー）を意味し、セルロースエステル樹脂を意味するものではない。）を層中に５０質量％以上含有する層を意味する。ここで、ポリマー層中、ポリマー（Ｓ）の含有量は６０質量％以上が好ましく、７０質量％以上がより好ましく、８０質量％以上がさらに好ましく、８５質量％以上が特に好ましい。ポリマー層中のポリマー（Ｓ）の含有量が多い程、セルロースエステル樹脂層との密着性をより高めることができ、また積層体の光学特性の劣化、保護フィルムとして用いた際の偏光子の劣化をより抑えることができる点で好ましい。したがって、ポリマー層中のポリマー（Ｓ）の含有量は１００質量％でもよく、通常は９９質量％以下である。上記ポリマー層中のポリマー（Ｓ）の含有量が１００質量％でない場合、残部は各種の慣用添加剤又は樹脂を含むことができる。かかる添加剤としては、可塑剤、有機酸、色素、ポリマー、レターデーション調整剤、紫外線吸収剤、酸化防止剤、マット剤などが例示される。 In the present invention, the “polymer layer” refers to a polymer having a repeating unit of the general formula (1) described later and having a glass transition temperature of 50 ° C. or higher (hereinafter referred to as “polymer (S)”. The term “polymer” refers to a polymer (S) or a polymer corresponding thereto (for example, a polymer to be compared with the polymer (S), and not a cellulose ester resin) unless otherwise specified. It means a layer containing 50% by mass or more. Here, the content of the polymer (S) in the polymer layer is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 85% by mass or more. The higher the content of the polymer (S) in the polymer layer, the higher the adhesion to the cellulose ester resin layer, and the deterioration of the optical properties of the laminate and the deterioration of the polarizer when used as a protective film. Is preferable in that it can be further suppressed. Therefore, the content of the polymer (S) in the polymer layer may be 100% by mass, and is usually 99% by mass or less. When the content of the polymer (S) in the polymer layer is not 100% by mass, the balance can contain various conventional additives or resins. Examples of such additives include plasticizers, organic acids, dyes, polymers, retardation modifiers, ultraviolet absorbers, antioxidants, matting agents, and the like.
－ポリマー（Ｓ）－
　上記ポリマー層を構成するポリマー（Ｓ）は、下記一般式（１）で表される繰り返し単位を有する。 -Polymer (S)-
The polymer (S) constituting the polymer layer has a repeating unit represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　上記一般式（１）において、Ｒａは水素原子、アルキル基又はアルコキシカルボニル基を示す。
　Ｒａがアルキル基の場合、このアルキル基は直鎖でも分岐を有してもよい。このアルキル基の炭素数は１～２０が好ましく、１～１０がより好ましく、１～８がさらに好ましく、１～６がさらに好ましく、１～４が特に好ましい。このアルキル基の好ましい具体例として、例えばメチル、エチル、プロピル、イソプロピル、ｎ－ブチル、ｔ－ブチル、ｓ－ブチル、イソブチルを挙げることができる。 In the general formula (1), R a represents a hydrogen atom, an alkyl group or an alkoxycarbonyl group.
When R a is an alkyl group, the alkyl group may be linear or branched. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 1 to 4. Preferable specific examples of this alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, s-butyl and isobutyl.
　Ｒａがアルコキシカルボニル基の場合、このアルコキシカルボニル基は直鎖でも分岐を有してもよい。このアルコキシカルボニル基の炭素数は２～２０が好ましく、２～１０がより好ましく、２～８がさらに好ましく、２～４がさらに好ましい。このアルコキシカルボニル基の好ましい具体例としては、メトキシカルボニル、エトキシカルボニルなどが挙げられる。 When R a is an alkoxycarbonyl group, the alkoxycarbonyl group may be linear or branched. The alkoxycarbonyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, further preferably 2 to 8 carbon atoms, and further preferably 2 to 4 carbon atoms. Preferable specific examples of this alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl and the like.
　Ｒａはより好ましくは水素原子又はメチルである。 R a is more preferably a hydrogen atom or methyl.
　Ｒｂ及びＲｃは水素原子、アルキル基、アリール基又はアルコキシカルボニル基を示す。
　Ｒｂ及びＲｃがアルキル基の場合、このアルキル基は直鎖でも分岐を有してもよい。このアルキル基の炭素数は１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましく、さらに好ましくはメチル又はエチルであり、さらに好ましくはメチルである。
　Ｒｂ及びＲｃがアリール基の場合、このアリール基は、その炭素数が６～２０が好ましく、６～１５がさらに好ましく、６～１２が特に好ましく、とりわけフェニルが好ましい。
　Ｒｂ及びＲｃがアルコキシカルボニル基の場合、このアルコキシカルボニル基は、その炭素数が２～１０が好ましく、２～５がさらに好ましく、さらに好ましくはメトキシカルボニル又はエトキシカルボニルである。
　Ｒｂ及びＲｃはさらに好ましくは水素原子である。 R b and R c represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
When R b and R c are alkyl groups, the alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, more preferably 1 to 3, more preferably methyl or ethyl, and still more preferably methyl.
When R b and R c are an aryl group, the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, particularly preferably 6 to 12 carbon atoms, and particularly preferably phenyl.
When R b and R c are alkoxycarbonyl groups, the alkoxycarbonyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and still more preferably methoxycarbonyl or ethoxycarbonyl.
R b and R c are more preferably a hydrogen atom.
　Ｌ１はアルキレン基、アリーレン基、－Ｃ（＝Ｏ）－、－Ｏ－及び－ＮＲ３－から選ばれる２価の基を２種以上組み合わせてなる２価の連結基を示す。但し、Ｌ１はその構造中に、－Ｃ（＝Ｏ）ＮＲ３－で表される基を含む。Ｌ１中の－Ｃ（＝Ｏ）ＮＲ３－の数は１～３個が好ましく、１又は２個がより好ましく、１個がさらに好ましい。なお、Ｌ１がその構造中に－ＮＲ３Ｃ（＝Ｏ）ＮＲ３－の構造（ウレア結合）を含む場合、この－ＮＲ３Ｃ（＝Ｏ）ＮＲ３－が有する－Ｃ（＝Ｏ）ＮＲ３－の数は１個とする。
　－Ｃ（＝Ｏ）ＮＲ３－がＬ１中に組み込まれる向きに特に制限はない。すなわち、Ｌ１が－Ｃ（＝Ｏ）ＮＲ３－で表される基を含む形態には、－Ｃ（＝Ｏ）ＮＲ３－のＣ（＝Ｏ）の側がＲ２側に結合した形態、及び、－Ｃ（＝Ｏ）ＮＲ３－のＮＲ３の側がＲ２側に結合した形態の両形態が含まれる。 L 1 represents a divalent linking group formed by combining two or more divalent groups selected from an alkylene group, an arylene group, —C (═O) —, —O—, and —NR 3 —. However, L 1 includes a group represented by —C (═O) NR 3 — in its structure. The number of —C (═O) NR 3 — in L 1 is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. Incidentally, L 1 is -NR 3 C in its structure (= O) NR 3 - if it contains structure (urea bond) of the -NR 3 C (= O) NR 3 - -C having the (= O) The number of NR 3 − is one.
There is no particular limitation on the direction in which —C (═O) NR 3 — is incorporated into L 1 . That is, in the form in which L 1 includes a group represented by —C (═O) NR 3 —, the form in which the C (═O) side of —C (═O) NR 3 — is bonded to the R 2 side, In addition, both forms in which the NR 3 side of —C (═O) NR 3 — is bonded to the R 2 side are included.
　Ｒ３は水素原子又は置換基を示す。Ｒ３が置換基の場合、この置換基としては、上述した置換基群Ｔから選ばれる基が挙げられ、なかでもアルキル基が好ましい。このアルキル基の炭素数は１～６が好ましく、１～４がより好ましく、メチル又はエチルがさらに好ましい。
　またＲ３はカルボニル基によって－Ｃ（＝Ｏ）ＮＲ３－における窒素原子と結合する基であることも好ましい。この場合、Ｒ３はＲ２が有する置換基と結合した形態を採ることが好ましい。このときは、Ｒ２はアリール基（好ましくはフェニル基）であることが好ましい。
　なかでもＲ３は水素原子であることが好ましい。 R 3 represents a hydrogen atom or a substituent. When R 3 is a substituent, examples of the substituent include a group selected from the substituent group T described above, and an alkyl group is particularly preferable. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably methyl or ethyl.
R 3 is preferably a group bonded to a nitrogen atom in —C (═O) NR 3 — by a carbonyl group. In this case, R 3 preferably takes a form in which R 3 is bonded to the substituent of R 2 . In this case, R 2 is preferably an aryl group (preferably a phenyl group).
Of these, R 3 is preferably a hydrogen atom.
　Ｌ１を構成しうる上記アルキレン基は直鎖でも分岐を有してもよい。このアルキレン基の炭素数は１～１０が好ましく、１～６がより好ましく、１～３がさらに好ましい。 The alkylene group that can constitute L 1 may be linear or branched. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.
　Ｌ１を構成しうる上記アリーレン基は、その炭素数が６～２０が好ましく、６～１５がさらに好ましく。６～１２がさらに好ましく、さらに好ましくはフェニレン基である。 The arylene group that can constitute L 1 preferably has 6 to 20 carbon atoms, and more preferably 6 to 15 carbon atoms. 6 to 12 are more preferable, and a phenylene group is more preferable.
　Ｌ１は、アルキレン基、－Ｃ（＝Ｏ）－、－Ｏ－及び－ＮＲ３－から選ばれる２価の基を２種以上組み合わせてなる２価の連結基であることが好ましい。
　Ｌ１はその分子量が１２～２４０が好ましく、４４～１５０がより好ましい。 L 1 is preferably a divalent linking group formed by combining two or more divalent groups selected from an alkylene group, —C (═O) —, —O—, and —NR 3 —.
L 1 has a molecular weight of preferably 12 to 240, more preferably 44 to 150.
　Ｒ２はアルキル基、シクロアルキル基又はアリール基を示す。ここで、本発明においてＲ２の構造中には、－Ｃ（＝Ｏ）－、酸素原子及び窒素原子のいずれも含まれない。すなわち、Ｒ２がアルキル基、シクロアルキル基又はアリール基である場合において、これらアルキル基、シクロアルキル基及びアリール基が置換基を有する形態である場合、かかる置換基中にはカルボニル基、酸素原子及び窒素原子のいずれも含まれない。 R 2 represents an alkyl group, a cycloalkyl group or an aryl group. Here, in the present invention, the structure of R 2 does not include any of —C (═O) —, an oxygen atom, and a nitrogen atom. That is, when R 2 is an alkyl group, a cycloalkyl group, or an aryl group, when these alkyl group, cycloalkyl group, and aryl group are in a form having a substituent, the substituent includes a carbonyl group, an oxygen atom And nitrogen atoms are not included.
　一般式（１）において、Ｒ２がアルキル基の場合、このアルキル基は、可能な限りの長鎖アルキル基（炭素原子数が最も多くなるアルキル基）となるように解釈するものとする。例えば、Ｌ１がＲ２側末端にアルキレン基を有さず、且つＲ２がエチルである場合、この形態は見方を変えれば、Ｌ１がＲ２側末端にメチレンを有し、且つＲ２がメチルである形態と解釈することも可能である。しかし、本発明においてはかかる形態を、Ｒ２がエチルであると解釈する。 In the general formula (1), when R 2 is an alkyl group, the alkyl group is interpreted to be as long as possible a long-chain alkyl group (an alkyl group having the largest number of carbon atoms). For example, if L 1 does not have an alkylene group at the R 2 side end and R 2 is ethyl, this form is, in a different way, L 1 has methylene at the R 2 side end and R 2 Can also be interpreted as the form in which is methyl. However, in the present invention, this form is interpreted as R 2 is ethyl.
　一般式（１）において、Ｒ２がアリール基の場合、このアリール基は、可能な限り分子量の大きなアリール基として解釈するものとする。例えば、Ｌ１がＲ２側末端にアリーレン基を有さず、且つＲ２が置換基としてフェニルを有するフェニル基である場合、この形態は見方を変えれば、Ｌ１がＲ２側末端にフェニレンを有し、且つＲ２がフェニルである形態と解釈することも可能である。しかし、本発明においてはかかる形態を、Ｒ２が置換基としてフェニルを有するフェニル基であると解釈する。 In the general formula (1), when R 2 is an aryl group, the aryl group should be interpreted as an aryl group having a molecular weight as large as possible. For example, L 1 is as free an arylene group R 2 side end, and a phenylene when R 2 is a phenyl group having a phenyl as a substituent, if this form another point of view, L 1 is the R 2 side end And R 2 is phenyl. However, in the present invention, this form is interpreted as a phenyl group in which R 2 has phenyl as a substituent.
　上記Ｒ２がアルキル基の場合、このアルキル基は直鎖でも分岐を有してもよい。また無置換でも置換基を有してもよい。このアルキル基の炭素数は１～１２が好ましく、１～１０がより好ましく、１～８がさらに好ましく、１～６がさらに好ましく、１～４がさらに好ましい。また、Ｌ１がＲ２側末端に－ＮＲ３－を有する形態である場合、アルキル基Ｒ２は、Ｒ３と連結して環を形成してもよい。かかる環構造の例としては、モルホリン環、ピロリドン環、イミダゾリドン環、及びスクシンイミド環を挙げることができ、モルホリン環が好ましい。 When R 2 is an alkyl group, the alkyl group may be linear or branched. Further, it may be unsubstituted or may have a substituent. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and further preferably 1 to 4. In addition, when L 1 has a form having —NR 3 — at the R 2 side terminal, the alkyl group R 2 may be linked to R 3 to form a ring. Examples of such a ring structure include a morpholine ring, a pyrrolidone ring, an imidazolidone ring, and a succinimide ring, and a morpholine ring is preferred.
　上記Ｒ２がシクロアルキル基の場合、このシクロアルキル基は無置換でも置換基を有してもよい。このシクロアルキルは、その炭素数が６～２０が好ましく、６～１５がより好ましく、６～１２がさらに好ましく、シクロペンチル基又はシクロヘキシル基であることがさらに好ましい。 When R 2 is a cycloalkyl group, the cycloalkyl group may be unsubstituted or may have a substituent. The cycloalkyl preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, still more preferably 6 to 12 carbon atoms, and even more preferably a cyclopentyl group or a cyclohexyl group.
　上記Ｒ２がアリール基の場合、このアリール基は無置換でも置換基を有してもよい。このアリール基は、その炭素数が６～２０が好ましく、６～１５がより好ましく、６～１２がさらに好ましく、フェニル基であることが特に好ましい。 When R 2 is an aryl group, the aryl group may be unsubstituted or may have a substituent. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, still more preferably 6 to 12 carbon atoms, and particularly preferably a phenyl group.
　上記一般式（１）で表される繰り返し単位は、下記一般式（２）又は（３）で表される繰り返し単位であることが好ましい。 The repeating unit represented by the general formula (1) is preferably a repeating unit represented by the following general formula (2) or (3).
Figure JPOXMLDOC01-appb-C000012
  
Figure JPOXMLDOC01-appb-C000012
  
　一般式（２）中、Ｒ１ａは水素原子又はメチルを示す。Ｒ２は上記一般式（１）におけるＲ２と同義であり、好ましい形態も同じである。 In general formula (2), R 1a represents a hydrogen atom or methyl. R 2 has the same meaning as R 2 in the general formula (1), and the preferred form is also the same.
　Ｌ２はアルキレン基、アルキレンオキシ基又はポリアルキレンオキシ基を示す。
　Ｌ２がアルキレン基の場合、このアルキレン基は直鎖でも分岐を有してもよく、直鎖であることが好ましい。このアルキレン基の炭素数は１～１０が好ましく、１～６がより好ましく、１～４がさらに好ましく、１～３がさらに好ましく、エチレンであることが特に好ましい。
　Ｌ２がアルキレンオキシ基の場合、このアルキレンオキシ基は直鎖でも分岐を有してもよく、直鎖であることが好ましい。このアルキレンオキシ基の炭素数は１～１０が好ましく、１～６がより好ましく、１～４がさらに好ましく、１～３がさらに好ましい。
　Ｌ２がポリアルキレンオキシ基の場合、このポリアルキレンオキシ基を構成するアルキレンオキシ基は直鎖でも分岐を有してもよく、直鎖であることが好ましい。このポリアルキレンオキシ基を構成するアルキレンオキシ基の炭素数は１～１０が好ましく、１～６がより好ましく、１～４がさらに好ましく、１～３がさらに好ましい。また、このポリアルキレンオキシ基全体の炭素数は１～１０が好ましく、１～６がより好ましい。また、このポリアルキレンオキシ基の酸素数は１～４が好ましく、１～３がより好ましく、１～２が特に好ましい。Ｌ２がポリアルキレンオキシ基の場合、ポリアルキレンオキシ基を構成するアルキレンオキシ基は同一でも異なっていてもよい。
　Ｌ２は、エチレンオキシ基であることが特に好ましい。
　Ｌ２がアルキレンオキシ基又はポリアルキレンオキシ基である場合、このアルキレンオキシ基又はポリアルキレンオキシ基中の酸素原子がＡと連結する。 L 2 represents an alkylene group, an alkyleneoxy group or a polyalkyleneoxy group.
When L 2 is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably ethylene.
When L 2 is an alkyleneoxy group, the alkyleneoxy group may be linear or branched, and is preferably linear. The alkyleneoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3.
When L 2 is a polyalkyleneoxy group, the alkyleneoxy group constituting the polyalkyleneoxy group may be linear or branched, and is preferably linear. The alkyleneoxy group constituting the polyalkyleneoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3. The total number of carbon atoms of the polyalkyleneoxy group is preferably 1 to 10, more preferably 1 to 6. The oxygen number of the polyalkyleneoxy group is preferably 1 to 4, more preferably 1 to 3, and particularly preferably 1 to 2. When L 2 is a polyalkyleneoxy group, the alkyleneoxy groups constituting the polyalkyleneoxy group may be the same or different.
L 2 is particularly preferably an ethyleneoxy group.
When L 2 is an alkyleneoxy group or a polyalkyleneoxy group, an oxygen atom in the alkyleneoxy group or polyalkyleneoxy group is linked to A.
　Ａは－Ｃ（＝Ｏ）ＮＲ３－又は－ＮＲ３－Ｃ（＝Ｏ）－ＮＲ３－を示す。Ｒ３は上記一般式（１）において説明したＲ３と同義であり、好ましい形態も同じである。またＡが－Ｃ（＝Ｏ）ＮＲ３－の場合、その向きに制限はない。すなわち、－Ｃ（＝Ｏ）ＮＲ３－のＮＲ３はＬ２の側に向いていてもよいしＲ２の側に向いていてもよい。 A represents —C (═O) NR 3 — or —NR 3 —C (═O) —NR 3 —. R 3 has the same meaning as R 3 described in the general formula (1), and the preferred form is also the same. When A is —C (═O) NR 3 —, the direction is not limited. That, -C (= O) NR 3 - in NR 3 is may be oriented on the side of the L 2 may face the side of R 2.
Figure JPOXMLDOC01-appb-C000013
  
Figure JPOXMLDOC01-appb-C000013
  
　一般式（３）中、Ｒ１ａ及びＲ２は、それぞれ上記一般式（２）におけるＲ１ａ及びＲ２と同義であり、好ましい形態も同じである。 In the general formula (3), R 1a and R 2 each have the same meaning as R 1a and R 2 in the general formula (2), a preferred form also the same.
　Ｒ３ａは水素原子又はアルキル基を示す。
　Ｒ３ａがアルキル基の場合、このアルキル基の炭素数は１～６が好ましく、１～４がより好ましく、メチル又はエチルがさらに好ましい。
　Ｒ２とＲ３ａが共にアルキル基の場合、これらは互いに連結して環を構成してもよい。この環構造の環構成原子には窒素原子以外のヘテロ原子が含まれていてもよい。この環構造の具体例としてモルホリン環、ピロリドン環、イミダゾリドン環、及びスクシンイミド環を挙げることができ、モルホリン環が好ましい。 R 3a represents a hydrogen atom or an alkyl group.
When R 3a is an alkyl group, the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably methyl or ethyl.
When R 2 and R 3a are both alkyl groups, they may be linked to each other to form a ring. The ring atoms of this ring structure may contain heteroatoms other than nitrogen atoms. Specific examples of this ring structure include a morpholine ring, a pyrrolidone ring, an imidazolidone ring, and a succinimide ring, and a morpholine ring is preferred.
　上記一般式（１）で表される繰り返し単位は、下記一般式（４）で表される繰り返し単位であることがさらに好ましい。 The repeating unit represented by the general formula (1) is more preferably a repeating unit represented by the following general formula (4).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　上記一般式（４）中、Ｒ１ａ及びＲ２は、それぞれ上記一般式（３）におけるＲ１ａ及びＲ２と同義であり、好ましい形態も同じである。 In the general formula (4), R 1a and R 2 each have the same meaning as R 1a and R 2 in the general formula (3), a preferred form also the same.
　上記一般式（１）で表される化合物の好ましい具体例を以下に示すが、本発明はこれらの形態に限定されるものではない。 Preferred specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited to these forms.
Figure JPOXMLDOC01-appb-C000015
  
Figure JPOXMLDOC01-appb-C000015
  
　上記ポリマー（Ｓ）は、上記一般式（１）で表される繰り返し単位のみからなっていてもよく、上記一般式（１）で表される繰り返し単位以外の繰り返し単位を有していてもよい。上記ポリマー（Ｓ）中の上記一般式（１）で表される繰り返し単位の含有量は、１０～１００質量％が好ましく、２０～１００質量％がより好ましい。 The polymer (S) may consist of only the repeating unit represented by the general formula (1) or may have a repeating unit other than the repeating unit represented by the general formula (1). . The content of the repeating unit represented by the general formula (1) in the polymer (S) is preferably 10 to 100% by mass, and more preferably 20 to 100% by mass.
　上記ポリマー（Ｓ）は、セルロースエステル樹脂層を形成する際に用いる塗布溶媒に対して溶解しやすい物性を有し、リサイクル性にも優れる。本発明の積層体の製造においては、セルロース樹脂層とポリマー層を有する積層構造を形成した後、得られた積層体を所望大きさに切断し、出荷される。切断された不要な断片は、セルロースエステル樹脂層を形成する材料中に許容される範囲内で（所望の光学特性等を損なわない範囲内で）混合され、リサイクルすることが想定される。その際には、セルロースエステル樹脂層を形成するために用いる塗布溶媒中に、ポリマー（Ｓ）が十分に溶解し、この塗布溶媒中においてポリマー（Ｓ）とセルロースエステル樹脂とが均質に混合される必要がある。上記ポリマー（Ｓ）はかかる溶媒に対する溶解性に優れ、リサイクル性にも優れるものである。
　上記ポリマー（Ｓ）は、下記一般式（５）で表される繰り返し単位を有することも好ましい。下記一般式（５）で表される繰り返し単位を有することにより上記塗布溶媒中への溶解性をより高めることができ、上述したリサイクル性をより向上させることができる。 The polymer (S) has physical properties that are easily dissolved in a coating solvent used when forming the cellulose ester resin layer, and is excellent in recyclability. In the production of the laminate of the present invention, after forming a laminated structure having a cellulose resin layer and a polymer layer, the obtained laminate is cut into a desired size and shipped. It is assumed that the cut unnecessary pieces are mixed and recycled within a range that is allowed in the material forming the cellulose ester resin layer (within a range that does not impair desired optical properties and the like). In that case, the polymer (S) is sufficiently dissolved in the coating solvent used to form the cellulose ester resin layer, and the polymer (S) and the cellulose ester resin are homogeneously mixed in the coating solvent. There is a need. The polymer (S) is excellent in solubility in such a solvent and excellent in recyclability.
The polymer (S) also preferably has a repeating unit represented by the following general formula (5). By having a repeating unit represented by the following general formula (5), the solubility in the coating solvent can be further increased, and the recyclability described above can be further improved.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　一般式（５）中、Ｒ６は水素原子又はアルキル基を示す。
　Ｒ６がアルキル基の場合、このアルキル基は直鎖でも分岐を有してもよい。このアルキル基の炭素数は１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましい。Ｒ６はより好ましくはメチル又はエチルであり、さらに好ましくはメチルである。
　Ｒ６はさらに好ましくは水素原子又はメチルである。 In general formula (5), R 6 represents a hydrogen atom or an alkyl group.
When R 6 is an alkyl group, the alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms. R 6 is more preferably methyl or ethyl, and even more preferably methyl.
R 6 is more preferably a hydrogen atom or methyl.
　Ｒ４及びＲ５は水素原子、アルキル基、アリール基又はアルコキシカルボニル基を示す。
　Ｒ４及びＲ５がアルキル基の場合、このアルキル基は直鎖でも分岐を有してもよい。このアルキル基の炭素数は１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましく、さらに好ましくはメチル又はエチルであり、さらに好ましくはメチルである。
　Ｒ４及びＲ５がアリール基の場合、このアリール基は、その炭素数が６～２０が好ましく、６～１５がさらに好ましく、６～１２が特に好ましく、とりわけフェニルが好ましい。
　Ｒ４及びＲ５がアルコキシカルボニル基の場合、このアルコキシカルボニル基は、その炭素数が２～１０が好ましく、２～５がさらに好ましく、さらに好ましくはメトキシカルボニル又はエトキシカルボニルである。
　Ｒ４及びＲ５はさらに好ましくは水素原子である。 R 4 and R 5 represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
When R 4 and R 5 are alkyl groups, the alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, more preferably 1 to 3, more preferably methyl or ethyl, and still more preferably methyl.
When R 4 and R 5 are an aryl group, the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, particularly preferably 6 to 12 carbon atoms, and particularly preferably phenyl.
When R 4 and R 5 are alkoxycarbonyl groups, the alkoxycarbonyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and still more preferably methoxycarbonyl or ethoxycarbonyl.
R 4 and R 5 are more preferably a hydrogen atom.
　Ｌ３は単結合であるか、又は、アルキレン基、アリーレン基、－Ｃ（＝Ｏ）－、－Ｏ－及び－ＮＲ３Ａ－から選ばれる２価の基もしくはこれらの基の２種以上を組合せてなる２価の連結基を示す。
　Ｒ３Ａは水素原子又は置換基を示す。Ｒ３Ａが置換基の場合、この置換基としては、上述した置換基群Ｔから選ばれる基が挙げられ、なかでもアルキル基が好ましい。このアルキル基の炭素数は１～６が好ましく、１～４がより好ましく、メチル又はエチルがさらに好ましい。
　上記の２種以上を組み合わせてなる２価の連結基において、組み合わされる上記連結基の数は、特に限定されないが、例えば、２～９個が好ましく、２個又は３個がより好ましい。また、連結基の組み合わせも、特に限定されず、例えば、－Ｃ（＝Ｏ）－、－Ｏ－及びアルキレン基の組み合わせ、又は、－Ｃ（＝Ｏ）－、－Ｏ－及びアリーレン基の組み合わせが好ましく、－Ｃ（＝Ｏ）－、－Ｏ－及びアルキレン基の組み合わせがより好ましい。なかでも、Ｌ３が－Ｃ（＝Ｏ）－を含む連結基であり、－Ｃ（＝Ｏ）－が主鎖（Ｒ６が結合している炭素原子）に結合することが更に好ましい。 L 3 is a single bond, or a divalent group selected from an alkylene group, an arylene group, —C (═O) —, —O— and —NR 3A —, or a combination of two or more of these groups And a divalent linking group.
R 3A represents a hydrogen atom or a substituent. When R 3A is a substituent, examples of the substituent include a group selected from the substituent group T described above, and an alkyl group is particularly preferable. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably methyl or ethyl.
In the divalent linking group formed by combining two or more of the above, the number of the linking groups to be combined is not particularly limited, but is preferably 2 to 9, and more preferably 2 or 3. Also, the combination of the linking groups is not particularly limited. For example, the combination of —C (═O) —, —O— and an alkylene group, or the combination of —C (═O) —, —O— and an arylene group. And a combination of —C (═O) —, —O— and an alkylene group is more preferred. Among these, it is more preferable that L 3 is a linking group containing —C (═O) —, and —C (═O) — is bonded to the main chain (the carbon atom to which R 6 is bonded).
　アルキレン基Ｌ３、又はＬ３中に組み込まれるアルキレン基は直鎖であることが好ましい。また、このアルキレン基の炭素数は１～５が好ましく、１～４がより好ましく、１～３がさらに好ましく、２が特に好ましい。
　アリーレン基Ｌ３、又はＬ３中に組み込まれるアリーレン基は、その炭素数が６～２０が好ましく、６～１５がさらに好ましく、６～１２が特に好ましく、とりわけフェニレンが好ましい。 The alkylene group L 3 or the alkylene group incorporated in L 3 is preferably linear. The alkylene group preferably has 1 to 5 carbon atoms, more preferably 1 to 4, more preferably 1 to 3, and particularly preferably 2.
The arylene group L 3 or the arylene group incorporated in L 3 preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, particularly preferably 6 to 12 carbon atoms, and particularly preferably phenylene.
　上記一般式（５）で表される繰り返し単位の好ましい具体例を以下に示すが、本発明はこれらの例に限定されるものではない。 Preferred specific examples of the repeating unit represented by the general formula (5) are shown below, but the present invention is not limited to these examples.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　上記ポリマー（Ｓ）が上記一般式（５）で表される繰り返し単位を有する場合、ポリマー（Ｓ）中の、上記一般式（５）で表される繰り返し単位の含有量は５～３０質量％が好ましく、１０～２０質量％がさらに好ましい。 When the polymer (S) has a repeating unit represented by the general formula (5), the content of the repeating unit represented by the general formula (5) in the polymer (S) is 5 to 30% by mass. 10 to 20% by mass is more preferable.
　上記ポリマー（Ｓ）が、上記一般式（１）で表される繰り返し単位と共に上記一般式（１）で表される繰り返し単位以外の繰り返し単位を含む場合には、上記ポリマー（Ｓ）中から上記一般式（１）で表される繰り返し単位を除いた残部が、上記一般式（５）で表される繰り返し単位、及び／又は、上記一般式（１）で表される繰り返し単位に包含されず且つ上記一般式（５）で表される繰り返し単位にも包含されない（メタ）アクリル酸エステル由来の繰り返し単位で構成されていることが好ましい。（以下、上記一般式（１）で表される繰り返し単位に包含されず且つ上記一般式（５）で表される繰り返し単位にも包含されない（メタ）アクリル酸エステル由来の繰り返し単位を、「繰り返し単位（Ｒ）」という。）
　上記繰り返し単位（Ｒ）としては、（メタ）アクリル酸アルキルエステル由来も繰り返し単位がより好ましい。上記繰り返し単位（Ｒ）の好ましい具体例として、例えば、ベンジル（メタ）アクリレート由来の繰り返し単位、メチル（メタ）アクリレート由来の繰り返し単位、エチル（メタ）アクリレート由来の繰り返し単位、フェノキシエチル（メタ）アクリレート由来の繰り返し単位、イソプロピル（メタ）アクリレート由来の繰り返し単位、ｎ－ブチル（メタ）アクリレート由来の繰り返し単位、イソブチル（メタ）アクリレート由来の繰り返し単位、エチルヘキシル（メタ）アクリレート由来の繰り返し単位、シクロヘキシル（メタ）アクリレート由来の繰り返し単位、イソボルニル（メタ）アクリレート由来の繰り返し単位、ジシクロペンテニルオキシエチル（メタ）アクリレート由来の繰り返し単位を挙げることができる。 When the polymer (S) contains a repeating unit other than the repeating unit represented by the general formula (1) together with the repeating unit represented by the general formula (1), The remainder excluding the repeating unit represented by the general formula (1) is not included in the repeating unit represented by the general formula (5) and / or the repeating unit represented by the general formula (1). And it is preferable to be comprised by the repeating unit derived from the (meth) acrylic acid ester which is not included in the repeating unit represented by the said General formula (5). (Hereinafter, a repeating unit derived from a (meth) acrylic acid ester not included in the repeating unit represented by the general formula (1) and not included in the repeating unit represented by the general formula (5) is referred to as “repeating Unit (R) ")
As said repeating unit (R), the repeating unit derived from (meth) acrylic-acid alkylester is more preferable. Preferable specific examples of the repeating unit (R) include, for example, a repeating unit derived from benzyl (meth) acrylate, a repeating unit derived from methyl (meth) acrylate, a repeating unit derived from ethyl (meth) acrylate, and phenoxyethyl (meth) acrylate. Repeating units derived from isopropyl (meth) acrylate, repeating units derived from n-butyl (meth) acrylate, repeating units derived from isobutyl (meth) acrylate, repeating units derived from ethylhexyl (meth) acrylate, cyclohexyl (meth ) A repeating unit derived from acrylate, a repeating unit derived from isobornyl (meth) acrylate, and a repeating unit derived from dicyclopentenyloxyethyl (meth) acrylate.
　上記ポリマー（Ｓ）中において、上記一般式（１）で表される繰り返し単位と、上記一般式（５）で表される繰り返し単位と、繰り返し単位（Ｒ）の総モル量中、上記一般式（１）で表される繰り返し単位のモル量は１０～１００モル％が好ましく、１５～１００モル％がより好ましく、２０～９５モル％がさらに好ましい。
　また、上記ポリマー（Ｓ）が上記一般式（５）で表される繰り返し単位を有する場合、上記ポリマー（Ｓ）中において、上記一般式（１）で表される繰り返し単位と、上記一般式（５）で表される繰り返し単位と、繰り返し単位（Ｒ）の総モル量中、上記一般式（５）で表される繰り返し単位のモル量は５～５０モル％が好ましく、１０～４０モル％がより好ましく、１５～３０モル％がさらに好ましい。
　また、上記ポリマー（Ｓ）が上記繰り返し単位（Ｒ）を有する場合、上記ポリマー（Ｓ）中において、上記一般式（１）で表される繰り返し単位と、上記一般式（５）で表される繰り返し単位と、繰り返し単位（Ｒ）の総モル量中、繰り返し単位（Ｒ）のモル量は１０～９５モル％が好ましく、１０～９０モル％がより好ましく、２０～９０モル％がさらに好ましい。 In the polymer (S), in the total molar amount of the repeating unit represented by the general formula (1), the repeating unit represented by the general formula (5), and the repeating unit (R), the general formula The molar amount of the repeating unit represented by (1) is preferably 10 to 100 mol%, more preferably 15 to 100 mol%, and further preferably 20 to 95 mol%.
Further, when the polymer (S) has a repeating unit represented by the general formula (5), the repeating unit represented by the general formula (1) in the polymer (S) and the general formula (1) In the total molar amount of the repeating unit represented by 5) and the repeating unit (R), the molar amount of the repeating unit represented by the general formula (5) is preferably 5 to 50 mol%, and preferably 10 to 40 mol%. Is more preferable, and 15 to 30 mol% is still more preferable.
Moreover, when the said polymer (S) has the said repeating unit (R), in the said polymer (S), it represents with the repeating unit represented by the said General formula (1), and the said General formula (5). In the total molar amount of the repeating unit and the repeating unit (R), the molar amount of the repeating unit (R) is preferably 10 to 95 mol%, more preferably 10 to 90 mol%, and further preferably 20 to 90 mol%.
　上記ポリマー（Ｓ）は、ガラス転移温度（Ｔｇ）が５０℃以上である。高温、高湿条件下における耐久性をより高める観点から、上記ポリマー（Ｓ）のＴｇは７０℃以上が好ましく、８０℃以上がより好ましく、９０℃以上がさらに好ましく、９５℃以上がさらに好ましい。上記ポリマー（Ｓ）のＴｇの上限に特に制限はなく、１８０℃以下とするのが実際的であり、通常は１３０℃以下である。すなわち上記ポリマー（Ｓ）は接着剤または粘着剤として用いられる類のポリマーとは物性が異なる。 The polymer (S) has a glass transition temperature (Tg) of 50 ° C. or higher. From the viewpoint of further improving durability under high temperature and high humidity conditions, the Tg of the polymer (S) is preferably 70 ° C or higher, more preferably 80 ° C or higher, further preferably 90 ° C or higher, and further preferably 95 ° C or higher. There is no restriction | limiting in particular in the upper limit of Tg of the said polymer (S), It is practical to set it as 180 degrees C or less, and it is 130 degrees C or less normally. That is, the polymer (S) has physical properties different from those of the polymers used as adhesives or pressure-sensitive adhesives.
　本発明においてＴｇは、示差走査熱量計（ＤＳＣ）を用いて測定される。
　本発明においては、後述の実施例に記載の方法を用いることができる。測定試料はポリマー粉末そのものの他、積層体からポリマー層を削りとった粉末を用いてもよい。なお、積層体からポリマー層を削りとった粉末を用いる場合は、必要に応じてポリマー以外の成分を除去（精製）してもよい。 In the present invention, Tg is measured using a differential scanning calorimeter (DSC).
In the present invention, the methods described in Examples described later can be used. As the measurement sample, in addition to the polymer powder itself, a powder obtained by scraping the polymer layer from the laminate may be used. In addition, when using the powder which removed the polymer layer from the laminated body, you may remove (purify) components other than a polymer as needed.
　上記ポリマー（Ｓ）の重量平均分子量の下限値は、フィルム面状の観点から、１０，０００以上であることが好ましく、２０，０００以上であることがより好ましく、３０，０００であることがさらに好ましい。一方、上記ポリマー（Ｓ）の重量平均分子量の上限値は、製膜性の観点から、５００，０００以下であることが好ましく、３００，０００以下であることがより好ましく、２００，０００以下であることがさらに好ましく、１５０，０００以下であることがさらに好ましい。
　重量平均分子量は、後述する実施例に記載の方法等で測定することができる。 The lower limit value of the weight average molecular weight of the polymer (S) is preferably 10,000 or more, more preferably 20,000 or more, and further preferably 30,000, from the viewpoint of film planarity. preferable. On the other hand, the upper limit of the weight average molecular weight of the polymer (S) is preferably 500,000 or less, more preferably 300,000 or less, and 200,000 or less, from the viewpoint of film forming properties. More preferably, it is more preferably 150,000 or less.
The weight average molecular weight can be measured by the method described in Examples described later.
　ポリマー（Ｓ）は、上記各繰り返し単位を導くモノマーを常法により重合させることで得ることができる。例えば、熱重合開始剤及び／又は光重合開始剤の共存下、熱処理及び／又は光照射することにより、モノマーを重合させて得ることができる。 The polymer (S) can be obtained by polymerizing a monomer that leads each of the above repeating units by a conventional method. For example, it can be obtained by polymerizing a monomer by heat treatment and / or light irradiation in the presence of a thermal polymerization initiator and / or a photopolymerization initiator.
　本発明において、上記ポリマー層の膜厚に特に制限はなく、１～２５μｍが好ましく、２～２０μｍがより好ましく、１～１５μｍが特に好ましい。また、上記ポリマー層の膜厚は２～１５μｍであることも好ましく、３～１５μｍであることも好ましく、５～１５μｍであることも好ましい。 In the present invention, the film thickness of the polymer layer is not particularly limited, preferably 1 to 25 μm, more preferably 2 to 20 μm, particularly preferably 1 to 15 μm. The film thickness of the polymer layer is preferably 2 to 15 μm, preferably 3 to 15 μm, and preferably 5 to 15 μm.
［セルロースエステル樹脂層］
　本発明の積層体を構成するセルロースエステル樹脂層は、層中にセルロースエステルを５０質量％以上含有する層である。セルロースエステル樹脂層中のセルロースエステルの含有量は６０質量％以上が好ましく、７０質量％以上がより好ましく、８０質量％以上がさらに好ましく、８５質量％以上がさらに好ましい。セルロースエステル樹脂層中のセルロースエステルの含有量の上限は、通常は９６質量％以下であり、９５質量％以下が好ましく、９２質量％以下がさらに好ましい。この場合、セルロースエステルを除く残部には、例えば後述する添加剤等が含まれる。 [Cellulose ester resin layer]
The cellulose ester resin layer which comprises the laminated body of this invention is a layer which contains 50 mass% or more of cellulose esters in a layer. 60 mass% or more is preferable, as for content of the cellulose ester in a cellulose-ester resin layer, 70 mass% or more is more preferable, 80 mass% or more is further more preferable, and 85 mass% or more is further more preferable. The upper limit of the content of the cellulose ester in the cellulose ester resin layer is usually 96% by mass or less, preferably 95% by mass or less, and more preferably 92% by mass or less. In this case, the remainder excluding the cellulose ester includes, for example, additives described later.
＜セルロースエステル＞
　本発明のセルロースエステル樹脂層の製造において、原料として用いるセルロースエステルについて説明する。
　本発明で使用されるセルロースエステルの原料のセルロースとしては、綿花リンタ、木材パルプ（広葉樹パルプ，針葉樹パルプ）などがあり、何れの原料セルロースから得られるセルロースでも使用でき、場合により混合して使用してもよい。原料セルロースは、例えば、丸澤、宇田著，「プラスチック材料講座（１７）繊維素系樹脂」，日刊工業新聞社（１９７０年発行）又は発明協会公開技報公技番号２００１－１７４５号（７頁～８頁）に記載のセルロースを用いることができる。
　セルロースエステルとしては、セルロースエステルフィルムの製造に用いられる公知のセルロースエステルを何ら制限なく用いることができる。なかでもセルロースアシレートを用いることが好ましい。 <Cellulose ester>
The cellulose ester used as a raw material in the production of the cellulose ester resin layer of the present invention will be described.
The cellulose ester raw material cellulose used in the present invention includes cotton linter, wood pulp (hardwood pulp, softwood pulp), etc., and any cellulose obtained from any raw material cellulose can be used. May be. The raw material cellulose is, for example, Marusawa, Uda, “Plastic Materials Course (17) Fibrous Resin”, Nikkan Kogyo Shimbun (published in 1970), or Japan Institute of Invention and Technology Publication No. 2001-1745 (page 7). To page 8) can be used.
As a cellulose ester, the well-known cellulose ester used for manufacture of a cellulose-ester film can be used without a restriction | limiting at all. Of these, cellulose acylate is preferably used.
（セルロースアシレート）
　本発明に用いるセルロースアシレートは、セルロースアシレートフィルムの製造に用いられる公知のセルロースアシレートを何ら制限なく用いることができる。
　セルロースを構成するβ－１，４結合しているグルコース単位は、２位、３位及び６位に遊離のヒドロキシ基を有している。セルロースアシレートは、これらのヒドロキシ基の一部をアシル基によりアシル化した重合体（ポリマー）である。
　アシル置換度（以下、単に「置換度」ということがある）は、２位、３位及び６位に位置するセルロースのヒドロキシ基のアシル化の度合いを示すものであり、全てのグルコース単位の２位、３位及び６位のヒドロキシ基がいずれもアシル化された場合、総アシル置換度は３である。例えば、全てのグルコース単位で、６位のみが全てアシル化された場合、総アシル置換度は１である。同様に、全グルコースの全ヒドロキシ基において、各々のグルコース単位で、６位及び２位のいずれか一方の全てがアシル化された場合も、総アシル置換度は１である。
　すなわち置換度は、グルコース分子中の全ヒドロキシ基が全てアシル化された場合を３として、アシル化の度合いを示すものである。
　セルロースアシレートの置換度は、手塚他，Ｃａｒｂｏｈｙｄｒａｔｅ．Ｒｅｓ．，２７３，８３－９１（１９９５）に記載の方法、又は、ＡＳＴＭ－Ｄ８１７－９６に規定の方法に準じて測定することができる。 (Cellulose acylate)
As the cellulose acylate used in the present invention, a known cellulose acylate used for producing a cellulose acylate film can be used without any limitation.
The β-1,4-bonded glucose unit constituting cellulose has free hydroxy groups at the 2nd, 3rd and 6th positions. Cellulose acylate is a polymer obtained by acylating a part of these hydroxy groups with an acyl group.
The degree of acyl substitution (hereinafter sometimes simply referred to as “degree of substitution”) indicates the degree of acylation of the hydroxy group of cellulose located at the 2-position, 3-position and 6-position, and is 2 for all glucose units. When the hydroxy groups at the 3rd, 6th and 6th positions are all acylated, the total degree of acyl substitution is 3. For example, in all glucose units, when only the 6-position is all acylated, the total acyl substitution degree is 1. Similarly, the total acyl substitution degree is 1 when all of any one of the 6-position and 2-position is acylated in each glucose unit in all hydroxy groups of all glucose.
That is, the degree of substitution indicates the degree of acylation, assuming that 3 is when all the hydroxy groups in the glucose molecule are all acylated.
The degree of substitution of cellulose acylate is described in Tezuka et al., Carbohydrate. Res. , 273, 83-91 (1995), or according to the method prescribed in ASTM-D817-96.
　本発明に用いるセルロースアシレートの総アシル置換度は透湿度の観点から１．５０以上３．００以下であることが好ましく、２．００～２．９７であることがより好ましく、２．３０以上２．９７未満であることが更に好ましく、２．３０～２．９５であることが特に好ましい。 The total acyl substitution degree of the cellulose acylate used in the present invention is preferably 1.50 or more and 3.00 or less, more preferably 2.00 to 2.97, from the viewpoint of moisture permeability, and 2.30 or more. More preferably, it is less than 2.97, and particularly preferably 2.30 to 2.95.
　本発明に用いるセルロースアシレートのアシル基に特に制限はなく、１種のアシル基を有する形態でもよいし、２種以上のアシル基を有する形態でもよい。本発明に用いうるセルロースアシレートは、炭素数２以上のアシル基を置換基として有することが好ましい。炭素数２以上のアシル基に特に制限はなく、脂肪族のアシル基でもよいし、芳香族のアシル基でもよい。炭素数２以上のアシル基の具体例として、アセチル、プロピオニル、ブタノイル、ヘプタノイル、ヘキサノイル、オクタノイル、デカノイル、ドデカノイル、トリデカノイル、テトラデカノイル、ヘキサデカノイル、オクタデカノイル、イソブタノイル、ｔｅｒｔ－ブタノイル、シクロヘキサンカルボニル、オレオイル、ベンゾイル、ナフチルカルボニル、シンナモイルなどが挙げられる。これらの中でも、アセチル、プロピオニル、ブタノイル、ドデカノイル、オクタデカノイル、ｔｅｒｔ－ブタノイル、オレオイル、ベンゾイル、ナフチルカルボニル、シンナモイルが好ましく、さらに好ましくはアセチル、プロピオニル、ブタノイルである。 The acyl group of the cellulose acylate used in the present invention is not particularly limited, and may be a form having one kind of acyl group or a form having two or more kinds of acyl groups. The cellulose acylate that can be used in the present invention preferably has an acyl group having 2 or more carbon atoms as a substituent. The acyl group having 2 or more carbon atoms is not particularly limited, and may be an aliphatic acyl group or an aromatic acyl group. Specific examples of the acyl group having 2 or more carbon atoms include acetyl, propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, isobutanoyl, tert-butanoyl, cyclohexanecarbonyl Oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like. Among these, acetyl, propionyl, butanoyl, dodecanoyl, octadecanoyl, tert-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, and cinnamoyl are preferable, and acetyl, propionyl, and butanoyl are more preferable.
　セルロースアシレートのアシル基としてアセチル基のみを用いたセルロースアセテートは本発明に好適に用いることができ、このセルロースアセテートの総アシル置換度は、透湿度及び光学特性の観点から、２．００～３．００であることが好ましく、２．２０～３．００であることがより好ましく、２．３０～３．００であることが更に好ましく、２．３０～２．９７であることが更に好ましく、２．３０～２．９５であることが特に好ましい。 Cellulose acetate using only an acetyl group as the acyl group of cellulose acylate can be preferably used in the present invention. The total acyl substitution degree of this cellulose acetate is 2.00 to 3 from the viewpoint of moisture permeability and optical properties. Is preferably 0.000, more preferably 2.20 to 3.00, still more preferably 2.30 to 3.00, still more preferably 2.30 to 2.97, Particularly preferred is 2.30 to 2.95.
　２種類以上のアシル基を有する混合脂肪酸エステルも本発明におけるセルロースアシレートとして好ましく用いることができる。また、特開２００８－２０８９６号公報の段落００２３～００３８に記載の、脂肪酸アシル基と置換もしくは無置換の芳香族アシル基とを有する混合酸エステルも好ましく用いることができる。なかでも混合脂肪酸エステルのアシル基には、アセチル基と炭素数が３～４のアシル基が含まれることが好ましい。また、混合脂肪酸エステルがアシル基としてアセチル基を含む場合、そのアセチル置換度は２．５未満が好ましく、１．９未満が更に好ましい。一方、炭素数が３～４のアシル基を含む場合の炭素数が３～４のアシル基の置換度は０．１～１．５であることが好ましく、０．２～１．２であることがより好ましく、０．５～１．１であることが特に好ましい。
　本発明に用いるセルロースエステル樹脂層として、後述の共流延法などにより、異なるセルロースアシレートからなる複数層からなる樹脂層を採用することも好ましい。 A mixed fatty acid ester having two or more kinds of acyl groups can also be preferably used as the cellulose acylate in the present invention. Also, mixed acid esters having fatty acid acyl groups and substituted or unsubstituted aromatic acyl groups described in paragraphs 0023 to 0038 of JP-A-2008-20896 can be preferably used. Among them, the acyl group of the mixed fatty acid ester preferably includes an acetyl group and an acyl group having 3 to 4 carbon atoms. When the mixed fatty acid ester contains an acetyl group as an acyl group, the degree of acetyl substitution is preferably less than 2.5 and more preferably less than 1.9. On the other hand, when an acyl group having 3 to 4 carbon atoms is contained, the degree of substitution of the acyl group having 3 to 4 carbon atoms is preferably 0.1 to 1.5, and preferably 0.2 to 1.2. Is more preferable, and 0.5 to 1.1 is particularly preferable.
As the cellulose ester resin layer used in the present invention, it is also preferable to employ a resin layer composed of a plurality of layers composed of different cellulose acylates by a co-casting method described later.
　本発明に用いるセルロースエステルないしセルロースアシレートは、その重合度が２５０～８００が好ましく、３００～６００が更に好ましい。また、本発明に用いるセルロースエステルないしセルロースアシレートは、その数平均分子量が４００００～２３００００が好ましく、６００００～２３００００が更に好ましく、７５０００～２０００００が最も好ましい。重合度は、ゲル浸透クロマトグラフィー（Ｇｅｌ　Ｐｅｒｍｅａｔｉｏｎ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙ；ＧＰＣ）によりポリスチレン換算で測定される数平均分子量をセルロースエステルないしセルロースアシレートのグルコピラノース単位の分子量で除することで求めることができる。 The cellulose ester or cellulose acylate used in the present invention preferably has a degree of polymerization of 250 to 800, more preferably 300 to 600. The number average molecular weight of the cellulose ester or cellulose acylate used in the present invention is preferably 40000 to 230,000, more preferably 60000 to 230,000, and most preferably 75,000 to 200000. The degree of polymerization can be determined by dividing the number average molecular weight measured in terms of polystyrene by gel permeation chromatography (GPC) by the molecular weight of the glucopyranose unit of cellulose ester or cellulose acylate.
　本発明に用いるセルロースエステルは常法により合成することができる。例えばセルロースアシレートであれば、アシル化剤として酸無水物、酸塩化物等を用いて合成できる。上記アシル化剤が酸無水物である場合は、反応溶媒として有機酸（例えば、酢酸）、塩化メチレン等が使用される。また、触媒として、硫酸のようなプロトン性触媒を用いることができる。アシル化剤が酸塩化物である場合は、触媒として塩基性化合物を用いることができる。セルロースアシレートの一般的な工業的生産では、セルロースを目的のアシル基に対応する有機酸（酢酸、プロピオン酸、酪酸等）又はそれらの酸無水物（無水酢酸、無水プロピオン酸、無水酪酸等）を用いてそのヒドロキシ基がエステル化される。
　例えば、綿花リンター又は木材パルプ由来のセルロースを原料とし、これを酢酸等の有機酸で活性化処理した後、硫酸触媒の存在下で、所望の構造の有機酸を用いてエステル化することによりセルロースアシレートを得ることができる。また、アシル化剤として有機酸無水物を用いる場合には、一般にセルロース中に存在するヒドロキシ基の量に対して有機酸無水物を過剰量で使用してセルロースをエステル化する。
　またセルロースアシレートは、例えば、特開平１０－４５８０４号公報に記載された方法により合成することもできる。 The cellulose ester used in the present invention can be synthesized by a conventional method. For example, cellulose acylate can be synthesized using an acid anhydride, acid chloride, or the like as an acylating agent. When the acylating agent is an acid anhydride, an organic acid (for example, acetic acid), methylene chloride, or the like is used as a reaction solvent. Further, a protic catalyst such as sulfuric acid can be used as the catalyst. When the acylating agent is an acid chloride, a basic compound can be used as a catalyst. In general industrial production of cellulose acylate, an organic acid (acetic acid, propionic acid, butyric acid, etc.) corresponding to the desired acyl group or an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride, etc.) of cellulose is used. Is used to esterify the hydroxy group.
For example, a cellulose derived from cotton linter or wood pulp is used as a raw material, and this is activated with an organic acid such as acetic acid and then esterified with an organic acid having a desired structure in the presence of a sulfuric acid catalyst. Acylate can be obtained. When an organic acid anhydride is used as the acylating agent, cellulose is generally esterified using an excess amount of the organic acid anhydride relative to the amount of hydroxy groups present in the cellulose.
Cellulose acylate can also be synthesized, for example, by the method described in JP-A-10-45804.
　また、本発明のセルロースエステル樹脂層中には、本発明の効果を損なわない範囲でセルロースエステルに加えて他の樹脂（例えば（メタ）アクリル樹脂等）を併用して用いることもできる。セルロースエステルフィルム中の上記他の樹脂の含有量は、セルロースエステルフィルム中、４０質量％以下が好ましく、３０質量％以下がより好ましく、２０質量％以下がさらに好ましく、１５質量％以下がさらに好ましく、１０質量％以下がさらに好ましい。 Further, in the cellulose ester resin layer of the present invention, other resins (for example, (meth) acrylic resin etc.) can be used in combination with the cellulose ester within a range not impairing the effects of the present invention. The content of the other resin in the cellulose ester film is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and further preferably 15% by mass or less in the cellulose ester film. 10 mass% or less is still more preferable.
＜セルロースエステル樹脂層の形成＞
　続いて上記セルロースエステル樹脂層の形成について説明する。
　上記セルロースエステル樹脂層の形成は、特に限定されるものではなく、例えば溶融製膜法又は溶液製膜法（ソルベントキャスト法）により形成することが好ましく、添加剤の揮散、分解等を考慮すると溶液製膜法（ソルベントキャスト法）により形成することがより好ましい。ソルベントキャスト法を利用したフィルムの製造例については、米国特許第２，３３６，３１０号、同第２，３６７，６０３号、同第２，４９２，０７８号、同第２，４９２，９７７号、同第２，４９２，９７８号、同第２，６０７，７０４号、同第２，７３９，０６９号及び同第２，７３９，０７０号の各明細書、英国特許第６４０７３１号及び同第７３６８９２号の各明細書、並びに特公昭４５－４５５４号、同４９－５６１４号、特開昭６０－１７６８３４号、同６０－２０３４３０号及び同６２－１１５０３５号等の各公報を参考にすることができる。また、上記セルロースエステル樹脂層は、延伸処理が施されていてもよい。延伸処理の方法及び条件については、例えば、特開昭６２－１１５０３５号、特開平４－１５２１２５号、同４－２８４２１１号、同４－２９８３１０号、同１１－４８２７１号等の各公報を参考にすることができる。 <Formation of cellulose ester resin layer>
Next, the formation of the cellulose ester resin layer will be described.
The formation of the cellulose ester resin layer is not particularly limited. For example, the cellulose ester resin layer is preferably formed by a melt film formation method or a solution film formation method (solvent casting method). More preferably, it is formed by a film forming method (solvent casting method). Examples of film production using the solvent cast method are described in U.S. Pat. Nos. 2,336,310, 2,367,603, 2,492,078, 2,492,977, Nos. 2,492,978, 2,607,704, 2,739,069 and 2,739,070, British Patent Nos. 640731 and 736892 And the Japanese Patent Publications Nos. 45-4554, 49-5614, JP-A-60-176834, JP-A-60-203430, and JP-A-62-115035. Moreover, the said cellulose-ester resin layer may be extended | stretched. For the stretching method and conditions, refer to, for example, JP-A-62-115035, JP-A-4-152125, 4-284221, 4-298310, and 11-48271. can do.
（流延）
　溶液の流延方法としては、調製されたドープを加圧ダイから金属支持体上に均一に押し出す方法、一旦金属等の支持体上に流延されたドープをブレードで膜厚を調節するドクターブレードによる方法、逆回転するロールで調節するリバースロールコーターによる方法等があり、加圧ダイによる方法が好ましい。加圧ダイにはコートハンガータイプ、Ｔダイタイプ等があるが、いずれも好ましく用いることができる。また、ここで挙げた方法以外にも、従来知られているセルロースエステル溶液を流延製膜する種々の方法で実施することができ、用いる溶媒の沸点等の違いを考慮して各条件を設定することができる。 (Casting)
As a method of casting the solution, a method of uniformly extruding the prepared dope from a pressure die onto a metal support, a doctor blade for adjusting the film thickness with a blade of the dope once cast on a support of metal or the like And a method using a reverse roll coater that adjusts with a reversely rotating roll, and a method using a pressure die is preferred. The pressure die includes a coat hanger type and a T die type, and any of them can be preferably used. In addition to the methods listed here, it can be carried out by various known methods for casting a cellulose ester solution, and each condition is set in consideration of differences in the boiling point of the solvent used. can do.
　セルロースエステル樹脂層は単層であっても複層であってもよく、複層とする場合には、共流延法、逐次流延法、塗布法などの積層流延法を用いることが好ましく、特に同時共流延（同時多層共流延ともいう。）法を用いることが、安定製造及び生産コスト低減の観点から特に好ましい。
　共流延法及び逐次流延法によりセルロースエステル樹脂層を製造する場合には、先ず、各層用のセルロースエステル溶液（ドープともいう）を調製し、この溶液を支持体上に流延する。
　共流延法（重層同時流延）では、まず流延用支持体（バンド又はドラム）の上に、各層（３層あるいはそれ以上でもよい）各々の流延用ドープを別々のスリットなどから同時に押出すことができる流延用ダイを用いてドープを押出して、各層同時に流延する。流延後、適当な時間をおいて支持体から剥ぎ取って、乾燥しフィルムを成形する流延法である。共流延ダイを用いることにより、例えば、流延用支持体の上に表層用ドープから形成された表層２層と、これら表層に挟まれたコア層用ドープからなるコア層の計３層を、支持体上に同時に押出して流延することができる。 The cellulose ester resin layer may be a single layer or multiple layers, and in the case of multiple layers, it is preferable to use a lamination casting method such as a co-casting method, a sequential casting method, or a coating method. In particular, the simultaneous co-casting (also referred to as simultaneous multi-layer co-casting) method is particularly preferable from the viewpoint of stable production and production cost reduction.
When producing a cellulose ester resin layer by the co-casting method and the sequential casting method, first, a cellulose ester solution (also referred to as a dope) for each layer is prepared, and this solution is cast on a support.
In the co-casting method (multi-layer simultaneous casting), first, a casting dope for each layer (which may be three layers or more) is simultaneously applied from a separate slit or the like on a casting support (band or drum). The dope is extruded using a casting die that can be extruded, and the layers are cast simultaneously. It is a casting method in which after casting, the film is peeled off from the support after an appropriate time and dried to form a film. By using a co-casting die, for example, a total of three layers: a surface layer two layers formed from a surface layer dope on a casting support, and a core layer composed of a core layer dope sandwiched between these surface layers. It can be extruded and cast simultaneously on a support.
　逐次流延法では、流延用支持体の上に先ず第１層用の流延用ドープを流延用ダイから押出して、流延し、乾燥あるいは乾燥することなく、その上に第２層用の流延用ドープを流延用ダイから押出して流延する要領で、必要なら第３層以上まで逐次ドープを流延・積層して、適当な時間をおいて支持体から剥ぎ取って乾燥し、セルロースエステル樹脂層を形成する。
　また塗布法では、一般的には、コア層を溶液製膜法によりフィルム状に形成し、その表層に、目的のセルロースエステル溶液である塗布液を塗布し、乾燥して、積層構造のセルロースエステル樹脂層を形成する。 In the sequential casting method, the casting dope for the first layer is first extruded from the casting die on the casting support, cast, and dried on the second layer without drying or drying. The dope for casting is extruded from the casting die, and if necessary, the dope is cast and laminated sequentially up to the third layer or more, and peeled off from the support after a suitable time and dried. Then, a cellulose ester resin layer is formed.
In the coating method, generally, a core layer is formed into a film by a solution casting method, and a coating solution that is a target cellulose ester solution is applied to the surface layer, followed by drying to form a cellulose ester having a laminated structure. A resin layer is formed.
（延伸）
　上記セルロースエステル樹脂層は、上記の流延、乾燥後、延伸処理されていることも好ましい。セルロースエステル樹脂層の延伸方向はフィルム搬送方向（ＭＤ(Machine　Direction)方向）と搬送方向に直交する方向（ＴＤ（Transverse　Direction）方向）のいずれでもよい。後に続く偏光板加工プロセスを考慮すると、ＴＤ方向であることが好ましい。延伸処理は２段階以上に分けて複数回行ってもよい。 (Stretching)
The cellulose ester resin layer is preferably stretched after casting and drying. The stretching direction of the cellulose ester resin layer may be either the film transport direction (MD (Machine Direction) direction) or the direction orthogonal to the transport direction (TD (Transverse Direction) direction). Considering the subsequent polarizing plate processing process, the TD direction is preferable. The stretching process may be performed a plurality of times in two or more stages.
　ＴＤ方向に延伸する方法は、例えば、特開昭６２－１１５０３５号、特開平４－１５２１２５号、同４－２８４２１１号、同４－２９８３１０号、同１１－４８２７１号などの各公報に記載されている。ＴＤ方向の延伸の場合、フィルムの巾をテンターで保持しながら搬送して、テンターの巾を徐々に広げることによって延伸することができる。またフィルムの乾燥後に、延伸機を用いて延伸すること（好ましくはロング延伸機を用いる一軸延伸）もできる。
　ＭＤ方向の延伸の場合、例えば、フィルムの搬送ローラーの速度を調節して、フィルムの剥ぎ取り速度よりも巻き取り速度を速くすることで行うことができる。 Methods for stretching in the TD direction are described in, for example, JP-A-62-115035, JP-A-4-152125, JP-A-2842211, JP-A-298310, and JP-A-11-48271. Yes. In the case of stretching in the TD direction, the film can be stretched by conveying the film while holding the film with a tenter and gradually widening the width of the tenter. Further, after the film is dried, it can be stretched using a stretching machine (preferably uniaxial stretching using a long stretching machine).
In the case of stretching in the MD direction, for example, it can be performed by adjusting the speed of the film transport roller to make the winding speed faster than the film peeling speed.
　本発明の積層体を偏光子の保護膜（偏光板保護フィルムとも呼ぶ）として使用する場合には、偏光板を斜めから見たときの光漏れを抑制するため、偏光子の透過軸とセルロースエステル樹脂層の面内の遅相軸を平行に配置する態様が好ましい。連続的に製造されるロールフィルム状の偏光子の透過軸は、一般的に、ロールフィルムの幅方向に平行であるので、上記ロールフィルム状の偏光子とロールフィルム状のセルロースエステル樹脂層からなる保護膜を連続的に貼り合せるためには、ロールフィルム状の保護膜の面内遅相軸は、セルロースエステル樹脂層の幅方向に平行であることが必要となる。従ってＴＤ方向により多く延伸することが好ましい。また延伸処理は、製膜工程の途中で行ってもよいし、製膜して巻き取った原反を延伸処理してもよい。 When the laminate of the present invention is used as a protective film for a polarizer (also referred to as a polarizing plate protective film), in order to suppress light leakage when the polarizing plate is viewed obliquely, the transmission axis of the polarizer and the cellulose ester An embodiment in which slow axes in the plane of the resin layer are arranged in parallel is preferable. Since the transmission axis of the roll film-like polarizer produced continuously is generally parallel to the width direction of the roll film, it is composed of the roll film-like polarizer and the roll film-like cellulose ester resin layer. In order to continuously bond the protective film, the in-plane slow axis of the roll film-shaped protective film needs to be parallel to the width direction of the cellulose ester resin layer. Therefore, it is preferable to stretch more in the TD direction. The stretching process may be performed in the middle of the film forming process, or the original fabric that has been formed and wound may be stretched.
　ＴＤ方向の延伸は５～１００％が好ましく、より好ましくは５～８０％、特に好ましくは５～４０％とする。なお、未延伸の場合、延伸は０％となる。延伸処理は製膜工程の途中で行ってもよいし、製膜して巻き取った原反を延伸処理してもよい。前者の場合には残留溶剤量を含んだ状態で延伸を行ってもよく、残留溶剤量＝（残存揮発分質量／加熱処理後フィルム質量）×１００％が０．０５～５０％の状態で延伸することが好ましい。残留溶剤量が０．０５～５％の状態で５～８０％延伸することがより好ましい。 The stretching in the TD direction is preferably 5 to 100%, more preferably 5 to 80%, and particularly preferably 5 to 40%. In the case of unstretched, the stretching is 0%. The stretching process may be performed in the middle of the film forming process, or the original fabric that has been formed and wound may be stretched. In the former case, stretching may be performed in a state including the residual solvent amount, and the residual solvent amount = (residual volatile matter mass / film mass after heat treatment) × 100% is stretched in a state of 0.05 to 50%. It is preferable to do. It is more preferable to stretch 5 to 80% in a state where the residual solvent amount is 0.05 to 5%.
＜添加剤＞
　上記セルロースエステル樹脂層は、本発明の効果を損なわない範囲で、添加剤を含んでいてもよい。添加剤としては、公知の可塑剤、有機酸、色素、ポリマー、レターデーション調整剤、紫外線吸収剤、酸化防止剤、マット剤などが例示される。これらについては、特開２０１２－１５５２８７号公報の段落番号００６２～００９７の記載を参酌でき、これらの内容は本願明細書に組み込まれる。また、添加剤としては、剥離促進剤、有機酸、多価カルボン酸誘導体を挙げることもできる。これらについては、国際公開第２０１５／００５３９８号段落０２１２～０２１９の記載を参酌でき、これらの内容は本願明細書に組み込まれる。更に、添加剤として、後述する、ラジカル捕捉剤、劣化防止剤又はバルビツール酸化合物なども挙げることができる。
　添加剤の含有量（上記セルロースエステル樹脂層が二種以上の添加剤を含有する場合には、それらの合計含有量）は、セルロースエステル１００質量部に対して５０質量部以下であることが好ましく、３０質量部以下であることがより好ましく、５～３０質量部であることがさらに好ましい。 <Additives>
The cellulose ester resin layer may contain an additive as long as the effects of the present invention are not impaired. Examples of the additive include known plasticizers, organic acids, dyes, polymers, retardation adjusting agents, ultraviolet absorbers, antioxidants, matting agents, and the like. Regarding these, the description of paragraph numbers 0062 to 0097 of JP2012-155287A can be referred to, and the contents thereof are incorporated in the present specification. Examples of the additive include a peeling accelerator, an organic acid, and a polyvalent carboxylic acid derivative. With respect to these, the description of WO2015 / 005398, paragraphs 0212 to 0219 can be referred to, and the contents thereof are incorporated in the present specification. Furthermore, examples of the additive include a radical scavenger, a deterioration inhibitor, and a barbituric acid compound, which will be described later.
The content of the additive (when the cellulose ester resin layer contains two or more additives) is preferably 50 parts by mass or less with respect to 100 parts by mass of the cellulose ester. 30 parts by mass or less, more preferably 5 to 30 parts by mass.
（可塑剤）
　好ましい添加剤の１つとしては、可塑剤を挙げることができる。可塑剤をセルロースエステル樹脂層に添加することにより、セルロースエステル樹脂層の疎水性を高めることができる。この点は、セルロースエステル樹脂層の含水率を低下させる観点から好ましい。このような可塑剤を使用することは、セルロースエステル樹脂層を有する積層体を、偏光板保護フィルムとして用いた場合、湿度に起因する画像表示装置の表示ムラを発生しにくくすることができるため、好ましい。 (Plasticizer)
One preferred additive is a plasticizer. By adding a plasticizer to the cellulose ester resin layer, the hydrophobicity of the cellulose ester resin layer can be increased. This point is preferable from the viewpoint of reducing the water content of the cellulose ester resin layer. The use of such a plasticizer can reduce the occurrence of display unevenness of the image display device due to humidity when the laminate having a cellulose ester resin layer is used as a polarizing plate protective film. preferable.
　可塑剤の分子量は、添加することによる上記効果を良好に得る観点からは、３０００以下であることが好ましく、１５００以下であることがより好ましく、１０００以下であることが更に好ましい。また、可塑剤の分子量は、低揮散性の観点からは、例えば３００以上であり、好ましくは３５０以上である。なお多量体の可塑剤については、分子量とは、数平均分子量をいうものとする。 The molecular weight of the plasticizer is preferably 3000 or less, more preferably 1500 or less, and still more preferably 1000 or less, from the viewpoint of obtaining the above-described effect by adding it satisfactorily. The molecular weight of the plasticizer is, for example, 300 or more, preferably 350 or more, from the viewpoint of low volatility. In the case of multimeric plasticizers, the molecular weight is the number average molecular weight.
　可塑剤としては、多価アルコールの多価エステル化合物（以下、「多価アルコールエステル可塑剤」とも記載する。）、重縮合エステル化合物（以下、「重縮合エステル可塑剤」とも記載する。）、炭水化物化合物（以下、「炭水化物誘導体可塑剤」とも記載する。）を挙げることができる。多価アルコールエステル可塑剤については、国際公開第２０１５／００５３９８号段落００８１～００９８、重縮合エステル可塑剤については、同公報段落００９９～０１２２、炭水化物誘導体可塑剤については、同公報段落０１２３～０１４０を参照でき、これらの内容は本願明細書に組み込まれる。これらの可塑剤の含有量は、可塑剤の添加効果と可塑剤の析出抑制とを両立する観点から、可塑剤を添加する層の樹脂（セルロースエステル）１００質量部に対して１～２０質量部とすることが好ましく、２～１５質量部とすることがより好ましく、５～１５質量部とすることが更に好ましい。
　なお、これらの可塑剤は２種類以上添加してもよい。２種類以上添加する場合も、添加量の具体例および好ましい範囲は上記と同一である。 As the plasticizer, a polyhydric ester compound of polyhydric alcohol (hereinafter also referred to as “polyhydric alcohol ester plasticizer”), a polycondensed ester compound (hereinafter also referred to as “polycondensed ester plasticizer”), And carbohydrate compounds (hereinafter also referred to as “carbohydrate derivative plasticizers”). For polyhydric alcohol ester plasticizers, WO2015 / 005398 paragraphs 0081 to 0098, for polycondensed ester plasticizers, paragraphs 00099 to 0122, and for carbohydrate derivative plasticizers, paragraphs 0123 to 0140. The contents of which are hereby incorporated by reference. The content of these plasticizers is 1 to 20 parts by mass with respect to 100 parts by mass of the resin (cellulose ester) of the layer to which the plasticizer is added from the viewpoint of achieving both the effect of adding the plasticizer and suppressing the precipitation of the plasticizer. Preferably, the content is 2 to 15 parts by mass, more preferably 5 to 15 parts by mass.
Two or more kinds of these plasticizers may be added. Also when adding 2 or more types, the specific example and preferable range of addition amount are the same as the above.
（酸化防止剤）
　好ましい添加剤の１つとしては、酸化防止剤を挙げることもできる。酸化防止剤については、国際公開第２０１５／００５３９８号段落０１４３～０１６５の記載も参酌でき、これらの内容は本願明細書に組み込まれる。 (Antioxidant)
One preferable additive may include an antioxidant. Regarding the antioxidant, the description of WO 2015/005398, paragraphs 0143 to 0165 can be referred to, and the contents thereof are incorporated in the present specification.
（ラジカル捕捉剤）
　好ましい添加剤の１つとしては、ラジカル補捉剤を挙げることもできる。ラジカル補捉剤については、国際公開第２０１５／００５３９８号段落０１６６～０１９９の記載を参酌でき、これらの内容は本願明細書に組み込まれる。 (Radical scavenger)
One preferred additive may include a radical scavenger. Regarding the radical scavenger, reference can be made to the description of WO 2015/005398, paragraphs 0166 to 0199, the contents of which are incorporated herein.
（劣化防止剤）
　好ましい添加剤の１つとしては、劣化防止剤を挙げることもできる。劣化防止剤については、国際公開第２０１５／００５３９８号段落０２０５～０２０６の記載を参酌でき、これらの内容は本願明細書に組み込まれる。 (Deterioration inhibitor)
As one of preferable additives, a deterioration preventing agent can be mentioned. Regarding the deterioration preventing agent, the description in WO2015 / 005398 paragraphs 0205 to 0206 can be referred to, and the contents thereof are incorporated in the present specification.
（バルビツール酸化合物）
　上記セルロースエステル樹脂層は、バルビツール酸構造を有する化合物（バルビツール酸化合物）を含有することもできる。バルビツール酸化合物は、この化合物を添加することにより、セルロースエステル樹脂層に各種機能を発現させることができる化合物である。例えば、バルビツール酸化合物は、セルロースエステル樹脂層の硬度向上に有効である。また、バルビツール酸化合物は、この化合物を含むセルロースエステル樹脂層を備えた偏光板の光、熱、湿度等に対する耐久性の改良にも有効である。上記セルロースエステル樹脂層に添加可能なバルビツール酸化合物については、例えば国際公開第２０１５／００５３９８号段落００２９～００６０段落の記載を参酌でき、これらの内容は本願明細書に組み込まれる。 (Barbituric acid compound)
The cellulose ester resin layer can also contain a compound having a barbituric acid structure (barbituric acid compound). A barbituric acid compound is a compound which can express various functions in a cellulose-ester resin layer by adding this compound. For example, the barbituric acid compound is effective for improving the hardness of the cellulose ester resin layer. The barbituric acid compound is also effective in improving the durability against light, heat, humidity and the like of a polarizing plate provided with a cellulose ester resin layer containing this compound. With respect to the barbituric acid compound that can be added to the cellulose ester resin layer, for example, the description in paragraphs 0029 to 0060 of WO 2015/005398 can be referred to, and the contents thereof are incorporated in the present specification.
＜鹸化処理＞
　上記セルロースエステル樹脂層は、アルカリ鹸化処理することにより、ポリビニルアルコールのような偏光子の材料との密着性を高めることができる。
　鹸化の方法については、特開２００７－８６７４８号公報の段落番号０２１１及び段落番号０２１２に記載されている方法を用いることができる。 <Saponification treatment>
The cellulose ester resin layer can be improved in adhesion to a polarizer material such as polyvinyl alcohol by alkali saponification treatment.
As the saponification method, the method described in paragraph No. 0211 and paragraph No. 0212 of JP-A-2007-86748 can be used.
　例えば、セルロースエステル樹脂層に対するアルカリ鹸化処理は、フィルム表面をアルカリ溶液に浸漬した後、酸性溶液で中和し、水洗して乾燥するサイクルで行われることが好ましい。アルカリ溶液としては、水酸化カリウム溶液、水酸化ナトリウム溶液が挙げられる。水酸化イオンの濃度は０．１～５．０モル／Ｌの範囲が好ましく、０．５～４．０モル／Ｌの範囲がさらに好ましい。アルカリ溶液温度は、室温～９０℃の範囲が好ましく、４０～７０℃の範囲がさらに好ましい。 For example, the alkali saponification treatment for the cellulose ester resin layer is preferably performed in a cycle in which the film surface is immersed in an alkali solution, neutralized with an acidic solution, washed with water and dried. Examples of the alkaline solution include potassium hydroxide solution and sodium hydroxide solution. The concentration of hydroxide ions is preferably in the range of 0.1 to 5.0 mol / L, more preferably in the range of 0.5 to 4.0 mol / L. The alkaline solution temperature is preferably in the range of room temperature to 90 ° C, more preferably in the range of 40 to 70 ° C.
　アルカリ鹸化処理の代わりに、特開平６－９４９１５号公報、特開平６－１１８２３２号公報に記載されているような易接着加工を施してもよい。 Instead of the alkali saponification treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed.
　上記セルロースエステル樹脂層の膜厚は、１～８０μｍが好ましく、１～６０μｍがより好ましく、３～６０μｍがさらに好ましい。また上記セルロースエステル樹脂層の膜厚は、１０～６０μｍであることも好ましく、２０～６０μｍであることも好ましく、２０～５０μｍであることも好ましい。 The film thickness of the cellulose ester resin layer is preferably 1 to 80 μm, more preferably 1 to 60 μm, and further preferably 3 to 60 μm. The film thickness of the cellulose ester resin layer is preferably 10 to 60 μm, more preferably 20 to 60 μm, and also preferably 20 to 50 μm.
［積層体の製造方法］
　本発明の積層体の製造方法について説明する。
　本発明の積層体の製造方法は、特に限定されるものではなく、公知の方法を採用することができる。溶融製膜法、溶液製膜法（ソルベントキャスト法）の他、セルロースエステル樹脂層を作製した後、各種公知の塗布方法によりポリマー（Ｓ）を含む層を形成し、これを乾燥して積層体を製造することもできる。上記塗布方法としては特に制限はないが、マイクログラビア塗工方式を好ましく用いることができる。なお、いずれの塗布方法を用いた場合であっても、上記モノマーを、適宜の溶媒に適宜の濃度で溶解したものであれば、塗布液は特に限定されず、塗工条件及び成膜条件も特に限定されない。
　なお、量産適性の観点から、溶融製膜法、溶液製膜法（ソルベントキャスト法）により製膜することができる。溶融製膜法としては、Ｔ－ダイ法などの製造法を用いることが好ましく、特に同時共押し出し法を用いることが好ましい。溶液製膜法としては、上記共流延法、逐次流延法、塗布法などの積層流延法を用いることが好ましく、特に同時共流延（同時多層共流延ともいう。）法を用いることが、安定製造及び生産コスト低減の観点から特に好ましい。 [Manufacturing method of laminate]
The manufacturing method of the laminated body of this invention is demonstrated.
The manufacturing method of the laminated body of this invention is not specifically limited, A well-known method is employable. In addition to the melt film forming method and the solution film forming method (solvent cast method), after preparing the cellulose ester resin layer, a layer containing the polymer (S) is formed by various known coating methods, and this is dried to obtain a laminate. Can also be manufactured. Although there is no restriction | limiting in particular as said application | coating method, A micro gravure coating system can be used preferably. In any case, any coating method may be used as long as the monomer is dissolved in an appropriate solvent at an appropriate concentration. There is no particular limitation.
In addition, from the viewpoint of suitability for mass production, the film can be formed by a melt film forming method or a solution film forming method (solvent casting method). As the melt film forming method, it is preferable to use a manufacturing method such as a T-die method, and it is particularly preferable to use a simultaneous coextrusion method. As the solution casting method, it is preferable to use a lamination casting method such as the above-mentioned co-casting method, sequential casting method, coating method or the like, and particularly a simultaneous co-casting method (also referred to as simultaneous multi-layer co-casting) method is used. Is particularly preferable from the viewpoints of stable production and production cost reduction.
　本発明の積層体は、積層体中、上記ポリマー（Ｓ）の含有量が１～３０質量％であることが好ましく、５～２８質量％がより好ましく、８～２５質量％がさらに好ましい。積層体中の上記ポリマー（Ｓ）の含有量を上記好ましい範囲内とすることにより、層間密着性をより高めることができる。 In the laminate of the present invention, the content of the polymer (S) in the laminate is preferably 1 to 30% by mass, more preferably 5 to 28% by mass, and further preferably 8 to 25% by mass. By setting the content of the polymer (S) in the laminate within the preferred range, interlayer adhesion can be further improved.
＜積層体の物性値＞
（ヘイズ値）
　本発明の積層体は、全ヘイズ値が２．００％以下であることが好ましい。全ヘイズ値が２．００％以下であると、積層体の透明性が高く、液晶表示装置のコントラスト比、輝度向上等に効果がある。全ヘイズ値は、１．００％以下がより好ましく、０．５０％以下であることが更に好ましく、０．３０％以下が特に好ましく、０．２０％以下が最も好ましい。全ヘイズ値は低いほど光学的性能が優れるが原料選択、製造管理、ロールフィルムのハンドリング性等も考慮すると０．０１％以上であることが好ましい。
　本発明の積層体の内部ヘイズ値は、１．００％以下であることが好ましい。内部ヘイズ値を１．００％以下とすることで、液晶表示装置のコントラスト比を向上させ、優れた表示特性を実現することができる。内部ヘイズ値は、０．５０％以下がより好ましく、０．２０％以下が更に好ましく、０．１０％以下が特に好ましく、０．０５％以下が最も好ましい。原料選択、製造管理等の観点からは０．０１％以上であることが好ましい。
　本発明の積層体としては、特に、全ヘイズ値が０．３０％以下であり、内部ヘイズ値が０．１０％以下であることが好ましい。
　全ヘイズ値及び内部ヘイズ値は、フィルム材料の種類、添加量、添加剤の選択（特に、マット剤粒子の粒径、屈折率、添加量）、更にはフィルム製造条件（延伸時の温度や延伸倍率など）等により調整することができる。
　なおヘイズ値の測定は、フィルム試料４０ｍｍ×８０ｍｍを、２５℃、相対湿度６０％で、ヘイズメーター（ＨＧＭ－２ＤＰ、スガ試験機）で、ＪＩＳ　Ｋ－７１３６（２０００）に従って測定することができる。 <Physical properties of the laminate>
(Haze value)
The laminate of the present invention preferably has a total haze value of 2.00% or less. When the total haze value is 2.00% or less, the laminate has high transparency, and is effective in improving the contrast ratio and brightness of the liquid crystal display device. The total haze value is more preferably 1.00% or less, further preferably 0.50% or less, particularly preferably 0.30% or less, and most preferably 0.20% or less. The lower the total haze value, the better the optical performance, but it is preferably 0.01% or more considering raw material selection, production control, roll film handling properties, and the like.
The internal haze value of the laminate of the present invention is preferably 1.00% or less. By setting the internal haze value to 1.00% or less, the contrast ratio of the liquid crystal display device can be improved and excellent display characteristics can be realized. The internal haze value is more preferably 0.50% or less, further preferably 0.20% or less, particularly preferably 0.10% or less, and most preferably 0.05% or less. From the viewpoint of raw material selection, production control, etc., 0.01% or more is preferable.
In particular, the laminate of the present invention preferably has a total haze value of 0.30% or less and an internal haze value of 0.10% or less.
Total haze value and internal haze value are the type of film material, amount added, selection of additives (particularly, particle size, refractive index, amount added), and film production conditions (stretching temperature and stretching) The magnification can be adjusted.
The haze value can be measured on a film sample of 40 mm × 80 mm at 25 ° C. and a relative humidity of 60% with a haze meter (HGM-2DP, Suga Test Machine) according to JIS K-7136 (2000).
（膜厚）
　本発明の積層体の膜厚は、用途に応じ適宜定めることができるが、例えば、５～１００μｍとすることができる。５μｍ以上とすることにより、ウェブ状のフィルムを作製する際のハンドリング性が向上し好ましい。また、１００μｍ以下とすることにより、湿度変化に対応しやすく、光学特性を維持しやすくなる。積層体の膜厚は、８～８０μｍがより好ましく、１０～７０μｍが更に好ましい。 (Film thickness)
The film thickness of the laminate of the present invention can be appropriately determined according to the application, but can be set to, for example, 5 to 100 μm. When the thickness is 5 μm or more, the handling property when producing a web-like film is improved, which is preferable. Moreover, by setting it as 100 micrometers or less, it becomes easy to respond to a humidity change and it becomes easy to maintain an optical characteristic. The film thickness of the laminate is more preferably 8 to 80 μm, still more preferably 10 to 70 μm.
（透湿度）
　上記積層体の透湿度は、ＪＩＳ　Ｚ－０２０８をもとに、４０℃、相対湿度９０％の条件において測定される。
　本発明の積層体の透湿度は、１６００ｇ／ｍ２／ｄａｙ（２４時間）以下であることが好ましく、１０００ｇ／ｍ２／ｄａｙ以下であることがより好ましく、６００ｇ／ｍ２／ｄａｙ以下であることがさらに好ましく、２００ｇ／ｍ２／ｄａｙ以下であることが特に好ましい。積層体の透湿度を上記範囲に制御することで、本発明の積層体を搭載した液晶表示装置の常温、高湿及び高温高湿環境経時後の、液晶セルの反りや、黒表示時の表示ムラを抑制できる。 (Moisture permeability)
The moisture permeability of the laminate is measured under the conditions of 40 ° C. and relative humidity 90% based on JIS Z-0208.
The moisture permeability of the laminate of the present invention is preferably 1600 g / m 2 / day (24 hours) or less, more preferably 1000 g / m 2 / day or less, and 600 g / m 2 / day or less. More preferably, it is particularly preferably 200 g / m 2 / day or less. By controlling the moisture permeability of the laminated body within the above range, the liquid crystal display device mounted with the laminated body of the present invention is warped or displayed during black display after normal temperature, high humidity and high temperature and high humidity environments. Unevenness can be suppressed.
（含水率）
　上記積層体の含水率（平衡含水率）は、偏光板の保護フィルムとして用いる際、ポリビニルアルコールなどの親水性熱可塑性樹脂との接着性を損なわないために、膜厚に関わらず、２５℃、相対湿度８０％における含水率が、０～４．０質量％であることが好ましい。０～２．５質量％であることがより好ましく、０～１．５質量％であることが更に好ましい。平衡含水率が４．０質量％以下であれば、レターデーションの湿度変化による依存性が大きくなり過ぎず、液晶表示装置の常温、高湿及び高温高湿環境経時後の黒表示時の表示ムラを抑止の点からも好ましい。
　含水率の測定法は、フィルム試料７ｍｍ×３５ｍｍを水分測定器、試料乾燥装置「ＣＡ－０３」及び「ＶＡ－０５」（共に三菱化学（株）製）を用いてカールフィッシャー法で測定することができる。含水率は水分量（ｇ）を試料質量（ｇ）で除して算出できる。 (Moisture content)
The moisture content of the laminate (equilibrium moisture content) is 25 ° C., regardless of the film thickness, so as not to impair the adhesion with a hydrophilic thermoplastic resin such as polyvinyl alcohol when used as a protective film for a polarizing plate. The water content at a relative humidity of 80% is preferably 0 to 4.0% by mass. The content is more preferably 0 to 2.5% by mass, and still more preferably 0 to 1.5% by mass. If the equilibrium moisture content is 4.0% by mass or less, the dependence of retardation on humidity changes does not become too large, and the display unevenness of the liquid crystal display device during black display after aging at room temperature, high humidity, and high temperature and high humidity. Is also preferred from the standpoint of deterrence.
The moisture content is measured by measuring the film sample 7 mm x 35 mm by the Karl Fischer method using a moisture meter and sample drying devices “CA-03” and “VA-05” (both manufactured by Mitsubishi Chemical Corporation). Can do. The moisture content can be calculated by dividing the moisture content (g) by the sample mass (g).
［偏光板］
　本発明の偏光板は、偏光子と、この偏光子の保護フィルムとして本発明の積層体を少なくとも１枚含む。 [Polarizer]
The polarizing plate of the present invention includes a polarizer and at least one laminate of the present invention as a protective film for the polarizer.
　偏光子としては、例えば、ポリビニルアルコールフィルムをヨウ素溶液中に浸漬して延伸したもの等を用いることができる。ポリビニルアルコールフィルムをヨウ素溶液中に浸漬して延伸した偏光子を用いる場合、例えば、接着剤を用いて偏光子の少なくとも一方の面に、上記積層体におけるセルロースエステル樹脂層の鹸化処理面を貼り合わせることができる。上記接着剤としては、ポリビニルアルコール又はポリビニルアセタール（例えば、ポリビニルブチラール）の水溶液、ビニル系ポリマー（例えば、ポリブチルアクリレート）のラテックス、紫外線硬化型の接着剤を用いることができる。特に好ましい接着剤は、紫外線硬化型の接着剤または完全鹸化ポリビニルアルコールの水溶液である。 As the polarizer, for example, a film obtained by immersing and stretching a polyvinyl alcohol film in an iodine solution can be used. When using a polarizer obtained by immersing and stretching a polyvinyl alcohol film in an iodine solution, for example, the saponification surface of the cellulose ester resin layer in the laminate is bonded to at least one surface of the polarizer using an adhesive. be able to. Examples of the adhesive include an aqueous solution of polyvinyl alcohol or polyvinyl acetal (for example, polyvinyl butyral), a latex of a vinyl-based polymer (for example, polybutyl acrylate), and an ultraviolet curable adhesive. Particularly preferred adhesives are UV curable adhesives or aqueous solutions of fully saponified polyvinyl alcohol.
　本発明の偏光板の作製方法は特に限定されず、一般的な方法に準じて作製することができる。例えば、本発明の積層体をアルカリ処理し、ポリビニルアルコールフィルムを沃素溶液中に浸漬延伸して作製した偏光子の両面に完全ケン化ポリビニルアルコール水溶液を用いて貼り合わせる方法がある。アルカリ処理の代わりに特開平６－９４９１５号、特開平６－１１８２３２号に記載されているような易接着加工を施してもよい。また前述のような表面処理を行ってもよい。
　積層体がセルロースエステル樹脂層の片面に上記ポリマー層が設けられた形態である場合、上記積層体の偏光子との貼合面は、上記ポリマー層の側でもよいし、セルロースエステル樹脂層の側でも良い。偏光子からの色素の吸収を抑える観点からは、上記ポリマー層の側を偏光子と貼り合わせることが好ましい。 The production method of the polarizing plate of the present invention is not particularly limited, and can be produced according to a general method. For example, there is a method in which the laminate of the present invention is treated with an alkali and bonded to both surfaces of a polarizer produced by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed. Further, the surface treatment as described above may be performed.
When the laminate is in the form in which the polymer layer is provided on one side of the cellulose ester resin layer, the laminate surface of the laminate with the polarizer may be on the polymer layer side or on the cellulose ester resin layer side. But it ’s okay. From the viewpoint of suppressing the absorption of the dye from the polarizer, the polymer layer side is preferably bonded to the polarizer.
　本発明の積層体の偏光子への貼り合せは、偏光子の透過軸と本発明の積層体の遅相軸が平行、直交又は４５°となるように貼り合せることが好ましい。遅相軸の測定は、公知の種々の方法で測定することができ、例えば、複屈折計（ＫＯＢＲＡＤＨ、王子計測機器（株）製）を用いて行うことができる。
　ここで、平行、直交又は４５°については、本発明が属する技術分野において許容される誤差の範囲を含む。例えば、それぞれ平行、直交及び４５°に関する厳密な角度から±１０°の範囲内であることを意味し、厳密な角度との誤差は、±５°の範囲内が好ましく、±３°の範囲内がより好ましい。
　偏光子の透過軸と本発明の積層体の遅相軸についての平行とは、本発明の積層体の主屈折率ｎｘの方向と偏光子の透過軸の方向とが±１０°の角度で交わっていることを意味する。この角度は、±５°の範囲内が好ましく、より好ましくは±３°の範囲内、さらに好ましくは±１°の範囲内、最も好ましくは±０．５°の範囲内である。
　また、偏光子の透過軸と本発明の積層体の遅相軸についての直交とは、本発明の積層体の主屈折率ｎｘの方向と偏光子の透過軸の方向とが９０°±１０°の範囲内の角度で交わっていることを意味する。この角度は、好ましくは９０°±５°の範囲内、より好ましくは９０°±３°の範囲内、さらに好ましくは９０°±１°の範囲内、最も好ましくは９０°±０．１°の範囲内である。上述のような範囲であれば、偏光板クロスニコル下における偏光度性能の低下が抑制され、光抜けが低減され好ましい。 The lamination of the laminate of the present invention is preferably bonded to the polarizer so that the transmission axis of the polarizer and the slow axis of the laminate of the present invention are parallel, orthogonal or 45 °. The slow axis can be measured by various known methods, for example, using a birefringence meter (KOBRADH, manufactured by Oji Scientific Instruments).
Here, parallel, orthogonal, or 45 ° includes a range of errors allowed in the technical field to which the present invention belongs. For example, it means that it is within the range of ± 10 ° from the strict angle with respect to parallel, orthogonal and 45 °, respectively, and the error from the strict angle is preferably within the range of ± 5 °, and within the range of ± 3 ° Is more preferable.
The parallel of the transmission axis of the polarizer and the slow axis of the laminate of the present invention means that the direction of the main refractive index nx of the laminate of the present invention and the direction of the transmission axis of the polarizer intersect at an angle of ± 10 °. Means that This angle is preferably within a range of ± 5 °, more preferably within a range of ± 3 °, further preferably within a range of ± 1 °, and most preferably within a range of ± 0.5 °.
Further, the orthogonality of the transmission axis of the polarizer and the slow axis of the laminate of the present invention means that the direction of the main refractive index nx of the laminate of the present invention and the direction of the transmission axis of the polarizer are 90 ° ± 10 °. It means that they intersect at an angle within the range of. This angle is preferably in the range of 90 ° ± 5 °, more preferably in the range of 90 ° ± 3 °, even more preferably in the range of 90 ° ± 1 °, most preferably 90 ° ± 0.1 °. Within range. If it is the above ranges, the fall of the polarization degree performance under polarizing plate cross Nicol will be suppressed, and light omission is reduced and it is preferable.
　偏光板は偏光子及びその両面を保護する保護フィルムで構成されており、保護フィルムの少なくとも１枚を、本発明の積層体とすることが好ましい。更に通常は、この偏光板の一方の面にプロテクトフィルムを、反対面にセパレートフィルムを貼合して構成される。プロテクトフィルム及びセパレートフィルムは偏光板出荷時、製品検査時等において偏光板を保護する目的で用いられる。この場合、プロテクトフィルムは、偏光板の表面を保護する目的で貼合され、偏光板を液晶板へ貼合する面の反対面側に用いられる。又、セパレートフィルムは液晶板へ貼合する接着層をカバーする目的で用いられ、偏光板を液晶板へ貼合する面側に用いられる。 The polarizing plate is composed of a polarizer and protective films protecting both surfaces thereof, and at least one of the protective films is preferably a laminate of the present invention. Further, usually, a protective film is bonded to one surface of the polarizing plate, and a separate film is bonded to the other surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the adhesive layer bonded to a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal plate.
＜偏光度＞
　本発明の偏光板は、偏光度が９５．０％以上が好ましく、９８．０％以上がより好ましく、最も好ましくは９９．５％以上である。 <Degree of polarization>
In the polarizing plate of the present invention, the degree of polarization is preferably 95.0% or more, more preferably 98.0% or more, and most preferably 99.5% or more.
　本発明において、偏光板の偏光度は、日本分光（株）製自動偏光フィルム測定装置ＶＡＰ－７０７０を用いて測定することができる。より詳細には、波長３８０ｎｍ～７００ｎｍで測定した直交透過率及び平行透過率から以下の式により偏光度スペクトルを算出し、さらに光源（補助イルミナントＣ）とＣＩＥ視感度（Ｙ）の重み付け平均を計算することにより求めることができる。 In the present invention, the degree of polarization of the polarizing plate can be measured using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation. More specifically, the polarization degree spectrum is calculated from the orthogonal transmittance and the parallel transmittance measured at wavelengths of 380 nm to 700 nm by the following formula, and the weighted average of the light source (auxiliary illuminant C) and the CIE visibility (Y) is calculated. Can be obtained.
　偏光度（％）
　＝｛（平行透過率－直交透過率）／（平行透過率＋直交透過率）｝１／２×１００ Polarization degree (%)
= {(Parallel transmittance−orthogonal transmittance) / (parallel transmittance + orthogonal transmittance)} 1/2 × 100
＜偏光度変化量＞
　本発明の偏光板は、湿熱経時条件下における耐久性に優れる。このため、後述する偏光板耐久性試験前後での偏光度の変化量は小さい。
　本発明の偏光板は、日本分光（株）製自動偏光フィルム測定装置ＶＡＰ－７０７０を用いて直交透過率及び平行透過率を測定し、上記式により偏光度を算出し、特に、８５℃、相対湿度８５％の環境下で５００時間保存した場合の偏光度変化量が５％未満であるのが好ましい。 <Change in polarization degree>
The polarizing plate of the present invention is excellent in durability under wet heat aging conditions. For this reason, the amount of change in the degree of polarization before and after the polarizing plate durability test described later is small.
The polarizing plate of the present invention was measured for orthogonal transmittance and parallel transmittance using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation, and the degree of polarization was calculated by the above formula. It is preferable that the amount of change in polarization degree is less than 5% when stored in an environment of 85% humidity for 500 hours.
＜その他の特性＞
　本発明の偏光板のその他の好ましい光学特性等については特開２００７－０８６７４８号公報の段落番号０２３８～０２５５に記載されており、これらの特性を満たすことが好ましい。 <Other characteristics>
Other preferable optical characteristics of the polarizing plate of the present invention are described in paragraph Nos. 0238 to 0255 of JP-A-2007-086748, and it is preferable that these characteristics are satisfied.
［画像表示装置］
　本発明の偏光板は画像表示装置用途として好ましく用いられる。かかる画像表示装置として、液晶表示装置、有機エレクトロルミネッセンス表示装置等が挙げられる。有機エレクトロルミネッセンス表示装置に用いる場合、例えば反射防止用途に用いられる。なかでも本発明の偏光板は液晶表示装置に好適に用いられる。
＜液晶表示装置＞
　本発明の画像表示装置としての一実施形態である液晶表示装置は、液晶セルと、この液晶セルの少なくとも一方に配置された本発明の偏光板とを含む。 [Image display device]
The polarizing plate of the present invention is preferably used for an image display device. Examples of such an image display device include a liquid crystal display device and an organic electroluminescence display device. When used for an organic electroluminescence display device, for example, it is used for antireflection applications. Especially, the polarizing plate of this invention is used suitably for a liquid crystal display device.
<Liquid crystal display device>
The liquid crystal display device which is one embodiment as the image display device of the present invention includes a liquid crystal cell and the polarizing plate of the present invention disposed in at least one of the liquid crystal cells.
　上記液晶表示装置の好ましい実施形態について説明する。
　図２は、上記液晶表示装置の一実施形態を示す概略図である。図２において、液晶表示装置２０は、液晶層２４とこの上下に配置された液晶セル上電極基板２３及び液晶セル下電極基板２５とを有する液晶セル、液晶セルの両側に配置された上側偏光板２１及び下側偏光板２６からなる。液晶セルと各偏光板との間にカラーフィルターを配置してもよい。液晶表示装置２０を透過型として使用する場合は、冷陰極あるいは熱陰極蛍光管、あるいは発光ダイオード、フィールドエミッション素子、エレクトロルミネッセント素子を光源とするバックライトを背面に配置する。液晶セルの基板は、一般に５０μｍ～２ｍｍの厚さを有する。 A preferred embodiment of the liquid crystal display device will be described.
FIG. 2 is a schematic view showing an embodiment of the liquid crystal display device. In FIG. 2, the liquid crystal display device 20 includes a liquid crystal cell having a liquid crystal layer 24 and a liquid crystal cell upper electrode substrate 23 and a liquid crystal cell lower electrode substrate 25 disposed above and below, and upper polarizing plates disposed on both sides of the liquid crystal cell. 21 and the lower polarizing plate 26. A color filter may be disposed between the liquid crystal cell and each polarizing plate. When the liquid crystal display device 20 is used as a transmission type, a cold cathode or hot cathode fluorescent tube, or a backlight having a light emitting diode, field emission element, or electroluminescent element as a light source is disposed on the back surface. The substrate of the liquid crystal cell generally has a thickness of 50 μm to 2 mm.
　上側偏光板２１及び下側偏光板２６は、通常は、それぞれ２枚の偏光板保護フィルムで偏光子を挟むように積層した構成を有している。本発明の液晶表示装置２０は、少なくとも一方の偏光板が本発明の偏光板であることが好ましい。本発明の液晶表示装置２０が備える偏光板２１及び２６は、装置の外側（液晶セルから遠い側）から順に、偏光板保護フィルムとしての本発明の積層体、偏光子、一般の透明保護フィルムの順序で各層が積層された形態が好ましい。また、上記一般の透明保護フィルムに代えて、本発明の積層板を位相差フィルムとして用いた形態も好ましい。
　液晶セルの基板は、一般に５０μｍ～２ｍｍの厚さを有する。 The upper polarizing plate 21 and the lower polarizing plate 26 usually have a configuration in which a polarizer is sandwiched between two polarizing plate protective films. In the liquid crystal display device 20 of the present invention, it is preferable that at least one polarizing plate is the polarizing plate of the present invention. The polarizing plates 21 and 26 included in the liquid crystal display device 20 of the present invention are the laminate of the present invention as a polarizing plate protective film, a polarizer, and a general transparent protective film in order from the outside of the device (the side far from the liquid crystal cell). A form in which each layer is laminated in order is preferable. Moreover, it replaces with the said general transparent protective film, and the form which used the laminated board of this invention as a phase difference film is also preferable.
The substrate of the liquid crystal cell generally has a thickness of 50 μm to 2 mm.
（液晶表示装置の種類）
　本発明のセルロースエステルフィルムは、様々な表示モードの液晶セルに用いることができる。ＴＮ（Ｔｗｉｓｔｅｄ Ｎｅｍａｔｉｃ）、ＩＰＳ（Ｉｎ－ＰｌａｎｅＳｗｉｔｃｈｉｎｇ）、ＦＬＣ（Ｆｅｒｒｏｅｌｅｃｔｒｉｃ　Ｌｉｑｕｉｄ Ｃｒｙｓｔａｌ）、ＡＦＬＣ（Ａｎｔｉ－ｆｅｒｒｏｅｌｅｃｔｒｉｃＬｉｑｕｉｄ　Ｃｒｙｓｔａｌ）、ＯＣＢ（Ｏｐｔｉｃａｌｌｙ　Ｃｏｍｐｅｎｓａｔｏｒｙ　Ｂｅｎｄ）、ＳＴＮ（Ｓｕｐｅｒ　Ｔｗｉｓｔｅｄ　Ｎｅｍａｔｉｃ）、ＶＡ（Ｖｅｒｔｉｃａｌｌｙ　Ａｌｉｇｎｅｄ）、ＥＣＢ（Ｅｌｅｃｔｒｉｃａｌｌｙ　Ｃｏｎｔｒｏｌｌｅｄ　Ｂｉｒｅｆｒｉｎｇｅｎｃｅ）、及びＨＡＮ（Ｈｙｂｒｉｄ　Ａｌｉｇｎｅｄ　Ｎｅｍａｔｉｃ）のような様々な表示モードが提案されている。また、上記表示モードを配向分割した表示モードも提案されている。本発明のセルロースエステルは、いずれの表示モードの液晶表示装置にも好適に用いることができる。また、透過型、反射型、半透過型のいずれの液晶表示装置にも好適に用いることができる。 (Types of liquid crystal display devices)
The cellulose ester film of the present invention can be used for liquid crystal cells in various display modes. TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-Frequency Liquid Crystal), OCB (Optically Charged Compensated). Various display modes have been proposed, such as Electrically Controlled Birefringence (HAN) and Hybrid Aligned Nematic (HAN). In addition, a display mode in which the above display mode is oriented and divided has been proposed. The cellulose ester of the present invention can be suitably used for a liquid crystal display device in any display mode. Further, it can be suitably used for any liquid crystal display device of a transmissive type, a reflective type, and a transflective type.
　本発明を実施例に基づきさらに詳細に説明するが、本発明は下記実施例に限定されるものではない。 The present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.
［合成例］
＜合成例１：ポリマーＰ－１の合成＞
　（２－ヒドロキシメチル）アクリル酸エチル（東京化成株式会社製）２０ｇ、フェニルイソシアネート（東京化成株式会社製）１９．２ｇ、反応溶媒として酢酸ブチル１００ミリリットル、触媒としてオクチルスズ系化合物（商品名：ネオスタンＵ－８３０、日東化成株式会社製、）７０ｍｇを３００ミリリットルフラスコに量り取り、窒素雰囲気下、反応容器内部を９０℃まで昇温させて反応させた。反応終了後、反応液を濃縮し、残渣をシリカゲルカラムクロマトグラフィーにより精製し、モノマーＭ－２（繰り返し単位Ａ－２を導くモノマー）を得た。下記式中、Ｅｔはエチルを示す。 [Synthesis example]
<Synthesis Example 1: Synthesis of Polymer P-1>
(2-hydroxymethyl) ethyl acrylate (Tokyo Kasei Co., Ltd.) 20 g, phenyl isocyanate (Tokyo Kasei Co., Ltd.) 19.2 g, butyl acetate 100 ml as a reaction solvent, octyltin compound as a catalyst (trade name: Neostan U -830 (manufactured by Nitto Kasei Co., Ltd.) 70 mg was weighed into a 300 ml flask, and the reaction vessel was heated to 90 ° C. in a nitrogen atmosphere to react. After completion of the reaction, the reaction mixture was concentrated, and the residue was purified by silica gel column chromatography to obtain monomer M-2 (monomer leading to repeating unit A-2). In the following formula, Et represents ethyl.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　続いて、攪拌機、温度計、還流冷却管、及び窒素ガス導入管を備えた２００ミリリットル三口フラスコに、ジメチルアセトアミド１５ｇを仕込んで、７５℃まで昇温した。窒素雰囲気下、反応容器内温度を７５℃に保ちながら、得られたモノマーＭ－２を１６ｇ、ベンジルメタクリレート４ｇ、ジメチルアセトアミド１５ｇ、及び「Ｖ－６０１」（和光純薬（株）製）０．１３ｇからなる混合溶液を、２．５時間で滴下が完了するように等速で滴下した。滴下完了後、さらに７５℃で３時間攪拌した。得られたポリマー溶液を室温まで冷却し、メタノール１２００ミリリットル、水３００ミリリットルの混合溶媒中に添加して攪拌し、再沈殿した。得られた粉末をろ別し、更にメタノール１０００ミリリットルで洗浄した後、６０℃で１２時間乾燥してポリマーＰ－１を得た。 Subsequently, 15 g of dimethylacetamide was charged into a 200 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, and the temperature was raised to 75 ° C. Under a nitrogen atmosphere, while maintaining the temperature in the reaction vessel at 75 ° C., 16 g of the obtained monomer M-2, 4 g of benzyl methacrylate, 15 g of dimethylacetamide, and “V-601” (manufactured by Wako Pure Chemical Industries, Ltd.) A mixed solution consisting of 13 g was added dropwise at a constant speed so that the addition was completed in 2.5 hours. After completion of dropping, the mixture was further stirred at 75 ° C. for 3 hours. The obtained polymer solution was cooled to room temperature, added to a mixed solvent of 1200 ml of methanol and 300 ml of water, stirred and reprecipitated. The obtained powder was filtered off, further washed with 1000 ml of methanol, and dried at 60 ° C. for 12 hours to obtain polymer P-1.
＜合成例２～８：ポリマーＰ－２～Ｐ－９の合成＞
　上記合成例１において、使用するモノマー種及び仕込み比を変更したこと以外は、合成例１と同様にして、下記表１に示すポリマーＰ－２～Ｐ－９を得た。 <Synthesis Examples 2 to 8: Synthesis of Polymers P-2 to P-9>
Polymers P-2 to P-9 shown in Table 1 below were obtained in the same manner as in Synthesis Example 1 except that the monomer type and charge ratio used in Synthesis Example 1 were changed.
＜比較合成例１及び２：比較ポリマーＨＰ－１及びＨＰ－２の合成＞
　上記合成例１において、使用するモノマー種及び仕込み比を下記表１に示す通りに変更したこと以外は合成例１と同様にして、比較ポリマーＨＰ－１及びＨＰ－２を得た。
　なお、下記表１中のＡ－２、Ａ－４、Ａ－５、Ａ－６、Ａ－７、Ａ－９、Ａ－１０、Ａ－１１は、上記例示の繰り返し単位に対応する。 <Comparative Synthesis Examples 1 and 2: Synthesis of Comparative Polymers HP-1 and HP-2>
Comparative Polymers HP-1 and HP-2 were obtained in the same manner as in Synthesis Example 1 except that the monomer type and charge ratio used in Synthesis Example 1 were changed as shown in Table 1 below.
In Table 1 below, A-2, A-4, A-5, A-6, A-7, A-9, A-10, and A-11 correspond to the repeating units exemplified above.
　下記表１には上記各合成例及び比較合成例で得られたポリマーの重量平均分子量を示した。ポリマーの重量平均分子量は、ゲル浸透クロマトグラフィー（Ｇｅｌ　Ｐｅｒｍｅａｔｉｏｎ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙ；ＧＰＣ）によりポリスチレン換算で測定される重量平均分子量を採用した。具体的な測定条件を以下に示す。
　ＧＰＣ装置：東ソー社製ＧＰＣ装置（ＨＬＣ－８３２０ＧＰＣ、Ｅｃｏｓｅｃ）
　カラム：ＴＳＫ　ｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｈ、ＴＳＫ　ｇｅｌ　ＳｕｐｅｒＨＺ４０００、ＴＳＫ　ｇｅｌ　ＳｕｐｅｒＨＺ２０００併用、（東ソー製、４．６ｍｍＩＤ（内径）×１５．０ｃｍ）
　溶離液：テトラヒドロフラン（ＴＨＦ） Table 1 below shows the weight average molecular weights of the polymers obtained in the above synthesis examples and comparative synthesis examples. As the weight average molecular weight of the polymer, a weight average molecular weight measured in terms of polystyrene by gel permeation chromatography (GPC) was adopted. Specific measurement conditions are shown below.
GPC equipment: GPC equipment manufactured by Tosoh Corporation (HLC-8320GPC, Ecosec)
Column: TSK gel SuperHZM-H, TSK gel SuperHZ4000, TSK gel SuperHZ2000 combined use (Tosoh, 4.6 mm ID (inner diameter) x 15.0 cm)
Eluent: Tetrahydrofuran (THF)
［試験例１：ポリマーの溶解性試験］
　バイアル瓶に、上記で合成したポリマー０．２ｇと、塩化メチレン／メタノール（＝８０／２０（ｗ／ｗ））混合溶媒の所定量（ポリマー濃度が１０ｗｔ％、５ｗｔ％、１ｗｔ％となるように調整）とを量りとり、ローター（アズワン社製、ＭＩＸ　ＲＯＴＯＲ　ＶＭＲ－ＳＲ）を用いて、室温にて３時間攪拌した。攪拌終了後、目視にて溶解状態を観察し、下記評価基準にて評価した。
（溶解性評価基準）
Ａ：１０ｗｔ％で完溶する
Ｂ：５ｗｔ％で完溶するが、１０ｗｔ％では完溶しない
Ｃ：１ｗｔ％で完溶するが、５ｗｔ％では完溶しない
Ｄ：１ｗｔ％で不溶分がある
　結果を下記表１に示す。 [Test Example 1: Polymer solubility test]
In a vial, 0.2 g of the polymer synthesized above and a predetermined amount of methylene chloride / methanol (= 80/20 (w / w)) mixed solvent (so that the polymer concentration is 10 wt%, 5 wt%, 1 wt%) The mixture was weighed for 3 hours at room temperature using a rotor (manufactured by ASONE, MIX ROTOR VMR-SR). After completion of stirring, the dissolved state was visually observed and evaluated according to the following evaluation criteria.
(Solubility evaluation criteria)
A: Completely dissolved at 10 wt% B: Completely dissolved at 5 wt%, but not completely dissolved at 10 wt% C: Completely dissolved at 1 wt%, but not completely dissolved at 5 wt% D: Insoluble content at 1 wt% Is shown in Table 1 below.
［試験例２：ガラス転移温度Ｔｇの測定］
　示差走査熱量測定装置（Ｘ－ＤＳＣ７０００（アイティー計測制御（株）製））にて、ポリマー試料２０ｍｇを測定パンに入れ、これを窒素気流中で速度１０℃／分で３０℃から１２０℃まで昇温して１５分間保持した後、３０℃まで－２０℃／分で冷却した。この後、再度３０℃から２５０℃まで昇温して、ベースラインが低温側から変化し始める温度をガラス転移温度Ｔｇとした。 [Test Example 2: Measurement of glass transition temperature Tg]
Using a differential scanning calorimeter (X-DSC7000 (produced by IT Measurement Control Co., Ltd.)), 20 mg of a polymer sample is placed in a measurement pan, and this is heated from 30 ° C. to 120 ° C. at a rate of 10 ° C./min in a nitrogen stream. The temperature was raised and held for 15 minutes, and then cooled to 30 ° C. at −20 ° C./min. Thereafter, the temperature was raised again from 30 ° C. to 250 ° C., and the temperature at which the baseline began to change from the low temperature side was defined as the glass transition temperature Tg.
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
［製造例１：積層体Ｓ－１～Ｓ－９及び比較積層体ＨＳ－２及びＨＳ－３の作製］
＜セルロースエステル樹脂層ＣＡ－１の作製＞
　下記の組成物をミキシングタンクに投入し、加熱しながら攪拌して、各成分を溶解し、固形分濃度２２質量％のセルロースアセテート溶液（ドープＡ）を調製した。
［セルロースアセテート溶液（ドープＡ）の組成］
　アセチル置換度２．８６のセルロースアセテート　　　　　１００質量部
　トリフェニルホスフェート（可塑剤）　　　　　　　　　　７．８質量部
　ビフェニルジフェニルホスフェート（可塑剤）　　　　　　３．９質量部
　紫外線吸収剤（チヌビン３２８　チバ・ジャパン製）　　　０．９質量部
　紫外線吸収剤（チヌビン３２６　チバ・ジャパン製）　　　０．２質量部
　メチレンクロライド（第１溶媒）　　　　　　　　　　　　３３６質量部
　メタノール（第２溶媒）　　　　　　　　　　　　　　　　　２９質量部
　１－ブタノール（第３溶媒）　　　　　　　　　　　　　　　１１質量部 [Production Example 1: Production of laminates S-1 to S-9 and comparative laminates HS-2 and HS-3]
<Preparation of Cellulose Ester Resin Layer CA-1>
The following composition was put into a mixing tank, stirred while heating to dissolve each component, and a cellulose acetate solution (dope A) having a solid content concentration of 22% by mass was prepared.
[Composition of Cellulose Acetate Solution (Dope A)]
Cellulose acetate with an acetyl substitution degree of 2.86 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Ultraviolet absorber (Tinubin 328 manufactured by Ciba Japan) 0.9 Part by weight Ultraviolet absorber (manufactured by Tinuvin 326 Ciba Japan) 0.2 part by weight Methylene chloride (first solvent) 336 parts by weight Methanol (second solvent) 29 parts by weight 1-butanol (third solvent) 11 parts by weight
　バンド流延装置を用い、上記調製したドープを２０００ｍｍ幅でステンレス製のエンドレスバンド（流延支持体）に流延ダイから均一に流延した。ドープ中の残留溶媒量が４０質量％になった時点で流延支持体から高分子膜として剥離し、テンターにて積極的に延伸をせずに搬送し、乾燥ゾーンで１３０℃で乾燥を行った。得られたセルロースエステル樹脂層（セルロースエステルフィルム）ＣＡ－１の厚さは５５μｍであった。 Using a band casting apparatus, the prepared dope was uniformly cast from a casting die onto a stainless steel endless band (casting support) having a width of 2000 mm. When the amount of residual solvent in the dope reaches 40% by mass, it is peeled off from the casting support as a polymer film, conveyed without being actively stretched by a tenter, and dried at 130 ° C. in a drying zone. It was. The thickness of the obtained cellulose ester resin layer (cellulose ester film) CA-1 was 55 μm.
＜セルロースエステル樹脂層ＣＡ－２の作製＞
　バンド流延装置を用い、上記調製したドープを２０００ｍｍ幅でステンレス製のエンドレスバンド（流延支持体）に流延ダイから均一に流延した。ドープＡ中の残留溶媒量が４０質量％になった時点で流延支持体から高分子膜として剥離し、渡り部で下流側のローラの回転速度を上流側のローラの回転速度より速くすることにより搬送方向の延伸を行い、温度１７０℃で搬送方向(ＭＤ)に１．２倍及びテンターで搬送方向の直交方向（ＴＤ方向）に１．５倍延伸し（延伸倍率は面積比で１．８倍）、乾燥ゾーンで１３０℃で乾燥を行った。得られたセルロースエステル樹脂層（セルロースエステルフィルム）ＣＡ－２の膜厚は４０μｍであった。 <Preparation of cellulose ester resin layer CA-2>
Using the band casting apparatus, the prepared dope was uniformly cast from a casting die onto a stainless steel endless band (casting support) having a width of 2000 mm. When the residual solvent amount in the dope A reaches 40% by mass, the polymer film is peeled from the casting support, and the rotational speed of the downstream roller is made higher than the rotational speed of the upstream roller at the transition portion. Is stretched 1.2 times in the transport direction (MD) at a temperature of 170 ° C. and 1.5 times in the direction perpendicular to the transport direction (TD direction) with a tenter (stretch ratio is 1. 8 times), drying was performed at 130 ° C. in the drying zone. The film thickness of the obtained cellulose ester resin layer (cellulose ester film) CA-2 was 40 μm.
＜積層体Ｓ－１の作製＞
　上記ポリマーＰ－１を固形分１５％となるようにメチルエチルケトンと混合した後、攪拌機をつけたガラス製セパラブルフラスコに仕込み、室温にて５時間攪拌後、孔径５μｍのポリプロピレン製デプスフィルターでろ過し、ポリマー層形成用組成物を得た。次に、上記で作製したセルロースエステル樹脂層ＣＡ－１上に、上記ポリマー層形成用組成物を、グラビアコーターを用いて塗布した。次いで２５℃で１分間乾燥し、さらに１２０℃で約５分間乾燥して膜厚６０μｍの積層体Ｓ－１を得た。 <Preparation of laminate S-1>
The polymer P-1 was mixed with methyl ethyl ketone so as to have a solid content of 15%, charged into a glass separable flask equipped with a stirrer, stirred at room temperature for 5 hours, and filtered through a polypropylene depth filter having a pore size of 5 μm. A composition for forming a polymer layer was obtained. Next, the composition for forming a polymer layer was applied on the cellulose ester resin layer CA-1 prepared above using a gravure coater. Subsequently, it was dried at 25 ° C. for 1 minute and further dried at 120 ° C. for about 5 minutes to obtain a laminate S-1 having a thickness of 60 μm.
＜積層体Ｓ－２～Ｓ－１０及び比較積層体ＨＳ－２及びＨＳ－３の作製＞
　上記＜積層体Ｓ－１の作製＞において、ポリマー層形成用組成物に用いるポリマーＰ－１を下記表２に示す通りに変更し、またセルロースエステル樹脂層を下記表２に示す通りとした以外は、上記＜積層体Ｓ－１の作製＞と同様にして、積層体Ｓ－２～Ｓ－１０、比較積層体ＨＳ－２及びＨＳ－３を作製した。得られた各積層体の厚さはいずれも６０μｍであった。 <Production of Laminates S-2 to S-10 and Comparative Laminates HS-2 and HS-3>
In the above <Production of laminate S-1>, the polymer P-1 used in the polymer layer forming composition was changed as shown in Table 2 below, and the cellulose ester resin layer was changed as shown in Table 2 below. Produced laminates S-2 to S-10 and comparative laminates HS-2 and HS-3 in the same manner as in <Preparation of laminate S-1>. Each of the obtained laminates had a thickness of 60 μm.
［製造例２：ポリマー混合単層フィルムＨＳ－１の作製］
　セルロースエステル樹脂層ＣＡ－１の作製において、アセチル置換度２．８６のセルロースアセテート１００質量部を８０質量部とし、さらにポリマーＰ－６を２０質量部添加した以外は、ＣＡ－１の作製と同様にして、Ｐ－６とＣＡ－１の混合物からなる単層フィルムを作製した。 [Production Example 2: Production of polymer mixed monolayer film HS-1]
The production of the cellulose ester resin layer CA-1 was the same as the production of CA-1, except that 100 parts by mass of cellulose acetate having an acetyl substitution degree of 2.86 was 80 parts by mass, and 20 parts by mass of polymer P-6 was further added. Thus, a monolayer film made of a mixture of P-6 and CA-1 was produced.
［試験例２：積層体の層間密着性試験］
　積層体の層間密着性は、ＪＩＳ　Ｋ　５４００に準処した碁盤目試験を適用した。具体的な手順を以下に示す。
　上記で調製した各積層体のポリマー層側の面にカッターナイフ及びカッターガイドを用いて、１ｍｍ間隔の１１本の切り傷をつけ１００個の碁盤目を作製した。この碁盤目上にセロハンテープを強く圧着させた後、テープの端を４５°の角度で一気に剥がし、碁盤目の状態（碁盤目を構成する格子の剥がれの状態）を観察した。観察結果を下記評価基準に当てはめ評価した。 [Test Example 2: Interlayer adhesion test of laminate]
For the interlaminar adhesion of the laminate, a cross cut test according to JIS K 5400 was applied. The specific procedure is shown below.
Using a cutter knife and a cutter guide, 11 cuts with an interval of 1 mm were made on the surface on the polymer layer side of each laminate prepared above to produce 100 grids. After the cellophane tape was strongly pressure-bonded on the grid, the end of the tape was peeled off at an angle of 45 °, and the state of the grid (the state of peeling of the lattice constituting the grid) was observed. The observation results were evaluated by applying the following evaluation criteria.
（層間密着性評価基準）
　Ａ：どの格子の目も剥がれない
　Ｂ：格子の目の剥がれが５％未満である
　Ｃ：格子の目の剥がれが５％以上３０％未満である
　Ｄ：格子の目の剥がれが３０％以上である
　結果を下記表２に示す。 (Interlayer adhesion evaluation criteria)
A: None of the lattice eyes peel off B: The lattice eye separation is less than 5% C: The lattice eye separation is 5% or more and less than 30% D: The lattice eye separation is 30% or more Certain results are shown in Table 2 below.
［試験例３：ヘイズ値の変化を指標にした耐久性試験］
　ヘイズメーター（ＨＧＭ－２ＤＰ、スガ試験機）を使用し、ＪＩＳ　Ｋ－６７１４に従って積層体ないし単層フィルムのヘイズ値を測定した。各積層体ないし単層フィルムを４０ｍｍ×８０ｍｍに切り出し、これを２５℃、相対湿度６０％ＲＨでの条件で測定した。
　また、１０５℃、相対湿度１０％ＲＨの条件で７２時間保存した後に、上記と同様の条件でヘイズ値を測定した。得られたヘイズ値に基づきヘイズ値の変化量を下記式より算出し、下記評価基準により積層体ないし単層フィルムの耐久性を評価した。
　ヘイズ値の変化量（％）＝上記保存後のヘイズ値（％）－上記保存前のヘイズ値（％）
（耐久性評価基準）
　Ａ：ヘイズ値の変化量が０．５％未満
　Ｂ：ヘイズ値の変化量が０．５％以上１％未満
　Ｃ：ヘイズ値の変化量が１％以上２％未満
　Ｄ：ヘイズ値の変化量が２％以上
　結果を下記表２に示す。 [Test Example 3: Durability test using change in haze value as an index]
Using a haze meter (HGM-2DP, Suga Tester), the haze value of the laminate or single layer film was measured according to JIS K-6714. Each laminate or single-layer film was cut into a size of 40 mm × 80 mm and measured under conditions of 25 ° C. and a relative humidity of 60% RH.
Moreover, after preserve | saving for 72 hours on the conditions of 105 degreeC and relative humidity 10% RH, the haze value was measured on the conditions similar to the above. Based on the obtained haze value, the amount of change in haze value was calculated from the following formula, and the durability of the laminate or single layer film was evaluated according to the following evaluation criteria.
Change in haze value (%) = haze value after storage (%)-haze value before storage (%)
(Durability evaluation criteria)
A: Change amount of haze value is less than 0.5% B: Change amount of haze value is 0.5% or more and less than 1% C: Change amount of haze value is 1% or more and less than 2% D: Change amount of haze value The results are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
　表２に示される通り、ポリマー層にＨＰ－１を用いた場合には、ＨＰ－１の溶解性が低いため、所望の積層構造を形成することができなかった（比較例２）。また、一般式（１）の繰り返し単位を有さず、Ｔｇが本発明で規定するよりも低いポリマーを用いてポリマー層を形成した場合、層間の密着性は良好であったが、耐久性試験後にヘイズ値が大きく上昇した（比較例３）。
　これに対し、本発明で規定するポリマーを用いてポリマー層を形成した積層体は、いずれも層間密着性が良好で実用上の許容範囲内にあり、また耐久性試験後においてもヘイズ値の上昇が良好に抑制されていた（実施例１～１０）。 As shown in Table 2, when HP-1 was used for the polymer layer, the desired laminated structure could not be formed because of the low solubility of HP-1 (Comparative Example 2). In addition, when the polymer layer was formed using a polymer having no repeating unit of the general formula (1) and having a Tg lower than that defined in the present invention, the interlayer adhesion was good, but the durability test Later, the haze value increased significantly (Comparative Example 3).
On the other hand, all the laminates in which the polymer layer is formed using the polymer specified in the present invention have good interlayer adhesion and are within a practically acceptable range, and the haze value increases even after the durability test. Was well suppressed (Examples 1 to 10).
［製造例３：偏光板ＰＬ－１～ＰＬ－３及び比較偏光板ＨＰＬ－１の作製］
　下記のようにして、偏光板ＰＬ－１～ＰＬ－３及び比較偏光板ＨＰＬ－１を作製した。
（１）鹸化
　市販のセルロースアシレートフィルム（フジタック　ＺＲＤ４０、富士フイルム（株）製）と、上記で作製した積層体Ｓ－１、Ｓ－５、Ｓ－８及び単層フィルムＨＳ－１を、５５℃に保った１．５モル／ＬのＮａＯＨ水溶液（鹸化液）に２分間浸漬した後、ＺＲＤ４０及び各積層体を水洗した。次いで、ＺＲＤ４０及び上記各積層体を２５℃の０．０５モル／Ｌの硫酸水溶液に３０秒浸漬した後、更に水洗浴を３０秒流水下に通して、ＺＲＤ４０、各積層体及び単層フィルムを中性の状態にした。得られたＺＲＤ４０、各積層体及び単層フィルムに対し、エアナイフによる水切りを３回繰り返し、水を落とした後に７０℃の乾燥ゾーンに１５秒間滞留させて乾燥し、鹸化処理したＺＲＤ４０、各積層体及び単層フィルムを得た。 [Production Example 3: Production of polarizing plates PL-1 to PL-3 and comparative polarizing plate HPL-1]
The polarizing plates PL-1 to PL-3 and the comparative polarizing plate HPL-1 were produced as follows.
(1) Saponification Commercially available cellulose acylate film (Fujitack ZRD40, manufactured by Fuji Film Co., Ltd.), laminates S-1, S-5, S-8 and monolayer film HS-1 prepared above were After being immersed in a 1.5 mol / L NaOH aqueous solution (saponification solution) kept at ° C. for 2 minutes, the ZRD 40 and each laminate were washed with water. Next, after ZRD40 and each of the above laminates were immersed in a 0.05 mol / L sulfuric acid aqueous solution at 25 ° C. for 30 seconds, a water washing bath was further passed under running water for 30 seconds, and ZRD40, each laminate and single layer film were It was in a neutral state. The obtained ZRD40, each laminate and single-layer film were drained with an air knife three times, and after dropping water, it was retained in a drying zone at 70 ° C. for 15 seconds, dried, and saponified ZRD40, each laminate. And a single layer film was obtained.
（２）偏光子の作製
　特開２００１－１４１９２６号公報の実施例１に従い、延伸したポリビニルアルコールフィルムにヨウ素を吸着させて膜厚２７μｍの偏光子を作製した。 (2) Production of Polarizer According to Example 1 of Japanese Patent Application Laid-Open No. 2001-141926, iodine was adsorbed to a stretched polyvinyl alcohol film to produce a polarizer having a thickness of 27 μm.
（３）貼り合わせ
　上記の鹸化後の各積層体（各積層体のポリマー層の側を偏光子と接するように配置する）又は単層フィルム、上記で作製した偏光子、上記の鹸化後のセルロールアシレートフィルムＺＲＤ４０をこの順に、ＰＶＡ系接着剤で貼合し、熱乾燥して、偏光板ＰＬ－１～ＰＬ－３及び比較偏光板ＨＰＬ－１を作製した。
　この際、作製した偏光子のロールの長手方向と、各積層体のセルロースエステル樹脂層のロールの長手方向あるいは単層フィルムのロールの長手方向とが平行になるように配置した。また、偏光子のロールの長手方向と上記セルロールアシレートフィルムＺＲＤ４０のロールの長手方向とが、平行になるように配置した。 (3) Bonding Each laminated body after the above saponification (arranged so that the polymer layer side of each laminated body is in contact with the polarizer) or a single-layer film, the polarizer produced above, and the cell after the above saponification The roll acylate film ZRD40 was laminated with a PVA adhesive in this order and heat-dried to prepare polarizing plates PL-1 to PL-3 and a comparative polarizing plate HPL-1.
Under the present circumstances, it arrange | positioned so that the longitudinal direction of the roll of the produced polarizer and the longitudinal direction of the roll of the cellulose-ester resin layer of each laminated body or the longitudinal direction of the roll of a single layer film may become parallel. Moreover, it arrange | positioned so that the longitudinal direction of the roll of a polarizer and the longitudinal direction of the roll of the said cell roll acylate film ZRD40 may become parallel.
［試験例４：偏光板の偏光子耐久性の評価］
　偏光板の耐久性は、偏光板をガラスに粘着剤を介して貼り付けた形態で次のようにして直交透過率及び偏光度をそれぞれ測定した。
　ガラス板の上に偏光板を、積層体Ｓ－１、Ｓ－５、Ｓ－８及び単層フィルムＨＳ－１の側が空気界面側になるように（ガラス板から離れた側になるように）貼り付けたサンプル（約５ｃｍ×５ｃｍ）を２つ作製した。これらのサンプルについて、ガラス板側を光源に向けてセットして偏光度を測定した。２つのサンプルをそれぞれ測定し、算術平均した値を偏光板の偏光度とした。
　なお、偏光度は、以下の式により算出した。 [Test Example 4: Evaluation of polarizer durability of polarizing plate]
The durability of the polarizing plate was measured by measuring the orthogonal transmittance and the polarization degree in the following manner in a form in which the polarizing plate was attached to glass through an adhesive.
A polarizing plate is placed on the glass plate so that the side of the laminates S-1, S-5, S-8 and the single layer film HS-1 is on the air interface side (so that it is on the side away from the glass plate). Two pasted samples (about 5 cm × 5 cm) were prepared. About these samples, the glass plate side was set toward the light source, and the degree of polarization was measured. Each of the two samples was measured and the arithmetic average value was taken as the polarization degree of the polarizing plate.
The degree of polarization was calculated by the following formula.
偏光度（％）＝［（平行透過率－直交透過率）／（直交透過率＋平行透過率）］１／２×１００ Polarization degree (%) = [(parallel transmittance−orthogonal transmittance) / (orthogonal transmittance + parallel transmittance)] 1/2 × 100
　偏光度は、日本分光（株）製、自動偏光フィルム測定装置ＶＡＰ－７０７０を用いて３８０ｎｍ～７８０ｎｍの範囲で測定し、劣化の度合いが他の波長より顕著に出る波長４１０ｎｍにおける測定値を採用した。
　その後、温度８５℃、相対湿度８５％の環境下で５００時間保存した。次いで、上記と同様にして２つのサンプルについて偏光度を測定し、２つのサンプルの測定値を算術平均し、保存後の偏光板の偏光度とした。保存前後の偏光度の変化量に基づき、偏光板耐久性を下記評価基準に基づき評価した。
　ここで、偏光度変化量は下記式で算出される。 The degree of polarization was measured in the range of 380 nm to 780 nm using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation, and the measured value at a wavelength of 410 nm at which the degree of deterioration is more noticeable than other wavelengths was adopted. .
Thereafter, it was stored for 500 hours in an environment of a temperature of 85 ° C. and a relative humidity of 85%. Subsequently, the polarization degree was measured about two samples like the above, the measured value of two samples was arithmetically averaged, and it was set as the polarization degree of the polarizing plate after a preservation | save. Based on the amount of change in the degree of polarization before and after storage, the polarizing plate durability was evaluated based on the following evaluation criteria.
Here, the amount of change in polarization degree is calculated by the following equation.
　偏光度変化量（％）＝［上記保存前の偏光度（％）－上記保存後の偏光度（％）］ Polarization degree change (%) = [Polarization degree before storage (%) − Polarization degree after storage (%)]
＜偏光子耐久性評価基準＞
　Ａ　：偏光度変化量が０．０５％未満
　Ｂ　：偏光度変化量が０．０５％以上１．０％未満
　Ｃ　：偏光度変化量が１．０％以上２．０％未満
　Ｄ　：偏光度変化量が２．０％以上３．０％未満
　Ｅ　：偏光度変化量が３．０％以上
　結果を下記表３に示す。 <Polarizer durability evaluation criteria>
A: Polarization degree change amount is less than 0.05% B: Polarization degree change amount is 0.05% or more and less than 1.0% C: Polarization degree change amount is 1.0% or more and less than 2.0% D: Polarization degree Change amount is 2.0% or more and less than 3.0% E: Polarization degree change amount is 3.0% or more The results are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
　上記表３に記載される通り、本発明の積層体を保護フィルムとして用いた本発明の偏光板ＰＬ－１～ＰＬ－３は、高温、高湿の過酷条件下で長時間保存しても、偏光度の変化を３．０％未満と低く抑えることができ、優れた偏光子耐久性を示した。すなわち、本発明の積層体を偏光子の保護フィルムとして用いた偏光板を画像表示装置に組み込むことにより、高温高湿条件下で長時間使用しても画像品質の劣化を効果的に抑制できることがわかる。 As described in Table 3 above, the polarizing plates PL-1 to PL-3 of the present invention using the laminate of the present invention as a protective film can be stored for a long time under severe conditions of high temperature and high humidity. The change in the degree of polarization could be kept as low as less than 3.0%, and excellent polarizer durability was exhibited. That is, by incorporating a polarizing plate using the laminate of the present invention as a protective film for a polarizer into an image display device, deterioration in image quality can be effectively suppressed even when used for a long time under high temperature and high humidity conditions. Recognize.
　本発明をその実施態様とともに説明したが、我々は特に指定しない限り我々の発明を説明のどの細部においても限定しようとするものではなく、添付の請求の範囲に示した発明の精神と範囲に反することなく幅広く解釈されるべきであると考える。 While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.
　本願は、２０１６年２月２４日に日本国で特許出願された特願２０１６－０３２７８０に基づく優先権を主張するものであり、これはここに参照してその内容を本明細書の記載の一部として取り込む。 This application claims priority based on Japanese Patent Application No. 2016-032780 filed in Japan on February 24, 2016, which is hereby incorporated herein by reference. Capture as part.
１０　積層体（積層板）
　１１　セルロースエステル樹脂層
　１２　ポリマー層
２０　液晶表示装置
　２１　上側偏光板
　２２　上側偏光板吸収軸の方向
　２３　液晶セル上電極基板
　２４　液晶層
　２５　液晶セル下電極基板
　２６　下側偏光板
　２７　下側偏光板吸収軸の方向 10 Laminate (laminate)
DESCRIPTION OF SYMBOLS 11 Cellulose ester resin layer 12 Polymer layer 20 Liquid crystal display device 21 Upper polarizing plate 22 Upper polarizing plate absorption axis direction 23 Liquid crystal cell upper electrode substrate 24 Liquid crystal layer 25 Liquid crystal cell lower electrode substrate 26 Lower polarizing plate 27 Lower polarizing plate absorption Axial direction

Claims (7)

  1. 　セルロースエステル樹脂層と、このセルロースエステル樹脂層上に直接設けた、下記一般式（１）で表される繰り返し単位を有するポリマーを含有する層とを有し、該ポリマーのガラス転移温度が５０℃以上である、積層体。
    Figure JPOXMLDOC01-appb-C000001
     　一般式（１）中、Ｒａは水素原子、アルキル基又はアルコキシカルボニル基を示す。
    　Ｒｂ及びＲｃは水素原子、アルキル基、アリール基又はアルコキシカルボニル基を示す。
    　Ｒ２はアルキル基、シクロアルキル基又はアリール基を示す。
    　Ｌ１はアルキレン基、アリーレン基、－Ｃ（＝Ｏ）－、－Ｏ－及び－ＮＲ３－から選ばれる２価の基を２種以上組み合わせてなる２価の連結基を示す。但し、Ｌ１は－Ｃ（＝Ｏ）ＮＲ３－で表される基を含む。
    　Ｒ３は水素原子又は置換基を示す。     A cellulose ester resin layer, and a layer containing a polymer having a repeating unit represented by the following general formula (1) provided directly on the cellulose ester resin layer, and the glass transition temperature of the polymer is 50 ° C. That is the laminate.
    Figure JPOXMLDOC01-appb-C000001
     In General Formula (1), R a represents a hydrogen atom, an alkyl group, or an alkoxycarbonyl group.
    R b and R c represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
    R 2 represents an alkyl group, a cycloalkyl group or an aryl group.
    L 1 represents a divalent linking group formed by combining two or more divalent groups selected from an alkylene group, an arylene group, —C (═O) —, —O—, and —NR 3 —. However, L 1 includes a group represented by —C (═O) NR 3 —.
    R 3 represents a hydrogen atom or a substituent.
  2. 　前記一般式（１）で表される繰り返し単位が下記一般式（２）又は（３）で表される繰り返し単位である、請求項１記載の積層体。
    Figure JPOXMLDOC01-appb-C000002
     　一般式（２）中、Ｒ１ａは水素原子又はメチルを示す。
    　Ｒ２は一般式（１）におけるＲ２と同義である。
    　Ｌ２はアルキレン基、アルキレンオキシ基又はポリアルキレンオキシ基を示す。
    　Ａは－Ｃ（＝Ｏ）ＮＲ３－又は－ＮＲ３－Ｃ（＝Ｏ）－ＮＲ３－を示す。Ｒ３は前記一般式（１）におけるＲ３と同義である。
    Figure JPOXMLDOC01-appb-C000003
     　一般式（３）中、Ｒ１ａ及びＲ２は、それぞれ前記一般式（２）におけるＲ１ａ及びＲ２と同義である。
    　Ｒ３ａは水素原子又はアルキル基を示す。     The laminate according to claim 1, wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (2) or (3).
    Figure JPOXMLDOC01-appb-C000002
     In general formula (2), R 1a represents a hydrogen atom or methyl.
    R 2 has the same meaning as R 2 in the general formula (1).
    L 2 represents an alkylene group, an alkyleneoxy group or a polyalkyleneoxy group.
    A represents —C (═O) NR 3 — or —NR 3 —C (═O) —NR 3 —. R 3 has the same meaning as R 3 in Formula (1).
    Figure JPOXMLDOC01-appb-C000003
     In the general formula (3), R 1a and R 2 have the same meanings as R 1a and R 2 in each of the general formula (2).
    R 3a represents a hydrogen atom or an alkyl group.
  3. 　前記一般式（３）で表される繰り返し単位が下記一般式（４）で表される繰り返し単位である、請求項２記載の積層体。
    Figure JPOXMLDOC01-appb-C000004
     　一般式（４）中、Ｒ１ａ及びＲ２は、それぞれ前記一般式（３）におけるＲ１ａ及びＲ２と同義である。     The laminate according to claim 2, wherein the repeating unit represented by the general formula (3) is a repeating unit represented by the following general formula (4).
    Figure JPOXMLDOC01-appb-C000004
     In the general formula (4), R 1a and R 2 have the same meanings as R 1a and R 2 in each of the general formula (3).
  4. 　前記一般式（１）で表される繰り返し単位を有する前記ポリマーが、前記一般式（１）で表される繰り返し単位と、下記一般式（５）で表される繰り返し単位とを有する、請求項１～３のいずれか１項記載の積層体。
    Figure JPOXMLDOC01-appb-C000005
     　一般式（５）中、Ｒ４及びＲ５は水素原子、アルキル基、アリール基又はアルコキシカルボニル基を示す。
    　Ｒ６は水素原子又はアルキル基を示す。
    　Ｌ３は単結合であるか、又は、アルキレン基、アリーレン基、－Ｃ（＝Ｏ）－、－Ｏ－及び－Ｎ（Ｒ３Ａ）－から選ばれる２価の基もしくはこれらの基の２種以上を組合せてなる２価の連結基を示す。
    　Ｒ３Ａは水素原子又は置換基を示す。     The polymer having a repeating unit represented by the general formula (1) has a repeating unit represented by the general formula (1) and a repeating unit represented by the following general formula (5). 4. The laminate according to any one of 1 to 3.
    Figure JPOXMLDOC01-appb-C000005
     In General Formula (5), R 4 and R 5 represent a hydrogen atom, an alkyl group, an aryl group, or an alkoxycarbonyl group.
    R 6 represents a hydrogen atom or an alkyl group.
    L 3 is a single bond, a divalent group selected from an alkylene group, an arylene group, —C (═O) —, —O— and —N (R 3A ) —, or two of these groups A divalent linking group formed by combining the above is shown.
    R 3A represents a hydrogen atom or a substituent.
  5. 　前記積層体中、前記一般式（１）で表される繰り返し単位を有するポリマーの含有量が１～３０質量％である、請求項１～４のいずれか１項記載の積層体。 The laminate according to any one of claims 1 to 4, wherein the content of the polymer having the repeating unit represented by the general formula (1) in the laminate is 1 to 30% by mass.
  6. 　請求項１～５のいずれか１項記載の積層体と、偏光子とを有する偏光板。 A polarizing plate comprising the laminate according to any one of claims 1 to 5 and a polarizer.
  7. 　請求項６に記載の偏光板を有する画像表示装置。 An image display device having the polarizing plate according to claim 6.
PCT/JP2016/084796 2016-02-24 2016-11-24 Laminate, polarizing plate and image display device WO2017145469A1 (en)

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