WO2017057254A1 - Laminate, polarizing plate, and image display device - Google Patents

Laminate, polarizing plate, and image display device Download PDF

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Publication number
WO2017057254A1
WO2017057254A1 PCT/JP2016/078231 JP2016078231W WO2017057254A1 WO 2017057254 A1 WO2017057254 A1 WO 2017057254A1 JP 2016078231 W JP2016078231 W JP 2016078231W WO 2017057254 A1 WO2017057254 A1 WO 2017057254A1
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Prior art keywords
repeating unit
group
adhesive polymer
cellulose ester
general formula
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PCT/JP2016/078231
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French (fr)
Japanese (ja)
Inventor
寛 野副
佑起 中沢
一洋 雨宮
正人 名倉
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富士フイルム株式会社
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Priority claimed from JP2016016705A external-priority patent/JP2017065241A/en
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Publication of WO2017057254A1 publication Critical patent/WO2017057254A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04Layered 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
    • B32B23/08Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols

Definitions

  • the present invention relates to a laminate, a polarizing plate using the laminate, and an image display device.
  • Image display devices represented by electroluminescence displays (ELDs) and liquid crystal display devices (LCDs) are increasingly required to be thin.
  • 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 apparatus is partly caused by moisture entering the polarizing plate and degrading the polarizer.
  • the polarizer is protected by laminating a protective film (optical film) on the surface, but the protective film is also required to be thin.
  • the protective film is thinned, moisture is more likely to come into contact with the polarizer, and the image quality is likely to deteriorate.
  • such a decrease in image quality becomes more apparent when used in harsh environments such as outdoor applications.
  • the protective film cellulose resins and acrylic resins are widely used from the viewpoint of versatility and processability. Due to the necessity of further improving the durability, the optical film is being modified (for example, Patent Documents 1 to 5).
  • the present invention is a laminate provided with a cellulose ester resin layer, which is excellent in adhesion between layers, can effectively suppress moisture transmission even when thinned, and when used as a protective film for a polarizer It is an object of the present invention to provide a laminate capable of effectively suppressing deterioration of a polarizer, a polarizing plate using the laminated body, and an image display device using the polarizing plate.
  • the present inventors have found that a polymer having a repeating unit having a specific structure in which the solubility parameter is within a specific range, and a repeating unit having a specific structure in which the solubility parameter is different from the repeating unit.
  • the laminate in which the layer is directly provided on the cellulose ester resin layer has excellent adhesion between the polymer layer and the cellulose ester resin layer, and has a low moisture permeability and is used as a protective film for a polarizer. It has been found that deterioration of the polarizer can be effectively suppressed even under wet conditions.
  • the present invention has been further studied based on these findings and has been completed.
  • [1] It has a cellulose ester resin layer and an adhesive polymer layer provided directly on the cellulose ester resin layer, and the adhesive polymer constituting the adhesive polymer layer is at least one repeating unit of the following [a]: The laminated body which has at least 1 sort (s) of the repeating unit of following [b].
  • R 2 and R 3 represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
  • L is a single bond, or a divalent linking group selected from an alkylene group, an arylene group, —C ( ⁇ O) —, —O— and —N (R 4 ) —, or 2 of these linking groups.
  • a divalent linking group formed by combining more than one species is shown.
  • R 4 represents a hydrogen atom or an alkyl group.
  • R 6 and R 7 represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
  • R 8 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms.
  • substituents when there are a plurality of substituents, linking groups, and the like (hereinafter referred to as substituents) indicated by specific symbols, or when a plurality of substituents 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.
  • a salt of a compound for example, an acid addition salt of a compound formed with a compound and an inorganic acid or an organic acid, or a base addition salt of a compound formed with a compound and an inorganic base or an organic basic acid Etc.
  • 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.
  • 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.
  • the term “(meth) acrylic acid” is used to include both methacrylic acid and acrylic acid. The same applies to “(meth) acrylamide”. In this specification, the term “acrylic acid” is used in a broader sense than usual.
  • acrylic acid is used to include all compounds having the structure of R A —C ( ⁇ CR B 2 ) COOH (R A and R B each independently represent a hydrogen atom or a substituent, provided that , When R A is methyl, means methacrylic acid)).
  • R A and R B each independently represent a hydrogen atom or a substituent, provided that , When R A is methyl, means methacrylic acid)).
  • R A is methyl, means methacrylic acid
  • 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.
  • 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 and a sulfur atom.
  • halogen atom eg fluorine atom, chlorine atom, bromine atom, iodine atom
  • cyano group eg fluorine atom, chlorine atom, bromine atom, iodine atom
  • sulfo group carboxyl group
  • nitro group hydroxamic acid group
  • sulfino group e.g., sulfino group
  • a condensed ring is preferable, and specific examples include imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, and the like. (Preferably having 3 to 40 carbon atoms, more preferably 3 to 30, and particularly preferably 3 to 24, In example, a trimethylsilyl group, etc. triphenylsilyl group). 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.
  • the laminate of the present invention is excellent in adhesion between layers and can effectively suppress the permeation of moisture even if it is made thin.
  • the laminate of the present invention can effectively suppress the deterioration of the polarizer under high temperature and high humidity conditions by overlapping with the polarizer.
  • 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 severe 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 10 of the present invention has a cellulose ester resin layer 11 and an adhesive polymer layer 12 provided directly on the cellulose ester resin layer 11. Details of the cellulose ester resin layer 11 and the adhesive polymer layer 12 will be described later.
  • the laminate of the present invention may have an adhesive polymer layer 12 provided on one side of the cellulose ester resin layer 11 or an adhesive polymer layer 12 provided on both sides. Also good. More preferably, the laminate 10 of the present invention has a form in which the adhesive polymer layer 12 is provided on one side of the cellulose ester resin layer 11. As the adhesive polymer layer, two or more adhesive polymer layers having different composition ratios may be provided on 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 adhesive 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 “adhesive polymer layer” means a layer containing an adhesive polymer described later in an amount of 50% by mass or more.
  • the content of the adhesive polymer in the adhesive 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 adhesive polymer the higher the adhesiveness with the cellulose ester resin layer, which is preferable. Therefore, the content of the adhesive polymer in the adhesive polymer layer may be 100% by mass, and is usually 99% by mass or less.
  • the balance can contain various conventional additives.
  • additives include plasticizers, organic acids, dyes, polymers, retardation modifiers, ultraviolet absorbers, antioxidants, matting agents, and the like.
  • Two or more adhesive polymers may be used in combination. That is, dense polymers having different composition ratios and / or molecular weights may be used in combination. In this case, the total amount of the adhesive polymer is within the above range.
  • adheresive polymer simply means a polymer that can be in close contact with the cellulose ester resin layer, and is merely used to facilitate understanding of the present invention.
  • the “adhesive polymer” includes all polymers having a repeating unit as defined in the present invention regardless of the degree of adhesion. That is, in judging the gist and technical scope of the present invention, the term “adhesiveness” is not considered as an invention specific matter for interpreting the present invention in a limited manner.
  • the adhesive polymer constituting the adhesive polymer layer has at least one repeating unit of the following [a] and at least one repeating unit of the following [b] in one molecule.
  • [A] A repeating unit derived from a (meth) acrylic ester compound, an olefin compound, a vinylidene compound or a cyclic olefin compound and having a solubility parameter ⁇ t calculated by the Hoy method of 13.5 to 19.5.
  • the solubility parameter ⁇ t is literature "Properties of Polymers 3 rd, ELSEVIER , (1990)" The ⁇ t obtained for Amorphous Polymers according to the 214-220 pages, "2) Method of Hoy (1985,1989)” column of Meaning and calculated according to the description in the above column of the above document. Units of the solubility parameter ⁇ t in the present invention are "(cal / cm 3) 1/2.”
  • the repeating unit [a] is not particularly limited as long as the above [a] is satisfied.
  • the repeating unit satisfying the above [a] is derived from a (meth) acrylic acid ester compound
  • examples of the structure of the repeating unit include paragraphs [0021] to [0023] of JP-A No. 2004-323770, Reference may be made to paragraphs [0024] to [0059] of Japanese Unexamined Patent Publication No. 2014-185196.
  • the above [a] is a repeating unit derived from a (meth) acrylic acid ester compound, it is more preferably a repeating unit derived from a (meth) acrylic acid alkyl ester compound or a (meth) acrylic acid cycloalkyl ester compound. .
  • the alkyl group of this (meth) acrylic acid alkyl ester compound may be linear or branched.
  • the alkyl group constituting the (meth) acrylic acid alkyl ester compound preferably has 1 to 30 carbon atoms, more preferably 3 to 30 carbon atoms, still more preferably 4 to 20 carbon atoms, still more preferably 5 to 18 carbon atoms, and even more preferably 6 to 16 carbon atoms. .
  • (meth) acrylic acid ester compound and (meth) acrylic acid cycloalkyl ester compound for deriving the repeating unit [a] above include, for example, propyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylic acid iso-butyl, sec-butyl acrylate, tert-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, Mention may be made of n-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate.
  • repeating unit [a] is derived from an olefin compound
  • paragraph [0015] of JP-A No. 2000-159817 can be referred to as the structure of such a repeating unit.
  • Specific examples of the olefin compound for deriving the repeating unit [a] include ethylene, propylene, isoprene, butadiene, isobutene and vinyl chloride.
  • repeating unit [a] When the repeating unit [a] is derived from a vinylidene compound, examples of the structure of the repeating unit include paragraphs [0032] to [0041] of JP-A-2015-44967 and JP-A-8-67793. Paragraphs [0008] to [0009] and the like can be referred to.
  • Specific examples of the vinylidene compound for deriving the repeating unit [a] include, for example, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, trifluoroethylene chloride, and perfluoroalkoxytrifluoroethylene.
  • repeating unit [a] is derived from a cyclic olefin compound
  • specific examples of the cyclic olefin compound leading to the repeating unit [a] include, for example, cyclohexene, norbornene, tetracyclododecene, and the like. Mention may be made of the derived compounds.
  • the adhesive polymer preferably has a repeating unit represented by the following general formula 2 as the repeating unit [a].
  • General formula 2 :
  • R 5 represents a hydrogen atom or an alkyl group.
  • the alkyl group that can be adopted as R 5 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 5 is more preferably methyl or ethyl, and even more preferably methyl.
  • R 5 is preferably a hydrogen atom or methyl.
  • R 6 and R 7 represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
  • the alkyl group which can be taken as R 6 and R 7 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.
  • the alkyl group that can be taken as R 6 and R 7 is more preferably methyl or ethyl, and even more preferably methyl.
  • the aryl group that can be adopted as R 6 and R 7 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.
  • the alkoxycarbonyl group that can be employed as R 6 and R 7 preferably has 2 to 10 carbon atoms, and more preferably 2 to 5 carbon atoms.
  • the alkoxycarbonyl group which can be taken as R 6 and R 7 is more preferably methoxycarbonyl or ethoxycarbonyl.
  • R 8 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms that can be taken as R 8 may be linear or branched.
  • the alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 12, more preferably 1 to 10, still more preferably 1 to 8, and still more preferably 1 to 6.
  • the alkyl group having 1 to 20 carbon atoms that can be taken as R 8 has a substituent, a halogen atom is preferable, and a fluorine atom is more preferable.
  • the cycloalkyl group having 3 to 20 carbon atoms that can be adopted as R 8 has more preferably 4 to 15 carbon atoms, and further preferably 5 to 12 carbon atoms.
  • the cycloalkyl group having 3 to 20 carbon atoms that can be employed as R 8 is preferably in a form in which the substituents of the cycloalkyl group are connected to each other to form a condensed ring.
  • the cycloalkyl group having 3 to 20 carbon atoms that can be taken as R 8 has a substituent, it is preferably an alkyl group (which may be linear or branched), and has 1 to 4 carbon atoms.
  • An alkyl group is more preferable, and methyl, ethyl, or t-butyl is more preferable.
  • the molar amount of the repeating unit represented by the general formula 2 in the total molar amount of the repeating unit [a] is preferably 50 mol% or more, and 70 mol% or more. More preferably, it is 80 mol% or more, more preferably 90 mol% or more.
  • the adhesive polymer preferably has a molar amount of the repeating unit represented by the general formula 2 in the total molar amount of the repeating unit [a] of 100 mol% or less. It is also preferred that all of the repeating units [a] contained therein are repeating units represented by the general formula 2.
  • the adhesive polymer more preferably has a repeating unit represented by the following general formula 2-2 as the repeating unit of the above [a].
  • Formula 2-2 a repeating unit represented by the following general formula 2-2 as the repeating unit of the above [a].
  • R 5 and R 8 have the same meanings as R 5 and R 8 in General Formula 2, respectively, and preferred forms are also the same.
  • the molar amount of the repeating unit represented by the general formula 2-2 in the total molar amount of the repeating unit [a] is preferably 50 mol% or more, and 70 mol% or more. More preferably, it is more preferably 80 mol% or more, and still more preferably 90 mol% or more.
  • the adhesive polymer preferably has a molar amount of the repeating unit represented by the general formula 2-2 in the total molar amount of the repeating unit [a] of 100 mol% or less. It is also preferred that all of the repeating units [a] contained in the conductive polymer are repeating units represented by the general formula 2-2.
  • the (meth) acrylic acid ester compound includes a (meth) acrylic acid compound.
  • A-32 can also be interpreted as a repeating unit derived from a vinylidene compound.
  • a vinylidene compound when the structure consists of only a carbon atom and a hydrogen atom, it is classified as an olefin compound instead of a vinylidene compound.
  • the repeating unit [b] is not particularly limited as long as the above [b] is satisfied.
  • the repeating unit satisfying the above [b] is derived from a (meth) acrylic acid ester compound
  • examples of the structure of the repeating unit include paragraphs [0021] to [0023] of JP-A-2004-323770. Reference may be made to [0024] to [0059] of JP 2014-185196.
  • Specific examples of the (meth) acrylic acid ester compound for deriving the repeating unit [b] include, for example, 2-hydroxyethyl acrylate, 2-acetoacetoxyethyl acrylate, 2-isocyanatoethyl acrylate, and methacrylic acid. Examples thereof include 2-hydroxyethyl, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, and 2-isocyanatoethyl methacrylate.
  • repeating unit [b] is derived from a (meth) acrylic acid compound
  • paragraphs [0020] to [0027] of JP 2002-212221 A for example, as the structure of the repeating unit. be able to.
  • Specific examples of the (meth) acrylic acid compound from which the repeating unit [b] is derived include acrylic acid and its metal salt, and methacrylic acid and its metal salt.
  • a preferable structure when the repeating unit [b] is derived from a (meth) acrylamide compound is as shown in the structural formula exemplified later.
  • repeating unit [b] is derived from a vinyl acetate compound
  • paragraphs [0007] to [0008] of JP-A-2002-338609 can be referred to as the structure of such a repeating unit.
  • Specific examples of the vinyl acetate compound from which the repeating unit [b] is derived include vinyl acetate, vinyl propionate, vinyl pivalate, isopropenyl acetate and the like.
  • “vinyl acetate compound” is used to include a compound in which a hydrogen atom of vinyl acetate is substituted.
  • the repeating unit [b] is derived from a vinyl ketone compound
  • examples of the structure of the repeating unit include, for example, paragraphs [0010] to [0017] of JP-A-2007-230940 and JP-A-7-291886. Paragraphs [0009] to [0011] and the like can be referred to.
  • Specific examples of the vinyl ketone compound for deriving the repeating unit [b] include methyl vinyl ketone and ethyl vinyl ketone.
  • the vinyl ketone compound means a compound having the following structure and not an acrylate compound, an acrylamide compound, or an acrylic acid compound.
  • repeating unit [b] When the repeating unit [b] is derived from a maleic anhydride compound, examples of the structure of the repeating unit include, for example, paragraphs [0027] to [0029] of JP-A-2006-1111710 and JP-A-2008-156400. Reference may be made to paragraphs [0013] to [0015] and the like of the publication.
  • Specific examples of the maleic anhydride compound for deriving the repeating unit [b] include maleic anhydride, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like.
  • “maleic anhydride compound” is used to include a compound derived from maleic anhydride.
  • a preferable structure when the repeating unit [b] is derived from a styrene compound is as shown in the structural formula exemplified later.
  • the repeating unit [b] may be a repeating unit derived from a compound having an ethylenically unsaturated bond (carbon-carbon double bond) other than the repeating unit derived from each compound described above.
  • the adhesive polymer preferably has a repeating unit represented by the following general formula 1 as the repeating unit [b].
  • General formula 1 :
  • R 1 , R 2 and R 3 have the same meanings as R 5 , R 6 and R 7 in General Formula 2, respectively, and preferred forms are also the same.
  • L is a single bond, or a divalent linking group selected from an alkylene group, an arylene group, —C ( ⁇ O) —, —O— and —N (R 4 ) —, or 2 of these linking groups.
  • a divalent linking group formed by combining more than one species is shown.
  • R 4 has the same meaning as R 1 above, and the preferred form is also the same.
  • 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.
  • the combination of —C ( ⁇ O) —, —O— and an alkylene group or the combination of —C ( ⁇ O) —, —O— and an arylene group.
  • a combination of —C ( ⁇ O) —, —O— and an alkylene group is more preferred.
  • L is a linking group containing —C ( ⁇ O) —, and —C ( ⁇ O) — is bonded to the main chain (the carbon atom to which R 1 is bonded).
  • the alkylene group that can be taken as L is preferably a straight chain.
  • 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 that can be taken as L 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 molar amount of the repeating unit represented by the general formula 1 in the total molar amount of the repeating unit [b] is preferably 50 mol% or more, and 70 mol% or more. More preferably, it is 80 mol% or more, more preferably 90 mol% or more.
  • the adhesive polymer preferably has a molar amount of the repeating unit represented by the general formula 1 in the total molar amount of the repeating unit [b] of 100 mol% or less. It is also preferred that all of the repeating units [b] contained therein are repeating units represented by the above general formula 1.
  • the adhesive polymer more preferably has a repeating unit represented by the following general formula 1-1 as the repeating unit [b].
  • Formula 1-1 :
  • R 1 and L have the same meanings as R 1 and L in general formula 1, respectively, and preferred forms are also the same.
  • the molar amount of the repeating unit represented by the general formula 1-1 in the total molar amount of the repeating unit [b] is preferably 50 mol% or more, and 70 mol% or more. More preferably, it is more preferably 80 mol% or more, and still more preferably 90 mol% or more.
  • the adhesive polymer preferably has a molar amount of the repeating unit represented by the general formula 1-1 in the total molar amount of the repeating unit [b] of 100 mol% or less. It is also preferred that all of the repeating units [b] contained in the functional polymer are repeating units represented by the general formula 1-1.
  • the adhesive polymer is not particularly limited as to the content of each repeating unit as long as it has both the repeating unit [a] and the repeating unit [b]. That is, the adhesive polymer may have a repeating unit other than the repeating unit [a] and the repeating unit [b].
  • the molar amount of the repeating unit (b) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more.
  • the molar amount of the repeating unit (b) occupying in the total molar amount of the monomer component constituting the adhesive polymer is preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 80 mol% or less. .
  • the molar amount of the repeating unit [a] in the total molar amount of the monomer component constituting the adhesive polymer is determined. It is preferably 5 mol% or more, more preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 40 mol% or more, and 50 mol% or more. It is particularly preferred.
  • the molar amount of the repeating unit [a] in the total molar amount of the monomer component constituting the adhesive polymer is preferably 95 mol% or less, and more preferably 90 mol% or less.
  • the content of the repeating unit [a] and the content of the repeating unit [b] is preferably 50% by mass or more, more preferably 70% by mass or more. Preferably, it is 80 mass% or more, more preferably 90 mass% or more.
  • the adhesive polymer is also preferably in the form of the repeating unit [a] and the repeating unit [b].
  • the adhesive polymer may be a random polymer or a block polymer.
  • the layer using the polymer having the repeating unit [a] and the polymer having the repeating unit [b] is excellent in adhesion to the cellulose ester resin layer is not clear, but is estimated as follows. That is, the solubility parameter ⁇ t of the repeating unit in the condition [b] is relatively close to the solubility parameter ⁇ t of the cellulose ester, and it is considered that a partial gradient occurs in the affinity with the cellulose ester in the adhesive polymer layer. . And it is estimated that a part with a comparatively high affinity with a cellulose ester interacts effectively with a cellulose-ester resin layer, and improves interlayer adhesiveness.
  • the adhesive polymer also has the repeating unit [a] having a low solubility parameter ⁇ t, the moisture permeability of the laminate can be effectively suppressed. Furthermore, in the laminate in which the adhesive polymer layer and the cellulose ester resin layer are laminated, due to the laminated structure of different materials, diffusion of moisture that has entered inside is suppressed, and moisture permeability is more effectively suppressed. It is considered a thing.
  • the lower limit of the weight average molecular weight of the adhesive polymer used in the present invention is preferably 5,000 or more, more preferably 10,000 or more, and 15,000 or more from the viewpoint of the film surface shape. More preferably, it is more preferably 35,000 or more, and most preferably 75,000 or more.
  • the upper limit value of the weight average molecular weight of the adhesive polymer is preferably 2,000,000 or less, more preferably 1,500,000 or less, and 1,000, from the viewpoint of film forming properties. It is more preferable that it is 15,000 or less, it is further preferable that it is 750,000 or less, it is further more preferable that it is 500,000 or less, and it is most preferable that it is 350,000 or less.
  • the film thickness of the adhesive polymer layer is not particularly limited, preferably 1 to 25 ⁇ m, more preferably 1 to 20 ⁇ m, and particularly preferably 1 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, an additive described later.
  • cellulose ester used as a raw material in the production of the cellulose ester resin layer of the present invention will be described.
  • cellulose used as a raw material for the cellulose ester used in the present invention include cotton linter and wood pulp (hardwood pulp, softwood pulp). May be.
  • Raw material cellulose is, for example, Marusawa and Uda, “Plastic Materials Course (17) Fibrous Resin”, Nikkan Kogyo Shimbun (published in 1970) and JIII Journal of Technical Publication No. 2001-1745 (page 7). To page 8) can be used.
  • the cellulose ester normally 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 cellulose acylate commonly 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 either the 6-position and the 2-position are 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 ordering the number average molecular weight measured in terms of polystyrene by gel permeation chromatography (Gel Permeation Chromatography; GPC) with the molecular weight of the glucopyranose unit of cellulose ester or cellulose acylate.
  • GPC Gel Permeation Chromatography
  • the cellulose ester used in the present invention can be synthesized by a conventional method.
  • cellulose acylate can be synthesized using an acid anhydride or acid chloride as an acylating agent.
  • an organic acid for example, acetic acid
  • methylene chloride is used as a reaction solvent.
  • 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.) or an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride, etc.) corresponding to the desired acyl group in 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.
  • 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 membrane method (solvent cast 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. 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 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 conventional 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 polycondensation 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 manufacturing method of the laminated body of this invention is demonstrated.
  • the laminated body of this invention is not specifically limited, A normal method can be employ
  • the adhesive polymer layer is formed by various conventional coating methods to produce a laminate. You can also.
  • a micro gravure coating system can be used preferably.
  • a coating liquid will not be specifically limited, Coating conditions and film-forming conditions Is not particularly limited.
  • it can be produced by a melt casting method or a solution casting method (solvent casting method).
  • a melt film forming method a production method such as a T-die method is preferably used, and a simultaneous coextrusion method is particularly preferable.
  • 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. Is particularly preferable from the viewpoints of stable production and production cost reduction.
  • the haze measured by the following method is preferably 1% or less, more preferably 0.7% or less, and particularly preferably 0.5% or less.
  • a laminate exhibiting such haze is excellent in transparency and suitable as a film member for a liquid crystal display device.
  • the lower limit of haze is 0.001% or more, for example, it is not specifically limited.
  • the haze is measured in accordance with JIS K7136 (2000) using a haze meter (HGM-2DP, Suga Test Instruments) in an environment of 25 ° C. and a relative humidity of 60% using a laminate 40 mm ⁇ 80 mm.
  • the film thickness of the laminate of the present invention can be appropriately determined according to the application, but can be set to 5 to 100 ⁇ m, for example. 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% 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% 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 normal temperature, high humidity, and high temperature and high humidity environments is suppressed. This is also preferable.
  • 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.
  • a particularly preferred adhesive is an aqueous solution 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 adhesive polymer layer side, or the cellulose ester resin layer. You may be on the side. From the viewpoint of improving the adhesion between the polarizer and the laminate, it is preferable to directly bond the cellulose ester resin layer side 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 conventional methods. For example, a birefringence meter (KOBRADH, manufactured by Oji Scientific Instruments) can be used.
  • 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 will be 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 measures orthogonal transmittance and parallel transmittance using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation, and calculates the degree of polarization 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.
  • reaction solution after completion of the dropwise addition was further reacted at 85 ° C. for 6 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, diluted with 500 mL of methyl ethyl ketone, and reprecipitated with 5 L of methanol to obtain a white precipitate. The resulting white precipitate was filtered off, redispersed and washed 3 times with 2 L of methanol, and dried at 60 ° C. overnight to obtain 85.0 g of the target polymer P-1.
  • Synthesis of Polymers P-2 to P-26> the monomer type used was changed to a monomer that leads to the repeating unit shown in Table 1 below, and polymers P-2 to P-26 were obtained in the same manner as in Synthesis Example 1.
  • Table 1 below the numbers described in the “Structure” column of the repeating unit correspond to the numbers of the repeating unit exemplified above (the same applies hereinafter).
  • Table 1 below shows solubility parameters ⁇ t calculated by the Hoy method of the repeating units constituting the polymers obtained in the above synthesis examples and comparative synthesis examples.
  • Table 1 below also shows the molar amount (mol%) of each repeating unit in the polymers obtained in each of the above synthesis examples and comparative synthesis examples.
  • the mol% of the repeating unit in the polymer was identified by 1 H NMR measurement using a nuclear magnetic resonance spectrum measuring apparatus (NMR 300 MHz) manufactured by BRUKER.
  • Table 1 below shows the weight average molecular weights of the polymers obtained in the above synthesis examples and comparative synthesis examples.
  • GPC gel permeation chromatography
  • ⁇ 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.
  • the prepared dope A was uniformly cast from a casting die onto a stainless steel endless band (casting support) having a width of 2000 mm.
  • the amount of residual solvent in the dope A reaches 40% by mass, it is peeled off as a polymer film from the casting support, and is conveyed without being actively stretched by a tenter and dried at 130 ° C. in a drying zone. went.
  • the thickness of the obtained cellulose ester resin layer (cellulose ester film) CA-1 was 55 ⁇ m.
  • the prepared dope A 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.
  • ⁇ Creation of cellulose ester resin layer CA-3> The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution (dope B) having a solid content concentration of 22% by mass.
  • a cellulose acetate solution (dope B) Cellulose acetate with an acetyl substitution degree of 2.87 100 parts by weight Monopet (registered trademark) SB (plasticizer) manufactured by Daiichi Kogyo Kagaku Co. 9.0 parts by weight SAIB-100 (plasticizer) manufactured by Eastman Chemical Co. 3.0 Part by mass Ultraviolet absorber (UV-1) 2.0 parts by mass Methylene chloride (first solvent) 297.7 parts by mass Methanol (second solvent) 75.4 parts by mass 1-butanol (third solvent) 3.8 parts by mass Part
  • the prepared dope B was uniformly cast from a casting die onto a stainless steel endless band (casting support) having a width of 2000 mm.
  • the amount of residual solvent in the dope B reaches 40% by mass, it is peeled off as a polymer film from the casting support, transported without being actively stretched by a tenter, and dried at 130 ° C. in a drying zone. went.
  • the thickness of the obtained cellulose ester resin layer (cellulose ester film) CA-3 was 55 ⁇ m.
  • composition of cellulose ester resin layer CA-4 The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution (dope C) having a solid content concentration of 22% by mass.
  • Dope C Cellulose acetate with an acetyl substitution degree of 2.87 100 parts by weight
  • Polycondensation polymer (A) plasticizer
  • UV absorber (UV-1) 2.0 parts by weight Methylene chloride (first solvent) 297.7 Part by mass Methanol (second solvent) 75.4 parts by mass 1-butanol (third solvent) 3.8 parts by mass
  • Polycondensation polymer (A): Polyester composed of adipic acid and ethanediol (terminal is a hydroxy group) (number average molecular weight 1000)
  • the prepared dope C 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 C reaches 40% by mass, it is peeled off as a polymer film from the casting support, and conveyed without being actively stretched by a tenter and dried at 130 ° C. in a drying zone. went.
  • the obtained cellulose ester resin layer (cellulose ester film) CA-4 had a thickness of 55 ⁇ m.
  • the cellulose ester resin layer (cellulose ester film) CA-5 of the present invention was 55 ⁇ m thick except that 4.0 parts by mass of the following compound (1) was added. Got in.
  • Compound (1) is a barbituric acid compound (Exemplary Compound A-3) described in International Publication No. 2015/005398, and was synthesized by the method described in the publication.
  • Laminate S-2 ⁇ Production of Laminates S-2 to S-30 and Comparative Laminates HS-1 and HS-2>
  • the polymer P-1 used in the adhesive polymer forming composition was changed as shown in Table 2 below, and the cellulose ester resin layer was changed as shown in Table 2 below. Except for the above, laminates S-2 to S-30 and comparative laminates HS-1 and HS-2 were produced in the same manner as in ⁇ Preparation of laminate S-1> above. Each of the obtained laminates had a thickness of 60 ⁇ m.
  • A The eyes of any lattice do not peel off.
  • B Peeling of the lattice is less than 5%.
  • C The lattice peeling is 5% or more and less than 30%.
  • D The peeling of the lattice is 30% or more. The results are shown in Table 2 below.
  • a + The moisture permeability is less than 250 g / m 2 / day.
  • A The moisture permeability is 250 g / m 2 / day or more and less than 500 g.
  • B The moisture permeability is 500 g / m 2 / day or more and less than 1000 g / m 2 / day.
  • C moisture permeability is less than 1000g / m 2 / day or more 1600g / m 2 / day.
  • D The water vapor transmission rate is 1600 g / m 2 / day or more. The results are shown in Table 2 below.
  • the laminate HS-1 having a layer of polymer having the repeating unit of [a] defined in the present invention but not having the repeating unit of [b] on the cellulose ester resin layer, The result was inferior in interlayer adhesion (Comparative Example 1).
  • the laminate HS-2 in which a polymer layer having the repeating unit [b] defined in the present invention but not having the repeating unit [a] is provided on the cellulose ester resin layer has an adhesiveness between the layers.
  • the moisture permeability was high and the moisture barrier action was poor (Comparative Example 2).
  • the laminates S-1 to S-30 including the adhesive polymer layer having both the repeating unit [a] and the repeating unit [b] defined in the present invention have improved adhesion between layers.
  • the results were excellent, and the moisture permeability was low and the moisture barrier action was excellent (Examples 1 to 30).
  • the ZRD 40 and each laminate were washed with water.
  • the obtained ZRD40 and each laminate were repeatedly drained with an air knife three times, and after dropping water, they were retained in a drying zone at 70 ° C. for 15 seconds and dried to obtain a saponified ZRD40 and each laminate.
  • Polarizer plates PL-4 and PL-8 to PL-10 were produced as follows.
  • the laminates S-8 and S-28 to S-30 produced above were subjected to corona treatment on the adhesive polymer layer side.
  • the active energy ray-curable adhesive composition prepared above was applied to an MCD coater (manufactured by Fuji Machine Co., Ltd., cell shape: honeycomb, number of gravure roll wires: 1000 / INCH, rotation speed 140%
  • the film was applied so as to have a thickness of 0.5 ⁇ m.
  • a cycloolefin film having a thickness of 40 ⁇ m (Arton G7810 manufactured by JSR) was prepared, and the surface thereof was subjected to corona treatment.
  • the active energy ray-curable adhesive composition was applied to the corona-treated surface so as to have a thickness of 0.5 ⁇ m in the same manner as described above. Subsequently, the surface on which the active energy ray-curable adhesive composition of laminates S-8 and S-28 to S-30 was applied, and the surface on which the active energy ray-curable adhesive composition of the cycloolefin film was applied Were bonded to both sides of the polarizer prepared above to prepare a polarizing plate precursor. Then, it heated at 50 degreeC using IR heater from both surfaces of this polarizing plate precursor.
  • the active energy ray shown below was irradiated to both surfaces of the polarizing plate precursor, and the said active energy ray hardening-type adhesive composition was hardened. Thereafter, it was dried with hot air at 70 ° C. for 3 minutes to obtain polarizing plates PL-4 and PL-8 to PL-10.
  • active energy rays ultraviolet rays (gallium filled metal halide lamp), irradiation apparatus: Fusion UV Systems, Inc.
  • the illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell.
  • 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 after storage (%) ⁇ Polarization degree before storage (%)]
  • Polarization degree change (%) A +: Polarization degree change amount is less than 0.05% A: Polarization degree change amount is 0.05% or more and less than 2.0% B: Polarization degree change amount is 2.0% or more and less than 3.0% C: Polarization degree Change amount is 3.0% or more and less than 5.0% D: Polarization degree change amount is 5.0% or more The results are shown in Table 3 below.
  • the comparative polarizing plate HPL-1 using the comparative laminate HS-1 as a protective film has a poor interlayer adhesion of the protective film, and the cellulose ester resin layer and the polymer layer are peeled off. A polarizing plate capable of evaluating durability could not be obtained (Comparative Example 3).
  • the comparative polarizing plate HPL-2 using the comparative laminate HS-2 as a protective film resulted in greatly inferior polarizer durability (Comparative Example 4).
  • the polarizing plates PL-1 to PL-10 of the present invention using the laminate of the present invention as a protective film showed excellent polarizer durability.
  • 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

Provided are a laminate, a polarizing plate using this laminate, and an image display device using this polarizing plate. The laminate has a cellulose ester resin layer and an adhesive polymer layer provided directly upon the cellulose ester resin layer. An adhesive polymer constituting the adhesive polymer layer has a repeating unit [a] and a repeating unit [b]. [a]: A repeating unit derived from a specific compound and having a solubility parameter δt calculated by the Hoy method of 13.5-19.5. [b]: A repeating unit derived from a specific compound and having a solubility parameter δt calculated by the Hoy method of 20.0-26.0.

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及び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.
 エレクトロルミネッセンスディスプレイ(ELD)及び液晶表示装置(LCD)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、水分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、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分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、屋外用途等の過酷環境下での使用においてより顕在化する。
Image display devices represented by electroluminescence displays (ELDs) and liquid crystal display devices (LCDs) are increasingly required to be thin. 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 apparatus is partly caused by moisture entering the polarizing plate and degrading the polarizer. The polarizer is protected by laminating a protective film (optical film) on the surface, but the protective film is also required to be thin. When the protective film is thinned, moisture is more likely to come into contact with the polarizer, and the image quality is likely to deteriorate. In addition, such a decrease in image quality becomes more apparent when used in harsh environments such as outdoor applications.
 上記保護フィルムとしては、汎用性や加工性の観点からセルロース系樹脂及びアクリル系樹脂等が広く用いられている。耐久性をより高める必要性から、光学フィルムの改質が進められている(例えば特許文献1~5)。 As the protective film, cellulose resins and acrylic resins are widely used from the viewpoint of versatility and processability. Due to the necessity of further improving the durability, the optical film is being modified (for example, Patent Documents 1 to 5).
国際公開第2009/047924号公報International Publication No. 2009/047924 特開2012-172062号公報JP 2012-172062 A 特開2006-83225号公報JP 2006-83225 A 特開2013-101281号公報JP 2013-101281 A 特開平9-197128号公報JP-A-9-197128
 本発明者らは、偏光子の劣化を抑える観点で検討を重ねた結果、上記各特許文献記載のフィルムをはじめ従来の保護フィルムの構成では、上述した要求水準まで高度に薄膜化した際には水分の侵入を十分に防ぐことができず、偏光子の劣化を目的のレベルに抑えることが困難であることが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、薄膜化しても水分の透過を効果的に抑えることができ、偏光子の保護フィルムとして用いた際に偏光子の劣化を効果的に抑えることができる積層体、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 repeated investigations from the viewpoint of suppressing the deterioration of the polarizer, the inventors of the present invention have a structure of conventional protective films including the films described in the above patent documents. It has become clear that moisture penetration cannot be sufficiently prevented and it is difficult to suppress the deterioration of the polarizer to a target level.
The present invention is a laminate provided with a cellulose ester resin layer, which is excellent in adhesion between layers, can effectively suppress moisture transmission even when thinned, and when used as a protective film for a polarizer It is an object of the present invention to provide a laminate capable of effectively suppressing deterioration of a polarizer, a polarizing plate using the laminated body, 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、溶解度パラメータが特定範囲内にある特定構造の繰り返し単位と、この繰り返し単位とは溶解度パラメータが異なる特定構造の繰り返し単位とを有するポリマーの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、上記ポリマーの層とセルロースエステル樹脂層との層間の密着性に優れること、また透湿度が低く偏光子の保護フィルムとして用いることにより高温高湿条件下においても偏光子の劣化を効果的に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 have found that a polymer having a repeating unit having a specific structure in which the solubility parameter is within a specific range, and a repeating unit having a specific structure in which the solubility parameter is different from the repeating unit. The laminate in which the layer is directly provided on the cellulose ester resin layer has excellent adhesion between the polymer layer and the cellulose ester resin layer, and has a low moisture permeability and is used as a protective film for a polarizer. It has been found that deterioration of the polarizer can be effectively suppressed even under wet conditions.
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られた密着性ポリマー層とを有し、上記密着性ポリマー層を構成する密着性ポリマーが下記〔a〕の繰り返し単位の少なくとも1種と下記〔b〕の繰り返し単位の少なくとも1種とを有する積層体。
〔a〕:
 (メタ)アクリル酸エステル化合物、オレフィン化合物、ビニリデン化合物又は環状オレフィン化合物由来の繰り返し単位であって、Hoy法により算出される溶解度パラメータδtが13.5~19.5である繰り返し単位。
〔b〕:
 (メタ)アクリル酸エステル化合物、(メタ)アクリル酸化合物、(メタ)アクリルアミド化合物、酢酸ビニル化合物、ビニルケトン化合物、無水マレイン酸化合物もしくはスチレン化合物由来の繰り返し単位又はこれらの繰り返し単位以外でエチレン性不飽和結合を有する化合物由来の繰り返し単位であって、Hoy法により算出される溶解度パラメータδtが20.0~26.0である繰り返し単位。
[2]
 上記密着性ポリマーが、上記〔b〕の繰り返し単位として下記一般式1で表される繰り返し単位を有する、[1]に記載の積層体。
一般式1:
Figure JPOXMLDOC01-appb-C000005
 一般式1中、
は水素原子又はアルキル基を示す。
及びR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。
L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(R)-から選ばれる2価の連結基もしくはこれらの連結基の2種以上を組合せてなる2価の連結基を示す。
は水素原子又はアルキル基を示す。
[3]
 上記密着性ポリマーが、上記〔a〕の繰り返し単位として下記一般式2で表される繰り返し単位を有する、[1]又は[2]に記載の積層体。
一般式2:
Figure JPOXMLDOC01-appb-C000006
 一般式2中、
は水素原子又はアルキル基を示す。
及びR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。
は炭素数1~20のアルキル基又は炭素数3~10のシクロアルキル基を示す。
[4]
 上記密着性ポリマーを構成するモノマー成分の総モル量中に占める上記〔b〕の繰り返し単位のモル量が5モル%以上90モル%以下である、[1]~[3]のいずれかに記載の積層体。
[5]
 上記密着性ポリマーが、上記〔b〕の繰り返し単位として下記一般式1-1で表される繰り返し単位を有する、[1]~[4]のいずれかに記載の積層体;
一般式1-1:
Figure JPOXMLDOC01-appb-C000007
 一般式1-1中、R及びLは、それぞれ上記一般式1におけるR及びLと同義である。
[6]
 上記密着性ポリマーが、上記〔a〕の繰り返し単位として下記一般式2-2で表される繰り返し単位を有する、[1]~[5]のいずれかに記載の積層体。
一般式2-2
Figure JPOXMLDOC01-appb-C000008
 一般式2-2中、R及びRは、それぞれ上記一般式2におけるR及びRと同義である。
[7]
 上記セルロースエステル樹脂層を構成するセルロースエステルがセルロースアシレートである、[1]~[6]のいずれかに記載の積層体。
[8]
 [1]~[7]のいずれかに記載の積層体と、偏光子とを有する偏光板。
[9]
 [8]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 an adhesive polymer layer provided directly on the cellulose ester resin layer, and the adhesive polymer constituting the adhesive polymer layer is at least one repeating unit of the following [a]: The laminated body which has at least 1 sort (s) of the repeating unit of following [b].
[A]:
A repeating unit derived from a (meth) acrylic ester compound, an olefin compound, a vinylidene compound or a cyclic olefin compound and having a solubility parameter δt calculated by the Hoy method of 13.5 to 19.5.
[B]:
(Meth) acrylic acid ester compounds, (meth) acrylic acid compounds, (meth) acrylamide compounds, vinyl acetate compounds, vinyl ketone compounds, maleic anhydride compounds or repeating units derived from styrene compounds or ethylenically unsaturated other than these repeating units A repeating unit derived from a compound having a bond and having a solubility parameter δt calculated by the Hoy method of 20.0 to 26.0.
[2]
The laminate according to [1], wherein the adhesive polymer has a repeating unit represented by the following general formula 1 as the repeating unit of [b].
General formula 1:
Figure JPOXMLDOC01-appb-C000005
In general formula 1,
R 1 represents a hydrogen atom or an alkyl group.
R 2 and R 3 represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
L is a single bond, or a divalent linking group selected from an alkylene group, an arylene group, —C (═O) —, —O— and —N (R 4 ) —, or 2 of these linking groups. A divalent linking group formed by combining more than one species is shown.
R 4 represents a hydrogen atom or an alkyl group.
[3]
The laminate according to [1] or [2], wherein the adhesive polymer has a repeating unit represented by the following general formula 2 as the repeating unit of [a].
General formula 2:
Figure JPOXMLDOC01-appb-C000006
In general formula 2,
R 5 represents a hydrogen atom or an alkyl group.
R 6 and R 7 represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
R 8 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms.
[4]
Any one of [1] to [3], wherein the molar amount of the repeating unit [b] in the total molar amount of the monomer component constituting the adhesive polymer is 5 mol% or more and 90 mol% or less. Laminated body.
[5]
The laminate according to any one of [1] to [4], wherein the adhesive polymer has a repeating unit represented by the following general formula 1-1 as the repeating unit of [b];
Formula 1-1:
Figure JPOXMLDOC01-appb-C000007
In the Formula 1-1, R 1 and L are respectively the same meanings as R 1 and L in the above general formula 1.
[6]
The laminate according to any one of [1] to [5], wherein the adhesive polymer has a repeating unit represented by the following general formula 2-2 as the repeating unit of [a].
Formula 2-2
Figure JPOXMLDOC01-appb-C000008
In the Formula 2-2, R 5 and R 8 are the same meanings as R 5 and R 8 in the general formula 2.
[7]
The laminate according to any one of [1] to [6], wherein the cellulose ester constituting the cellulose ester resin layer is cellulose acylate.
[8]
A polarizing plate comprising the laminate according to any one of [1] to [7] and a polarizer.
[9]
The image display apparatus which has a polarizing plate as described in [8].
 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や連結基等(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, and the like (hereinafter referred to as substituents) indicated by specific symbols, or when a plurality of substituents 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(変性)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酸とで形成された、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。
 本明細書において、「(メタ)アクリル酸」との用語は、メタクリル酸及びアクリル酸の両方を包含する意味に用いる。このことは「(メタ)アクリルアミド」についても同様である。本明細書において、「アクリル酸」との用語は通常よりも広義の意味で用いている。すなわち、「アクリル酸」は、R-C(=CR )COOHの構造を有する化合物すべてを包含する意味に用いる(R及びRは各々独立に水素原子又は置換基を示す。ただし、Rがメチルである場合、メタクリル酸を意味する))。このことは、「アクリルアミド」についても同様である。
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 (modified) within a range where the desired effect is exhibited.
In addition, as a salt of a compound, for example, an acid addition salt of a compound formed with a compound and an inorganic acid or an organic acid, or a base addition salt of a compound formed with a compound and an inorganic base or an organic basic acid Etc. 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.
In this specification, the term “(meth) acrylic acid” is used to include both methacrylic acid and acrylic acid. The same applies to “(meth) acrylamide”. In this specification, the term “acrylic acid” is used in a broader sense than usual. That is, “acrylic acid” is used to include all compounds having the structure of R A —C (═CR B 2 ) COOH (R A and R B each independently represent a hydrogen atom or a substituent, provided that , When R A is methyl, means methacrylic acid)). The same applies to “acrylamide”.
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、硫黄原子が挙げられ、5員環若しくは6員環又はこれらの縮合環が好ましい。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 and a sulfur atom. A condensed ring is preferable, and specific examples include imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, and the like. (Preferably having 3 to 40 carbon atoms, more preferably 3 to 30, and particularly preferably 3 to 24, In example, a trimethylsilyl group, etc. triphenylsilyl group).
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、層間の密着性に優れ、薄膜化しても水分の透過を効果的に抑えることができる。本発明の積層体は偏光子と重ねあわせることにより高温高湿条件下での偏光子の劣化を効果的に抑えることができる。
 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、過酷な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」又は「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 is excellent in adhesion between layers and can effectively suppress the permeation of moisture even if it is made thin. The laminate of the present invention can effectively suppress the deterioration of the polarizer under high temperature and high humidity conditions by overlapping with the polarizer.
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 severe 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.
[積層体]
 本発明の積層体10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密着性ポリマー層12を有する。セルロースエステル樹脂層11と密着性ポリマー層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の片面に密着性ポリマー層12が設けられていてもよいし、両面に密着性ポリマー層12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10はセルロースエステル樹脂層11の片面に密着性ポリマー層12が設けられた形態である。
 なお、密着性ポリマー層として、組成比が異なる2層以上の密着性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。
[Laminate]
As shown in FIG. 1, the laminate 10 of the present invention has a cellulose ester resin layer 11 and an adhesive polymer layer 12 provided directly on the cellulose ester resin layer 11. Details of the cellulose ester resin layer 11 and the adhesive polymer layer 12 will be described later. As shown in FIG. 1, the laminate of the present invention may have an adhesive polymer layer 12 provided on one side of the cellulose ester resin layer 11 or an adhesive polymer layer 12 provided on both sides. Also good. More preferably, the laminate 10 of the present invention has a form in which the adhesive polymer layer 12 is provided on one side of the cellulose ester resin layer 11.
As the adhesive polymer layer, two or more adhesive polymer layers having different composition ratios may be provided on 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と密着性ポリマー層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。 Further, 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 adhesive 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.
<密着性ポリマー層>
 本発明の積層体を構成する密着性ポリマー層について説明する。
 本発明において、「密着性ポリマー層」とは、後述する密着性ポリマーを層中に50質量%以上含有する層を意味する。密着性ポリマー層中の密着性ポリマーの含有量は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。密着性ポリマーの含有量が多いほど、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好ましい。そのため、密着性ポリマー層中の密着性ポリマーの含有量は100質量%でもよく、通常は99質量%以下である。上記密着性ポリマー層中の密着性ポリマーの含有量が100質量%でない場合、残部は各種の慣用添加剤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。
 密着性ポリマーは2種以上を併用してもよい。すなわち、組成比及び/又は分子量等が異なる密性ポリマー同士を併用してもよい。この場合、密着性ポリマーの合計量が上記範囲内となる。
 なお、本明細書において「密着性ポリマー」との用語は、単にセルロースエステル樹脂層と密着しうるポリマーという意味合いで、本発明の理解を容易にするために用いているに過ぎない。かかる「密着性ポリマー」には、その密着性の度合にかかわらず、本発明で規定する繰り返し単位を有するポリマーのすべてが包含される。すなわち本発明の要旨ないし技術的範囲の判断に際し、「密着性」との用語が、本発明を限定的に解釈する発明特定事項として考慮されるものではない。
<Adhesive polymer layer>
The adhesion polymer layer which comprises the laminated body of this invention is demonstrated.
In the present invention, the “adhesive polymer layer” means a layer containing an adhesive polymer described later in an amount of 50% by mass or more. The content of the adhesive polymer in the adhesive 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 adhesive polymer, the higher the adhesiveness with the cellulose ester resin layer, which is preferable. Therefore, the content of the adhesive polymer in the adhesive polymer layer may be 100% by mass, and is usually 99% by mass or less. When the content of the adhesive polymer in the adhesive polymer layer is not 100% by mass, the balance can contain various conventional additives. Examples of such additives include plasticizers, organic acids, dyes, polymers, retardation modifiers, ultraviolet absorbers, antioxidants, matting agents, and the like.
Two or more adhesive polymers may be used in combination. That is, dense polymers having different composition ratios and / or molecular weights may be used in combination. In this case, the total amount of the adhesive polymer is within the above range.
In the present specification, the term “adhesive polymer” simply means a polymer that can be in close contact with the cellulose ester resin layer, and is merely used to facilitate understanding of the present invention. The “adhesive polymer” includes all polymers having a repeating unit as defined in the present invention regardless of the degree of adhesion. That is, in judging the gist and technical scope of the present invention, the term “adhesiveness” is not considered as an invention specific matter for interpreting the present invention in a limited manner.
- 密着性ポリマー -
 密着性ポリマー層を構成する密着性ポリマーは、1分子中に下記〔a〕の繰り返し単位の少なくとも1種と下記〔b〕の繰り返し単位の少なくとも1種とを有する。
-Adhesive polymer-
The adhesive polymer constituting the adhesive polymer layer has at least one repeating unit of the following [a] and at least one repeating unit of the following [b] in one molecule.
〔a〕:
 (メタ)アクリル酸エステル化合物、オレフィン化合物、ビニリデン化合物又は環状オレフィン化合物由来の繰り返し単位であって、Hoy法により算出される溶解度パラメータδtが13.5~19.5である繰り返し単位。
[A]:
A repeating unit derived from a (meth) acrylic ester compound, an olefin compound, a vinylidene compound or a cyclic olefin compound and having a solubility parameter δt calculated by the Hoy method of 13.5 to 19.5.
〔b〕:
 (メタ)アクリル酸エステル化合物、(メタ)アクリル酸化合物、(メタ)アクリルアミド化合物、酢酸ビニル化合物、ビニルケトン化合物、無水マレイン酸化合物もしくはスチレン化合物由来の繰り返し単位又はこれらの繰り返し単位以外でエチレン性不飽和結合を有する化合物由来の繰り返し単位であって、Hoy法により算出される溶解度パラメータδtが20.0~26.0である繰り返し単位。
[B]:
(Meth) acrylic acid ester compounds, (meth) acrylic acid compounds, (meth) acrylamide compounds, vinyl acetate compounds, vinyl ketone compounds, maleic anhydride compounds or repeating units derived from styrene compounds or ethylenically unsaturated other than these repeating units A repeating unit derived from a compound having a bond and having a solubility parameter δt calculated by the Hoy method of 20.0 to 26.0.
 上記溶解度パラメータδtは、文献“Properties of Polymers 3rd,ELSEVIER,(1990)”の第214~220頁、「2) Method of Hoy (1985,1989)」欄に記載のAmorphous Polymersについて求められるδtを意味し、上記文献の上記の欄の記載に従い算出される。本発明において溶解度パラメータδtの単位は「(cal/cm1/2」である。 The solubility parameter δt is literature "Properties of Polymers 3 rd, ELSEVIER , (1990)" The δt obtained for Amorphous Polymers according to the 214-220 pages, "2) Method of Hoy (1985,1989)" column of Meaning and calculated according to the description in the above column of the above document. Units of the solubility parameter δt in the present invention are "(cal / cm 3) 1/2."
 上記〔a〕の繰り返し単位としては、上記〔a〕を満たす限り特に限定されない。
 上記〔a〕を満たす繰り返し単位が(メタ)アクリル酸エステル化合物由来のものである場合、かかる繰り返し単位の構造として、例えば、特開2004-323770号公報の段落[0021]~[0023]、特開2014-185196号公報の段落[0024]~[0059]等を参照することができる。
 また、上記〔a〕が(メタ)アクリル酸エステル化合物由来の繰り返し単位である場合、(メタ)アクリル酸アルキルエステル化合物又は(メタ)アクリル酸シクロアルキルエステル化合物由来の繰り返し単位であることがより好ましい。この(メタ)アクリル酸アルキルエステル化合物のアルキル基は直鎖でも分岐を有してもよい。(メタ)アクリル酸アルキルエステル化合物を構成するアルキル基の炭素数は1~30が好ましく、3~30がより好ましく、4~20がさらに好ましく、5~18がさらに好ましく、6~16がさらに好ましい。
 上記〔a〕の繰り返し単位を導く上記(メタ)アクリル酸エステル化合物及び(メタ)アクリル酸シクロアルキルエステル化合物の具体例として、例えば、アクリル酸プロピル、アクリル酸イソプロピル、アクリル酸n-ブチル、アクリル酸iso-ブチル、アクリル酸sec-ブチル、アクリル酸tert-ブチル、アクリル酸ヘキシル、アクリル酸シクロヘキシル、アクリル酸2-エチルヘキシル、アクリル酸ドデシル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸イソプロピル、メタクリル酸n-ブチル、メタクリル酸ヘキシル、メタクリル酸シクロヘキシル、メタクリル酸2-エチルヘキシル、メタクリル酸ドデシルを挙げることができる。
The repeating unit [a] is not particularly limited as long as the above [a] is satisfied.
When the repeating unit satisfying the above [a] is derived from a (meth) acrylic acid ester compound, examples of the structure of the repeating unit include paragraphs [0021] to [0023] of JP-A No. 2004-323770, Reference may be made to paragraphs [0024] to [0059] of Japanese Unexamined Patent Publication No. 2014-185196.
Moreover, when the above [a] is a repeating unit derived from a (meth) acrylic acid ester compound, it is more preferably a repeating unit derived from a (meth) acrylic acid alkyl ester compound or a (meth) acrylic acid cycloalkyl ester compound. . The alkyl group of this (meth) acrylic acid alkyl ester compound may be linear or branched. The alkyl group constituting the (meth) acrylic acid alkyl ester compound preferably has 1 to 30 carbon atoms, more preferably 3 to 30 carbon atoms, still more preferably 4 to 20 carbon atoms, still more preferably 5 to 18 carbon atoms, and even more preferably 6 to 16 carbon atoms. .
Specific examples of the (meth) acrylic acid ester compound and (meth) acrylic acid cycloalkyl ester compound for deriving the repeating unit [a] above include, for example, propyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylic acid iso-butyl, sec-butyl acrylate, tert-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, Mention may be made of n-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate.
 上記〔a〕の繰り返し単位がオレフィン化合物由来のものである場合、かかる繰り返し単位の構造として、例えば、特開2000-159817号公報の段落[0015]等を参照することができる。
 上記〔a〕の繰り返し単位を導く上記オレフィン化合物の具体例として、例えば、エチレン、プロピレン、イソプレン、ブタジエン、イソブテン、塩化ビニルを挙げることができる。
When the repeating unit [a] is derived from an olefin compound, for example, paragraph [0015] of JP-A No. 2000-159817 can be referred to as the structure of such a repeating unit.
Specific examples of the olefin compound for deriving the repeating unit [a] include ethylene, propylene, isoprene, butadiene, isobutene and vinyl chloride.
 上記〔a〕の繰り返し単位がビニリデン化合物由来のものである場合、かかる繰り返し単位の構造として、例えば、特開2015-44967号公報の段落[0032]~[0041]、特開平8-67793号公報の段落[0008]~[0009]等を参照することができる。
 上記〔a〕の繰り返し単位を導く上記ビニリデン化合物の具体例として、例えば、塩化ビニリデン、フッ化ビニリデン、テトラフルオロエチレン、塩化トリフルオロエチレン、パーフルオロアルコキシトリフルオロエチレンを挙げることができる。
When the repeating unit [a] is derived from a vinylidene compound, examples of the structure of the repeating unit include paragraphs [0032] to [0041] of JP-A-2015-44967 and JP-A-8-67793. Paragraphs [0008] to [0009] and the like can be referred to.
Specific examples of the vinylidene compound for deriving the repeating unit [a] include, for example, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, trifluoroethylene chloride, and perfluoroalkoxytrifluoroethylene.
 上記〔a〕の繰り返し単位が環状オレフィン化合物由来のものである場合、上記〔a〕の繰り返し単位を導く上記環状オレフィン化合物の具体例として、例えば、シクロヘキセン、ノルボルネン、テトラシクロドデセン、及びそれらから導かれる化合物を挙げることができる。 When the repeating unit [a] is derived from a cyclic olefin compound, specific examples of the cyclic olefin compound leading to the repeating unit [a] include, for example, cyclohexene, norbornene, tetracyclododecene, and the like. Mention may be made of the derived compounds.
 上記密着性ポリマーは上記〔a〕の繰り返し単位として、下記一般式2で表される繰り返し単位を有することが好ましい。
一般式2:
Figure JPOXMLDOC01-appb-C000009
The adhesive polymer preferably has a repeating unit represented by the following general formula 2 as the repeating unit [a].
General formula 2:
Figure JPOXMLDOC01-appb-C000009
 一般式2中、Rは水素原子又はアルキル基を示す。
 Rとして採り得る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。R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。
 Rは水素原子又はメチルが好ましい。
In General Formula 2, R 5 represents a hydrogen atom or an alkyl group.
The alkyl group that can be adopted as R 5 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 5 is more preferably methyl or ethyl, and even more preferably methyl.
R 5 is preferably a hydrogen atom or methyl.
 R及びR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。
 R及びRとして採り得る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。R及びRとして採り得るアルキル基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。
 R及びRとして採り得るアリール基は、その炭素数は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。
 R及びRとして採り得る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がさらに好ましい。R及びRとして採り得るアルコキシカルボニル基は、より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。
 Rは炭素数1~20のアルキル基又は炭素数3~20のシクロアルキル基を示す。
 Rとして採り得る炭素数1~20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1~15が好ましく、1~12がより好ましく、1~10がさらに好ましく、1~8がさらに好ましく、1~6がさらに好ましい。
 また、Rとして採り得る炭素数1~20のアルキル基が置換基を有する場合、ハロゲン原子が好ましく、フッ素原子であることがより好ましい。
 Rとして採り得る炭素数3~20のシクロアルキル基は、その炭素数は4~15がより好ましく、5~12がさらに好ましい。Rとして採り得る炭素数3~20のシクロアルキル基は、このシクロアルキル基が有している置換基同士が互いに連結し、縮環を形成した形態であることも好ましい。
 また、Rとして採り得る炭素数3~20のシクロアルキル基が置換基を有する場合、アルキル基(直鎖でも分岐を有していてもよい)であることが好ましく、炭素数1~4のアルキル基であることがより好ましく、メチル、エチル又はt-ブチルであることがさらに好ましい。
R 6 and R 7 represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
The alkyl group which can be taken as R 6 and R 7 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. The alkyl group that can be taken as R 6 and R 7 is more preferably methyl or ethyl, and even more preferably methyl.
The aryl group that can be adopted as R 6 and R 7 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.
The alkoxycarbonyl group that can be employed as R 6 and R 7 preferably has 2 to 10 carbon atoms, and more preferably 2 to 5 carbon atoms. The alkoxycarbonyl group which can be taken as R 6 and R 7 is more preferably methoxycarbonyl or ethoxycarbonyl.
R 8 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.
The alkyl group having 1 to 20 carbon atoms that can be taken as R 8 may be linear or branched. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 12, more preferably 1 to 10, still more preferably 1 to 8, and still more preferably 1 to 6.
In addition, when the alkyl group having 1 to 20 carbon atoms that can be taken as R 8 has a substituent, a halogen atom is preferable, and a fluorine atom is more preferable.
The cycloalkyl group having 3 to 20 carbon atoms that can be adopted as R 8 has more preferably 4 to 15 carbon atoms, and further preferably 5 to 12 carbon atoms. The cycloalkyl group having 3 to 20 carbon atoms that can be employed as R 8 is preferably in a form in which the substituents of the cycloalkyl group are connected to each other to form a condensed ring.
Further, when the cycloalkyl group having 3 to 20 carbon atoms that can be taken as R 8 has a substituent, it is preferably an alkyl group (which may be linear or branched), and has 1 to 4 carbon atoms. An alkyl group is more preferable, and methyl, ethyl, or t-butyl is more preferable.
 上記密着性ポリマーは、上記〔a〕の繰り返し単位の総モル量中に占める上記一般式2で表される繰り返し単位のモル量が50モル%以上であることが好ましく、70モル%以上であることがより好ましく、80モル%以上であることがさらに好ましく、90モル%以上であることがさらに好ましい。また、上記密着性ポリマーは、上記〔a〕の繰り返し単位の総モル量中に占める上記一般式2で表される繰り返し単位のモル量が100モル%以下であることが好ましく、上記密着性ポリマー中に含まれる上記〔a〕の繰り返し単位のすべてが上記一般式2で表される繰り返し単位であることも好ましい。 In the adhesive polymer, the molar amount of the repeating unit represented by the general formula 2 in the total molar amount of the repeating unit [a] is preferably 50 mol% or more, and 70 mol% or more. More preferably, it is 80 mol% or more, more preferably 90 mol% or more. The adhesive polymer preferably has a molar amount of the repeating unit represented by the general formula 2 in the total molar amount of the repeating unit [a] of 100 mol% or less. It is also preferred that all of the repeating units [a] contained therein are repeating units represented by the general formula 2.
 上記密着性ポリマーは上記〔a〕の繰り返し単位として、下記一般式2-2で表される繰り返し単位を有することがより好ましい。
一般式2-2
Figure JPOXMLDOC01-appb-C000010
The adhesive polymer more preferably has a repeating unit represented by the following general formula 2-2 as the repeating unit of the above [a].
Formula 2-2
Figure JPOXMLDOC01-appb-C000010
 一般式2-2中、R及びRは、それぞれ上記一般式2におけるR及びRと同義であり、好ましい形態も同じである。 In General Formula 2-2, R 5 and R 8 have the same meanings as R 5 and R 8 in General Formula 2, respectively, and preferred forms are also the same.
 上記密着性ポリマーは、上記〔a〕の繰り返し単位の総モル量中に占める上記一般式2-2で表される繰り返し単位のモル量が50モル%以上であることが好ましく、70モル%以上であることがより好ましく、80モル%以上であることがさらに好ましく、90モル%以上であることがさらに好ましい。また、上記密着性ポリマーは、上記〔a〕の繰り返し単位の総モル量中に占める上記一般式2-2で表される繰り返し単位のモル量が100モル%以下であることが好ましく、上記密着性ポリマー中に含まれる上記〔a〕の繰り返し単位のすべてが上記一般式2-2で表される繰り返し単位であることも好ましい。 In the adhesive polymer, the molar amount of the repeating unit represented by the general formula 2-2 in the total molar amount of the repeating unit [a] is preferably 50 mol% or more, and 70 mol% or more. More preferably, it is more preferably 80 mol% or more, and still more preferably 90 mol% or more. The adhesive polymer preferably has a molar amount of the repeating unit represented by the general formula 2-2 in the total molar amount of the repeating unit [a] of 100 mol% or less. It is also preferred that all of the repeating units [a] contained in the conductive polymer are repeating units represented by the general formula 2-2.
 上記〔a〕の繰り返し単位の好ましい例を以下に構造式として示すが、本発明はこれらの例に限定されるものではない。 Preferred examples of the repeating unit [a] are shown below as structural formulas, but the present invention is not limited to these examples.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
 なお、上記〔a〕の繰り返し単位においては、(メタ)アクリル酸エステル化合物は(メタ)アクリル酸化合物を含むものとする。 In the above repeating unit [a], the (meth) acrylic acid ester compound includes a (meth) acrylic acid compound.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
 なお、上記A-32はビニリデン化合物由来の繰り返し単位とも解釈できる。しかし本発明においては、ビニリデン化合物と解釈できるものであっても、その構造が炭素原子と水素原子のみからなる場合には、ビニリデン化合物ではなくオレフィン化合物に分類する。 The above A-32 can also be interpreted as a repeating unit derived from a vinylidene compound. However, in the present invention, even if it can be interpreted as a vinylidene compound, when the structure consists of only a carbon atom and a hydrogen atom, it is classified as an olefin compound instead of a vinylidene compound.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
 上記〔b〕の繰り返し単位としては、上記〔b〕を満たす限り特に限定されない。
 上記〔b〕を満たす繰り返し単位が(メタ)アクリル酸エステル化合物由来のものである場合、かかる繰り返し単位の構造として、例えば、特開2004-323770号公報の段落[0021]~[0023]、特開2014-185196号公報の[0024]~[0059]等を参照することができる。
 上記〔b〕の繰り返し単位を導く上記(メタ)アクリル酸エステル化合物の具体例としては、例えば、アクリル酸2-ヒドロキシエチル、アクリル酸2-アセトアセトキシエチル、アクリル酸2-イソシアナトエチル、メタクリル酸2-ヒドロキシエチル、メタクリル酸2-ジメチルアミノエチル、メタクリル酸2-ジエチルアミノエチル、メタクリル酸2-イソシアナトエチルが挙げられる。
The repeating unit [b] is not particularly limited as long as the above [b] is satisfied.
When the repeating unit satisfying the above [b] is derived from a (meth) acrylic acid ester compound, examples of the structure of the repeating unit include paragraphs [0021] to [0023] of JP-A-2004-323770. Reference may be made to [0024] to [0059] of JP 2014-185196.
Specific examples of the (meth) acrylic acid ester compound for deriving the repeating unit [b] include, for example, 2-hydroxyethyl acrylate, 2-acetoacetoxyethyl acrylate, 2-isocyanatoethyl acrylate, and methacrylic acid. Examples thereof include 2-hydroxyethyl, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, and 2-isocyanatoethyl methacrylate.
 上記〔b〕の繰り返し単位が(メタ)アクリル酸化合物由来のものである場合、かかる繰り返し単位の構造として、例えば、特開2002-212221号公報の段落[0020]~[0027]等を参照することができる。
 上記〔b〕の繰り返し単位を導く(メタ)アクリル酸化合物の具体例としては、例えば、アクリル酸及びその金属塩、メタクリル酸及びその金属塩を挙げることができる。
When the repeating unit [b] is derived from a (meth) acrylic acid compound, refer to paragraphs [0020] to [0027] of JP 2002-212221 A, for example, as the structure of the repeating unit. be able to.
Specific examples of the (meth) acrylic acid compound from which the repeating unit [b] is derived include acrylic acid and its metal salt, and methacrylic acid and its metal salt.
 上記〔b〕の繰り返し単位が(メタ)アクリルアミド化合物由来のものである場合の好ましい構造は、後に例示する構造式中に示される通りである。 A preferable structure when the repeating unit [b] is derived from a (meth) acrylamide compound is as shown in the structural formula exemplified later.
 上記〔b〕の繰り返し単位が酢酸ビニル化合物由来のものである場合、かかる繰り返し単位の構造として、例えば、特開2002-338609号公報の段落[0007]~[0008]等を参照することができる。
 上記〔b〕の繰り返し単位を導く酢酸ビニル化合物の具体例としては、例えば、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、イソプロペニルアセテート等を挙げることができる。このように、本発明において「酢酸ビニル化合物」は、酢酸ビニルが有する水素原子が置換された形態の化合物を包含する意味に用いる。
When the repeating unit [b] is derived from a vinyl acetate compound, for example, paragraphs [0007] to [0008] of JP-A-2002-338609 can be referred to as the structure of such a repeating unit. .
Specific examples of the vinyl acetate compound from which the repeating unit [b] is derived include vinyl acetate, vinyl propionate, vinyl pivalate, isopropenyl acetate and the like. Thus, in the present invention, “vinyl acetate compound” is used to include a compound in which a hydrogen atom of vinyl acetate is substituted.
 上記〔b〕の繰り返し単位がビニルケトン化合物由来のものである場合、かかる繰り返し単位の構造として、例えば、特開2007-230940号公報の段落[0010]~[0017]、特開平7-291886号公報の段落[0009]~[0011]等を参照することができる。
 上記〔b〕の繰り返し単位を導くビニルケトン化合物の具体例としては、例えば、メチルビニルケトン、エチルビニルケトン等を挙げることができる。
 本発明においてビニルケトン化合物は、下記構造を有し、且つ、アクリル酸エステル化合物でなく、アクリルアミド化合物でなく、アクリル酸化合物でもない化合物を意味する。
When the repeating unit [b] is derived from a vinyl ketone compound, examples of the structure of the repeating unit include, for example, paragraphs [0010] to [0017] of JP-A-2007-230940 and JP-A-7-291886. Paragraphs [0009] to [0011] and the like can be referred to.
Specific examples of the vinyl ketone compound for deriving the repeating unit [b] include methyl vinyl ketone and ethyl vinyl ketone.
In the present invention, the vinyl ketone compound means a compound having the following structure and not an acrylate compound, an acrylamide compound, or an acrylic acid compound.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
 上記〔b〕の繰り返し単位が無水マレイン酸化合物由来のものである場合、かかる繰り返し単位の構造として、例えば、特開2006-111710号公報の段落[0027]~[0029]、特開2008-156400号公報の段落[0013]~[0015]等を参照することができる。
 上記〔b〕の繰り返し単位を導く無水マレイン酸化合物の具体例としては、例えば、無水マレイン酸、N-メチルマレイミド、N-シクロヘキシルマレイミド、N-フェニルマレイミド等を挙げることができる。このように、本発明において「無水マレイン酸化合物」は、無水マレイン酸から導かれる化合物を包含する意味に用いる。
When the repeating unit [b] is derived from a maleic anhydride compound, examples of the structure of the repeating unit include, for example, paragraphs [0027] to [0029] of JP-A-2006-1111710 and JP-A-2008-156400. Reference may be made to paragraphs [0013] to [0015] and the like of the publication.
Specific examples of the maleic anhydride compound for deriving the repeating unit [b] include maleic anhydride, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like. Thus, in the present invention, “maleic anhydride compound” is used to include a compound derived from maleic anhydride.
 上記〔b〕の繰り返し単位がスチレン化合物由来のものである場合の好ましい構造は、後に例示する構造式中に示される通りである。 A preferable structure when the repeating unit [b] is derived from a styrene compound is as shown in the structural formula exemplified later.
 また、上記〔b〕の繰り返し単位は、上述した各化合物由来の繰り返し単位以外であって、エチレン性不飽和結合(炭素-炭素二重結合)を有する化合物由来の繰り返し単位であってもよい。 The repeating unit [b] may be a repeating unit derived from a compound having an ethylenically unsaturated bond (carbon-carbon double bond) other than the repeating unit derived from each compound described above.
 上記密着性ポリマーは上記〔b〕の繰り返し単位として、下記一般式1で表される繰り返し単位を有することが好ましい。
一般式1:
Figure JPOXMLDOC01-appb-C000017
The adhesive polymer preferably has a repeating unit represented by the following general formula 1 as the repeating unit [b].
General formula 1:
Figure JPOXMLDOC01-appb-C000017
 一般式1中、R、R及びRは、それぞれ上記一般式2におけるR、R及びRと同義であり、好ましい形態も同じである。 In General Formula 1, R 1 , R 2 and R 3 have the same meanings as R 5 , R 6 and R 7 in General Formula 2, respectively, and preferred forms are also the same.
 L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(R)-から選ばれる2価の連結基もしくはこれらの連結基の2種以上を組合せてなる2価の連結基を示す。Rは上記Rと同義であり、好ましい形態も同じである。
 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、Lが-C(=O)-を含む連結基であり、-C(=O)-が主鎖(Rが結合する炭素原子)に結合することが更に好ましい。
L is a single bond, or a divalent linking group selected from an alkylene group, an arylene group, —C (═O) —, —O— and —N (R 4 ) —, or 2 of these linking groups. A divalent linking group formed by combining more than one species is shown. R 4 has the same meaning as R 1 above, and the preferred form is also the same.
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 is a linking group containing —C (═O) —, and —C (═O) — is bonded to the main chain (the carbon atom to which R 1 is bonded).
 Lとして採り得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。
 Lとして採り得るアリーレン基は、その炭素数は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 that can be taken as L is preferably a straight chain. 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 that can be taken as L 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.
 上記密着性ポリマーは、上記〔b〕の繰り返し単位の総モル量中に占める上記一般式1で表される繰り返し単位のモル量が50モル%以上であることが好ましく、70モル%以上であることがより好ましく、80モル%以上であることがさらに好ましく、90モル%以上であることがさらに好ましい。また、上記密着性ポリマーは、上記〔b〕の繰り返し単位の総モル量中に占める上記一般式1で表される繰り返し単位のモル量が100モル%以下であることが好ましく、上記密着性ポリマー中に含まれる上記〔b〕の繰り返し単位のすべてが上記一般式1で表される繰り返し単位であることも好ましい。 In the adhesive polymer, the molar amount of the repeating unit represented by the general formula 1 in the total molar amount of the repeating unit [b] is preferably 50 mol% or more, and 70 mol% or more. More preferably, it is 80 mol% or more, more preferably 90 mol% or more. The adhesive polymer preferably has a molar amount of the repeating unit represented by the general formula 1 in the total molar amount of the repeating unit [b] of 100 mol% or less. It is also preferred that all of the repeating units [b] contained therein are repeating units represented by the above general formula 1.
 上記密着性ポリマーは上記〔b〕の繰り返し単位として、下記一般式1-1で表される繰り返し単位を有することがより好ましい。
一般式1-1:
Figure JPOXMLDOC01-appb-C000018
 
The adhesive polymer more preferably has a repeating unit represented by the following general formula 1-1 as the repeating unit [b].
Formula 1-1:
Figure JPOXMLDOC01-appb-C000018
 一般式1-1中、R及びLは、それぞれ上記一般式1におけるR及びLと同義であり、好ましい形態も同じである。 In general formula 1-1, R 1 and L have the same meanings as R 1 and L in general formula 1, respectively, and preferred forms are also the same.
 上記密着性ポリマーは、上記〔b〕の繰り返し単位の総モル量中に占める上記一般式1-1で表される繰り返し単位のモル量が50モル%以上であることが好ましく、70モル%以上であることがより好ましく、80モル%以上であることがさらに好ましく、90モル%以上であることがさらに好ましい。また、上記密着性ポリマーは、上記〔b〕の繰り返し単位の総モル量中に占める上記一般式1-1で表される繰り返し単位のモル量が100モル%以下であることが好ましく、上記密着性ポリマー中に含まれる上記〔b〕の繰り返し単位のすべてが上記一般式1-1で表される繰り返し単位であることも好ましい。 In the adhesive polymer, the molar amount of the repeating unit represented by the general formula 1-1 in the total molar amount of the repeating unit [b] is preferably 50 mol% or more, and 70 mol% or more. More preferably, it is more preferably 80 mol% or more, and still more preferably 90 mol% or more. The adhesive polymer preferably has a molar amount of the repeating unit represented by the general formula 1-1 in the total molar amount of the repeating unit [b] of 100 mol% or less. It is also preferred that all of the repeating units [b] contained in the functional polymer are repeating units represented by the general formula 1-1.
 上記〔b〕の繰り返し単位の好ましい例を以下に構造式として示すが、本発明はこれらの例に限定されるものではない。 Preferred examples of the repeating unit [b] are shown below as structural formulas, but the present invention is not limited to these examples.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
 上記密着性ポリマーは、上記〔a〕の繰り返し単位と、上記〔b〕の繰り返し単位の両繰り返し単位を有すれば、各繰り返し単位の含有量については特に制限されない。すなわち、上記密着性ポリマーは、上記〔a〕の繰り返し単位および上記〔b〕の繰り返し単位以外の繰り返し単位を有していてもよい。 The adhesive polymer is not particularly limited as to the content of each repeating unit as long as it has both the repeating unit [a] and the repeating unit [b]. That is, the adhesive polymer may have a repeating unit other than the repeating unit [a] and the repeating unit [b].
 密着性ポリマー層とセルロースエステル樹脂層との親和性をより高め、層間の密着性に優れた積層体を得る観点からは、上記密着性ポリマーを構成するモノマー成分の総モル量中に占める上記〔b〕の繰り返し単位のモル量を、5モル%以上とすることが好ましく、10モル%以上とすることがより好ましく、20モル%以上とすることがさらに好ましい。上記密着性ポリマーを構成するモノマー成分の総モル量中に占める上記〔b〕の繰り返し単位のモル量は、95モル%以下が好ましく、90モル%以下がより好ましく、80モル%以下がさらに好ましい。 From the viewpoint of further improving the affinity between the adhesive polymer layer and the cellulose ester resin layer and obtaining a laminate excellent in interlayer adhesion, the above-mentioned [occupying in the total molar amount of the monomer components constituting the adhesive polymer [ The molar amount of the repeating unit (b) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more. The molar amount of the repeating unit (b) occupying in the total molar amount of the monomer component constituting the adhesive polymer is preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 80 mol% or less. .
 また、密着性と低透湿性をより高いレベルで両立した積層体を得る観点からは、上記密着性ポリマーを構成するモノマー成分の総モル量中に占める上記〔a〕の繰り返し単位のモル量を、5モル%以上とすることが好ましく、10モル%以上とすることがより好ましく、20モル%以上とすることがより好ましく、40モル%以上とすることがさらに好ましく、50モル%以上とすることが特に好ましい。上記密着性ポリマーを構成するモノマー成分の総モル量中に占める上記〔a〕の繰り返し単位のモル量は、95モル%以下が好ましく、90モル%以下がさらに好ましい。 In addition, from the viewpoint of obtaining a laminate having both adhesion and low moisture permeability at a higher level, the molar amount of the repeating unit [a] in the total molar amount of the monomer component constituting the adhesive polymer is determined. It is preferably 5 mol% or more, more preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 40 mol% or more, and 50 mol% or more. It is particularly preferred. The molar amount of the repeating unit [a] in the total molar amount of the monomer component constituting the adhesive polymer is preferably 95 mol% or less, and more preferably 90 mol% or less.
 上記密着性ポリマー中、上記〔a〕の繰り返し単位の含有量と上記〔b〕の繰り返し単位の含有量は、合計で50質量%以上であることが好ましく、70質量%以上であることがより好ましく、80質量%以上であることがさらに好ましく、90質量%以上であることがさらに好ましい。上記密着性ポリマーは上記〔a〕の繰り返し単位と上記〔b〕の繰り返し単位とからなる形態であることも好ましい。 In the adhesive polymer, the content of the repeating unit [a] and the content of the repeating unit [b] is preferably 50% by mass or more, more preferably 70% by mass or more. Preferably, it is 80 mass% or more, more preferably 90 mass% or more. The adhesive polymer is also preferably in the form of the repeating unit [a] and the repeating unit [b].
 上記密着性ポリマー中、上記〔a〕の繰り返し単位の含有量と、上記〔b〕の繰り返し単位の含有量は、モル比で、[〔a〕の繰り返し単位]/[〔b〕の繰り返し単位]=95/5~10/90を満たすことが好ましく、[〔a〕の繰り返し単位]/[〔b〕の繰り返し単位]=95/5~30/70を満たすことがより好ましく、[〔a〕の繰り返し単位]/[〔b〕の繰り返し単位]=92/8~50/50を満たすことがさらに好ましく、[〔a〕の繰り返し単位]/[〔b〕の繰り返し単位]=90/10~60/40を満たすことがさらに好ましく、[〔a〕の繰り返し単位]/[〔b〕の繰り返し単位]=90/10~75/25を満たすことがさらに好ましい。 In the adhesive polymer, the content of the repeating unit [a] and the content of the repeating unit [b] are in a molar ratio: [[a] repeating unit] / [[b] repeating unit. ] = 95/5 to 10/90, preferably [repeat unit of [a]] / [repeat unit of [b]] = 95/5 to 30/70, more preferably [[a ] [Repeat unit] / [repeat unit of [b]] = 92/8 to 50/50 is more preferable, and [repeat unit of [a]] / [repeat unit of [b]] = 90/10. It is more preferable to satisfy ˜60 / 40, and it is more preferable to satisfy [repeat unit of [[a]] / [repeat unit of [b]] = 90/10 to 75/25.
 上記密着性ポリマーはランダムポリマーでもよいしブロックポリマーでもよい。 The adhesive polymer may be a random polymer or a block polymer.
 上記〔a〕の繰り返し単位と上記〔b〕の繰り返し単位を有するポリマーを用いた層が、セルロースエステル樹脂層との密着性に優れる理由は定かではないが、次のように推定される。すなわち、条件〔b〕の繰り返し単位の溶解度パラメータδtは、セルロースエステルの溶解度パラメータδtと比較的近く、密着性ポリマー層中にはセルロースエステルとの親和性において部分的な傾斜が生じるものと考えられる。そして、セルロースエステルとの親和性が比較的高い部分が、セルロースエステル樹脂層と効果的に相互作用し、層間密着性を高めるものと推定される。しかも上記密着性ポリマーは溶解度パラメータδtが低い上記〔a〕の繰り返し単位も有するために、積層体の透湿性も効果的に抑えることができる。
 さらに上記密着性ポリマーの層とセルロースエステル樹脂層とを積層した積層体は、異なる素材の積層構造に起因して、内部に浸入した水分の拡散が抑制され、透湿度がより効果的に抑えられるものと考えられる。
The reason why the layer using the polymer having the repeating unit [a] and the polymer having the repeating unit [b] is excellent in adhesion to the cellulose ester resin layer is not clear, but is estimated as follows. That is, the solubility parameter δt of the repeating unit in the condition [b] is relatively close to the solubility parameter δt of the cellulose ester, and it is considered that a partial gradient occurs in the affinity with the cellulose ester in the adhesive polymer layer. . And it is estimated that a part with a comparatively high affinity with a cellulose ester interacts effectively with a cellulose-ester resin layer, and improves interlayer adhesiveness. Moreover, since the adhesive polymer also has the repeating unit [a] having a low solubility parameter δt, the moisture permeability of the laminate can be effectively suppressed.
Furthermore, in the laminate in which the adhesive polymer layer and the cellulose ester resin layer are laminated, due to the laminated structure of different materials, diffusion of moisture that has entered inside is suppressed, and moisture permeability is more effectively suppressed. It is considered a thing.
 本発明に用いる上記密着性ポリマーの重量平均分子量の下限値は、フィルム面状の観点から、5,000以上であることが好ましく、10,000以上であることがより好ましく、15,000以上であることがさらに好ましく、35,000以上であることがさらにより好ましく、75,000以上であることが最も好ましい。一方、上記密着性ポリマーの重量平均分子量の上限値は、製膜性の観点から、2,000,000以下であることが好ましく、1,500,000以下であることがより好ましく、1,000,000以下であることがさらに好ましく、750,000以下であることがさらに好ましく、500,000以下であることがさらにより好ましく、350,000以下であることが最も好ましい。 The lower limit of the weight average molecular weight of the adhesive polymer used in the present invention is preferably 5,000 or more, more preferably 10,000 or more, and 15,000 or more from the viewpoint of the film surface shape. More preferably, it is more preferably 35,000 or more, and most preferably 75,000 or more. On the other hand, the upper limit value of the weight average molecular weight of the adhesive polymer is preferably 2,000,000 or less, more preferably 1,500,000 or less, and 1,000, from the viewpoint of film forming properties. It is more preferable that it is 15,000 or less, it is further preferable that it is 750,000 or less, it is further more preferable that it is 500,000 or less, and it is most preferable that it is 350,000 or less.
 上記密着性ポリマー層の膜厚に特に制限はなく、1~25μmが好ましく、1~20μmがより好ましく、1~15μmが特に好ましい。 The film thickness of the adhesive polymer layer is not particularly limited, preferably 1 to 25 μm, more preferably 1 to 20 μm, and particularly preferably 1 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, an additive 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、綿花リンタおよび木材パルプ(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)や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常用される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.
Examples of cellulose used as a raw material for the cellulose ester used in the present invention include cotton linter and wood pulp (hardwood pulp, softwood pulp). May be. Raw material cellulose is, for example, Marusawa and Uda, “Plastic Materials Course (17) Fibrous Resin”, Nikkan Kogyo Shimbun (published in 1970) and JIII Journal of Technical Publication No. 2001-1745 (page 7). To page 8) can be used.
As a cellulose ester, the cellulose ester normally 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常用される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 cellulose acylate commonly 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 either the 6-position and the 2-position are 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序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 ordering the number average molecular weight measured in terms of polystyrene by gel permeation chromatography (Gel Permeation Chromatography; GPC) with 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や酸塩化物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)や塩化メチレンが使用される。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 or acid chloride as an acylating agent. When the acylating agent is an acid anhydride, an organic acid (for example, acetic acid) or methylene chloride 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.) or an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride, etc.) corresponding to the desired acyl group in 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、添加剤の揮散や分解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 membrane method (solvent cast 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や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。 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.
 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、常用の可塑剤、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 conventional 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 polycondensation 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。 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.
[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。
 本発明の積層体は、特に限定されるものではなく、常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、後述する方法でセルロースエステル樹脂層を作製した後、各種常用の塗布方法により密着性ポリマー層を形成し、積層体を製造することもできる。このような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、密着性ポリマーを、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)により製造することができる。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 laminated body of this invention is not specifically limited, A normal method can be employ | adopted. In addition to the melt film forming method and the solution film forming method (solvent casting method), after preparing the cellulose ester resin layer by the method described later, the adhesive polymer layer is formed by various conventional coating methods to produce a laminate. You can also. Although there is no restriction | limiting in particular as such a coating method, A micro gravure coating system can be used preferably. In addition, even if it is a case where any application | coating method is used, if an adhesive polymer is melt | dissolved in a suitable solvent by a suitable density | concentration, a coating liquid will not be specifically limited, Coating conditions and film-forming conditions Is not particularly limited.
In addition, from the viewpoint of suitability for mass production, it can be produced by a melt casting method or a solution casting method (solvent casting method). As the melt film forming method, a production method such as a T-die method is preferably used, and a simultaneous coextrusion method is particularly preferable. 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. Is particularly preferable from the viewpoints of stable production and production cost reduction.
<積層体の物性値>
(ヘイズ)
 本発明の積層体は、下記方法により測定されるヘイズが1%以下であることが好ましく、0.7%以下であることがより好ましく、0.5%以下であることが特に好ましい。このようなヘイズを示す積層体は、透明性に優れ、液晶表示装置のフィルム部材として好適である。ヘイズの下限値は、例えば0.001%以上であるが、特に限定されない。
 ヘイズは、積層体40mm×80mmを用いて、25℃、相対湿度60%の環境下で、ヘイズメーター(HGM-2DP、スガ試験機)を用いて、JIS K7136(2000)にしたがって測定する。
<Physical properties of the laminate>
(Haze)
In the laminate of the present invention, the haze measured by the following method is preferably 1% or less, more preferably 0.7% or less, and particularly preferably 0.5% or less. A laminate exhibiting such haze is excellent in transparency and suitable as a film member for a liquid crystal display device. Although the lower limit of haze is 0.001% or more, for example, it is not specifically limited.
The haze is measured in accordance with JIS K7136 (2000) using a haze meter (HGM-2DP, Suga Test Instruments) in an environment of 25 ° C. and a relative humidity of 60% using a laminate 40 mm × 80 mm.
(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 5 to 100 μm, for example. 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/m/day(24時間)以下であることが好ましく、1000g/m/day以下であることがより好ましく、600g/m/day以下であることがさらに好ましく、200g/m/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 at normal temperature, high humidity, and high temperature and high humidity, and displayed during black display. 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% 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% 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 normal temperature, high humidity, and high temperature and high humidity environments is suppressed. This is also preferable.
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、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. A particularly preferred adhesive is an aqueous solution 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密着性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、密着性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。偏光子と積層体との密着性を高める観点から、セルロースエステル樹脂層の側を偏光子と直接貼合することが好ましい。
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 has a form in which an adhesive 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 adhesive polymer layer side, or the cellulose ester resin layer. You may be on the side. From the viewpoint of improving the adhesion between the polarizer and the laminate, it is preferable to directly bond the cellulose ester resin layer side 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、常用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 conventional methods. For example, a birefringence meter (KOBRADH, manufactured by Oji Scientific Instruments) can be used.
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 a range of ± 10 ° from a strict angle with respect to parallel, orthogonal and 45 °, respectively, and the error from the strict angle is preferably within a range of ± 5 °, and within a 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 will be 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 measures orthogonal transmittance and parallel transmittance using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation, and calculates the degree of polarization 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、液晶表示装置および有機エレクトロルミネッセンス表示装置が挙げられる。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>
 温度計、攪拌羽根、還流環を備えた1Lの三つ口フラスコに、メチルエチルケトン75.0gを仕込み、窒素気流下、85℃で攪拌した。別途、300mL三角フラスコにメタクリル酸メチル(上記例示の繰り返し単位A-1を導くモノマー)131.1g、メタクリル酸2-ヒドロキシエチル(上記例示の繰り返し単位B-1を導くモノマー)18.9g、ジメチル2,2’-アゾビスイソブチレート0.08g、メチルエチルケトン75.0gを量りとり、これらを混合溶解させてモノマー組成物を調製した。
 次に、上記85℃に攪拌したメチルエチルケトン中に、上記モノマー組成物を、1.2mL/minの速度で滴下した。滴下にはケミカルポンプを使用した。滴下終了後の反応溶液を、さらに85℃で6時間反応させ、反応終了後、反応溶液を室温まで放冷し、メチルエチルケトン500mLで希釈し、メタノール5Lで再沈殿させて白色沈殿を得た。得られた白色沈殿をろ別した後、メタノール2Lで再分散洗浄を3回繰り返し、60℃で終夜乾燥することで目的のポリマーP-1を85.0g得た。
[Synthesis example]
<Synthesis Example 1: Synthesis of Polymer P-1>
In a 1 L three-necked flask equipped with a thermometer, stirring blades, and reflux ring, 75.0 g of methyl ethyl ketone was charged and stirred at 85 ° C. under a nitrogen stream. Separately, in a 300 mL Erlenmeyer flask, 131.1 g of methyl methacrylate (monomer leading to the repeating unit A-1 exemplified above), 18.9 g of 2-hydroxyethyl methacrylate (monomer leading to the repeating unit B-1 exemplified above), dimethyl A monomer composition was prepared by measuring 0.08 g of 2,2′-azobisisobutyrate and 75.0 g of methyl ethyl ketone and mixing and dissolving them.
Next, the monomer composition was dropped into methyl ethyl ketone stirred at 85 ° C. at a rate of 1.2 mL / min. A chemical pump was used for dripping. The reaction solution after completion of the dropwise addition was further reacted at 85 ° C. for 6 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, diluted with 500 mL of methyl ethyl ketone, and reprecipitated with 5 L of methanol to obtain a white precipitate. The resulting white precipitate was filtered off, redispersed and washed 3 times with 2 L of methanol, and dried at 60 ° C. overnight to obtain 85.0 g of the target polymer P-1.
<合成例2~26:ポリマーP-2~P-26の合成>
 上記合成例1において、使用するモノマー種を下記表1に示す繰り返し単位を導くモノマーに変更し、合成例1と同様にしてポリマーP-2~P-26を得た。
 なお、下記表1中、繰り返し単位の「構造」のカラムに記載された番号は、上記で例示した繰り返し単位の番号に対応している(以下同様)。
<Synthesis Examples 2 to 26: Synthesis of Polymers P-2 to P-26>
In Synthesis Example 1, the monomer type used was changed to a monomer that leads to the repeating unit shown in Table 1 below, and polymers P-2 to P-26 were obtained in the same manner as in Synthesis Example 1.
In Table 1 below, the numbers described in the “Structure” column of the repeating unit correspond to the numbers of the repeating unit exemplified above (the same applies hereinafter).
<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を下記表1に示す繰り返し単位を導くモノマーに変更し、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。
<Comparative Synthesis Examples 1 and 2: Synthesis of Comparative Polymers HP-1 and HP-2>
In Synthetic Example 1, the monomer species used were changed to monomers that lead to repeating units shown in Table 1 below, and Comparative Polymers HP-1 and HP-2 were obtained in the same manner as in Synthetic Example 1.
 上記各合成例及び比較合成例で得られたポリマーを構成する繰り返し単位の、Hoy法により算出される溶解度パラメータδtを下記表1に示す。
 また、上記各合成例及び比較合成例で得られたポリマー中の各繰り返し単位のモル量(モル%)についても下記表1に示す。ここで、ポリマー中の繰り返し単位のモル%は、BRUKER社製核磁気共鳴スペクトル測定装置(NMR300MHz)を用いたH NMR測定により同定した。
 また、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に示した。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 solubility parameters δt calculated by the Hoy method of the repeating units constituting the polymers obtained in the above synthesis examples and comparative synthesis examples.
Table 1 below also shows the molar amount (mol%) of each repeating unit in the polymers obtained in each of the above synthesis examples and comparative synthesis examples. Here, the mol% of the repeating unit in the polymer was identified by 1 H NMR measurement using a nuclear magnetic resonance spectrum measuring apparatus (NMR 300 MHz) manufactured by BRUKER.
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)
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
[製造例1:積層体S-1~S-30及びHS-1及びHS-2の作製] [Production Example 1: Production of laminates S-1 to S-30 and HS-1 and HS-2]
<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
<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A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、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 A 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 A reaches 40% by mass, it is peeled off as a polymer film from the casting support, and is conveyed without being actively stretched by a tenter and dried at 130 ° C. in a drying zone. went. 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A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 A 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.
<セルロースエステル樹脂層CA-3の作成>
 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B)を調製した。
[セルロースアセテート溶液(ドープB)の組成]
 アセチル置換度2.87のセルロースアセテート     100質量部
 第一工業化学社製モノペット(登録商標)SB(可塑剤) 9.0質量部
 イーストマン・ケミカル社製SAIB-100(可塑剤) 3.0質量部
 紫外線吸収剤(UV-1)               2.0質量部
 メチレンクロライド(第1溶媒)          297.7質量部
 メタノール(第2溶媒)               75.4質量部
 1-ブタノール(第3溶媒)              3.8質量部
<Creation of cellulose ester resin layer CA-3>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution (dope B) having a solid content concentration of 22% by mass.
[Composition of cellulose acetate solution (dope B)]
Cellulose acetate with an acetyl substitution degree of 2.87 100 parts by weight Monopet (registered trademark) SB (plasticizer) manufactured by Daiichi Kogyo Kagaku Co. 9.0 parts by weight SAIB-100 (plasticizer) manufactured by Eastman Chemical Co. 3.0 Part by mass Ultraviolet absorber (UV-1) 2.0 parts by mass Methylene chloride (first solvent) 297.7 parts by mass Methanol (second solvent) 75.4 parts by mass 1-butanol (third solvent) 3.8 parts by mass Part
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
 バンド流延装置を用い、上記調製したドープB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B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-3の厚さは55μmであった。 Using a band casting apparatus, the prepared dope B 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 B reaches 40% by mass, it is peeled off as a polymer film from the casting support, transported without being actively stretched by a tenter, and dried at 130 ° C. in a drying zone. went. The thickness of the obtained cellulose ester resin layer (cellulose ester film) CA-3 was 55 μm.
<セルロースエステル樹脂層CA-4の作成>
 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C)を調製した。
[セルロースアセテート溶液(ドープC)の組成]
 アセチル置換度2.87のセルロースアセテート     100質量部
 重縮合ポリマー(A)(可塑剤)           12.0質量部
 紫外線吸収剤(UV-1)               2.0質量部
 メチレンクロライド(第1溶媒)          297.7質量部
 メタノール(第2溶媒)               75.4質量部
 1-ブタノール(第3溶媒)              3.8質量部
<Creation of cellulose ester resin layer CA-4>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution (dope C) having a solid content concentration of 22% by mass.
[Composition of cellulose acetate solution (Dope C)]
Cellulose acetate with an acetyl substitution degree of 2.87 100 parts by weight Polycondensation polymer (A) (plasticizer) 12.0 parts by weight UV absorber (UV-1) 2.0 parts by weight Methylene chloride (first solvent) 297.7 Part by mass Methanol (second solvent) 75.4 parts by mass 1-butanol (third solvent) 3.8 parts by mass
 重縮合ポリマー(A):アジピン酸とエタンジオールからなるポリエステル(末端はヒドロキシ基)(数平均分子量=1000) Polycondensation polymer (A): Polyester composed of adipic acid and ethanediol (terminal is a hydroxy group) (number average molecular weight = 1000)
 バンド流延装置を用い、上記調製したドープC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C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-4の厚さは55μmであった。 Using a band casting apparatus, the prepared dope C 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 C reaches 40% by mass, it is peeled off as a polymer film from the casting support, and conveyed without being actively stretched by a tenter and dried at 130 ° C. in a drying zone. went. The obtained cellulose ester resin layer (cellulose ester film) CA-4 had a thickness of 55 μm.
<セルロースエステル樹脂層CA-5の作成>
 上記セルロースエステル樹脂層CA-3の作製において、下記化合物(1)を4.0質量部加えた以外は同様にして、本発明の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-5を厚さ55μmで得た。
<Creation of cellulose ester resin layer CA-5>
In the production of the cellulose ester resin layer CA-3, the cellulose ester resin layer (cellulose ester film) CA-5 of the present invention was 55 μm thick except that 4.0 parts by mass of the following compound (1) was added. Got in.
Figure JPOXMLDOC01-appb-C000030
 
Figure JPOXMLDOC01-appb-C000030
 
 なお、化合物(1)は国際公開第2015/005398号記載のバルビツール酸化合物(例示化合物A-3)であり、同公報記載の方法で合成したものである。 Compound (1) is a barbituric acid compound (Exemplary Compound A-3) described in International Publication No. 2015/005398, and was synthesized by the method described in the publication.
<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、密着性ポリマー形成用組成物を得た。次に、上述した手順で作製したセルロースエステル樹脂層CA-1上に、上記密着性ポリマー形成用組成物を、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 an adhesive polymer was obtained. Next, the above-mentioned composition for forming an adhesive polymer was applied on the cellulose ester resin layer CA-1 produced by the above-described procedure 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 film thickness of 60 μm.
<積層体S-2~S-30及び比較積層体HS-1及びHS-2の作製>
 上記<積層体S-1の作製>において、密着性ポリマー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-30、比較積層体HS-1及びHS-2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-30 and Comparative Laminates HS-1 and HS-2>
In <Preparation of Laminate S-1>, the polymer P-1 used in the adhesive polymer forming composition was changed as shown in Table 2 below, and the cellulose ester resin layer was changed as shown in Table 2 below. Except for the above, laminates S-2 to S-30 and comparative laminates HS-1 and HS-2 were produced in the same manner as in <Preparation of laminate S-1> above. Each of the obtained laminates had a thickness of 60 μm.
[試験例1: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密着性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、密着性を評価した。
[Test Example 1: 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 the cutter knife and the cutter guide, 11 cuts with an interval of 1 mm were made on the surface on the adhesive 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 applied to the following evaluation criteria to evaluate the adhesion.
 A:どの格子の目も剥がれがない。
 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。
A: The eyes of any lattice do not peel off.
B: Peeling of the lattice is less than 5%.
C: The lattice peeling is 5% or more and less than 30%.
D: The peeling of the lattice is 30% or more.
The results are shown in Table 2 below.
[試験例2:積層体の透湿度(40℃90%相対湿度での透湿度)の評価]
 透湿度は、「高分子の物性II」(高分子実験講座4 共立出版)の285頁~294頁:蒸気透過量の測定(質量法、温度計法、蒸気圧法、吸着量法)を適用し、評価した。具体的な手順を以下に示す。
 JIS Z-0208の方法に準じて、上記で作製した各積層体を裁断し、この裁断した積層体を透湿カップに装着して試験試料とした。この試験試料を温度40℃、相対湿度90%の条件下で24時間調湿した。
 調湿前後における試験試料の質量をそれぞれ秤量し、調湿前の試験試料の質量をA、調質後の試料の質量をBとして、24時間で試料を通過する水分量Δmを、下記式より算出した。
 Δm=A-B
 次いで、上記Δmを試料面積1mあたりの値に換算し、透湿度(g/m/day)とした。得られた各積層体の透湿度を下記評価基準により評価した。
[Test Example 2: Evaluation of moisture permeability of laminated body (moisture permeability at 40 ° C. and 90% relative humidity)]
For moisture permeability, we applied “Measurement of vapor transmission (mass method, thermometer method, vapor pressure method, adsorption amount method)” on pages 285 to 294 of “Polymer Properties II” (Polymer Experiment Course 4, Kyoritsu Shuppan). ,evaluated. The specific procedure is shown below.
According to the method of JIS Z-0208, each of the laminates produced above was cut, and the cut laminate was attached to a moisture permeable cup to obtain a test sample. This test sample was conditioned for 24 hours under conditions of a temperature of 40 ° C. and a relative humidity of 90%.
The weight of the test sample before and after humidity conditioning is weighed, the mass of the test sample before humidity conditioning is A, and the mass of the sample after tempering is B. Calculated.
Δm = AB
Subsequently, the above Δm was converted to a value per 1 m 2 of the sample area and used as moisture permeability (g / m 2 / day). The moisture permeability of each obtained laminate was evaluated according to the following evaluation criteria.
 A+:透湿度が250g/m/day未満である。
 A:透湿度が250g/m/day以上500g未満である。
 B:透湿度が500g/m/day以上1000g/m/day未満である。
 C:透湿度が1000g/m/day以上1600g/m/day未満である。
 D:透湿度が1600g/m/day以上である。
 結果を下記表2に示す。
A +: The moisture permeability is less than 250 g / m 2 / day.
A: The moisture permeability is 250 g / m 2 / day or more and less than 500 g.
B: The moisture permeability is 500 g / m 2 / day or more and less than 1000 g / m 2 / day.
C: moisture permeability is less than 1000g / m 2 / day or more 1600g / m 2 / day.
D: The water vapor transmission rate is 1600 g / m 2 / day or more.
The results are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000031
 表2に示される通り、本発明で規定する〔a〕の繰り返し単位を有するが、〔b〕の繰り返し単位を有しないポリマーの層をセルロースエステル樹脂層上に設けた積層体HS-1は、層間の密着性に劣る結果となった(比較例1)。逆に、本発明で規定する〔b〕の繰り返し単位を有するが、〔a〕の繰り返し単位を有しないポリマーの層をセルロースエステル樹脂層上に設けた積層体HS-2は、層間の密着性には優れるが、透湿度が高く水分のバリア作用において劣る結果となった(比較例2)。
 これに対し、本発明で規定する〔a〕の繰り返し単位と〔b〕の繰り返し単位の両方を有する密着性ポリマーの層を備えた積層体S-1~S-30は、層間の密着性に優れ、且つ、透湿度が低く水分のバリア作用に優れる結果となった(実施例1~30)。
As shown in Table 2, the laminate HS-1 having a layer of polymer having the repeating unit of [a] defined in the present invention but not having the repeating unit of [b] on the cellulose ester resin layer, The result was inferior in interlayer adhesion (Comparative Example 1). On the contrary, the laminate HS-2 in which a polymer layer having the repeating unit [b] defined in the present invention but not having the repeating unit [a] is provided on the cellulose ester resin layer has an adhesiveness between the layers. However, the moisture permeability was high and the moisture barrier action was poor (Comparative Example 2).
On the other hand, the laminates S-1 to S-30 including the adhesive polymer layer having both the repeating unit [a] and the repeating unit [b] defined in the present invention have improved adhesion between layers. The results were excellent, and the moisture permeability was low and the moisture barrier action was excellent (Examples 1 to 30).
[製造例2:偏光板PL-1~PL-3、PL-5~PL-7並びに比較偏光板HPL-1及びHPL-2の作製]
 下記のようにして、偏光板PL-1~PL-3、PL-5~PL-7並びに比較偏光板HPL-1及びHPL-2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、上記で作製した各積層体S-1、S-6、S-7、S-28、S-29、S-30、HS-1及びHS-2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30秒流水下に通して水洗浴し、ZRD40及び各積層体を中性の状態にした。得られたZRD40及び各積層体に対し、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及び各積層体を得た。
[Production Example 2: Production of polarizing plates PL-1 to PL-3, PL-5 to PL-7 and comparative polarizing plates HPL-1 and HPL-2]
As described below, polarizing plates PL-1 to PL-3, PL-5 to PL-7, and comparative polarizing plates HPL-1 and HPL-2 were prepared.
(1) Saponification Commercially available cellulose acylate film (Fujitack ZRD40, manufactured by FUJIFILM Corporation) and each of the laminates S-1, S-6, S-7, S-28, S-29 prepared above, After immersing S-30, HS-1 and HS-2 in a 1.5 mol / L NaOH aqueous solution (saponification solution) maintained at 55 ° C. for 2 minutes, the ZRD 40 and each laminate were washed with water. Next, after immersing ZRD40 and each laminate in a 0.05 mol / L sulfuric acid aqueous solution at 25 ° C. for 30 seconds, they are further washed for 30 seconds under running water to bring ZRD40 and each laminate to a neutral state. did. The obtained ZRD40 and each laminate were repeatedly drained with an air knife three times, and after dropping water, they were retained in a drying zone at 70 ° C. for 15 seconds and dried to obtain a saponified ZRD40 and each laminate.
(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(各積層体の密着性ポリマー層を積層していない面(すなわちセルロースエステル樹脂層表面)を偏光子と接するように配置する)、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をこの順番で、PVA系接着剤で貼合し、熱乾燥して、偏光板PL-1~PL-3、PL-5~PL-7並びに比較偏光板HPL-1及びHPL-2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 laminate after the above saponification (arranged so that the adhesive polymer layer of each laminate is not laminated (that is, the cellulose ester resin layer surface is in contact with the polarizer)), produced above The polarizer and the cellulose acylate film ZRD40 after saponification are bonded in this order with a PVA adhesive, and thermally dried to obtain polarizing plates PL-1 to PL-3 and PL-5 to PL-. 7 and comparative polarizing plates HPL-1 and HPL-2 were prepared.
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 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.
[製造例3:偏光板PL-4およびPL-8~PL-10の作製]
 下記のようにして偏光板PL-4およびPL-8~PL-10を作製した。
[Production Example 3: Production of polarizing plates PL-4 and PL-8 to PL-10]
Polarizer plates PL-4 and PL-8 to PL-10 were produced as follows.
(1)活性エネルギー線硬化型接着剤組成物の調製
 各成分を下記に示す組成で混合し、50℃で1時間撹拌して、活性エネルギー線硬化型接着剤組成物を得た。
――――――――――――――――――――――――――――――――――
活性エネルギー線硬化型接着剤組成物の組成
――――――――――――――――――――――――――――――――――
ラジカル重合性化合物:東亜合成社製アロニックスM-220
                           20.0質量部
興人社製N-ヒドロキシルアクリルアミド        40.0質量部
興人社製アクロイルモルホリン             40.0質量部
ラジカル重合開始剤:日本化薬社製KAYACURE DETX-S
                            0.5質量部
ラジカル重合開始剤:BASF社製IRGACURE907
                            1.5質量部
――――――――――――――――――――――――――――――――――
(1) Preparation of active energy ray hardening-type adhesive composition Each component was mixed with the composition shown below, and it stirred at 50 degreeC for 1 hour, and obtained the active energy ray hardening-type adhesive composition.
――――――――――――――――――――――――――――――――――
Composition of active energy ray-curable adhesive composition ――――――――――――――――――――――――――――――――――
Radical polymerizable compound: Aronix M-220 manufactured by Toa Gosei Co., Ltd.
20.0 parts by mass Njin-Hydroxyacrylamide 40.0 parts by mass Acroyl morpholine 40.0 parts by mass Radical polymerization initiator: KAYACURE DETX-S manufactured by Nippon Kayaku Co., Ltd.
0.5 part by mass radical polymerization initiator: IRGACURE907 manufactured by BASF
1.5 parts by mass ――――――――――――――――――――――――――――――――――
 上記で作製した積層体S-8およびS-28~S-30の密着性ポリマー層側にコロナ処理を施した。このコロナ処理を施した表面に、上記で調製した活性エネルギー線硬化型接着剤組成物をMCDコーター(富士機械社製、セル形状:ハニカム、グラビアロール線数:1000本/INCH、回転速度140%/対ライン速)を用いて、厚み0.5μmになるように塗布した。
 また、別途、厚み40μmのシクロオレフィン系フィルム(JSR社製アートンG7810)を用意し、その表面にコロナ処理を施した。このコロナ処理を施した表面に上記と同様にして活性エネルギー線硬化型接着剤組成物を厚み0.5μmとなるように塗布した。
 続いて、積層体S-8およびS-28~S-30の活性エネルギー線硬化型接着剤組成物を塗布した面と、シクロオレフィン系フィルムの活性エネルギー線硬化型接着剤組成物を塗布した面を、上記で作製した偏光子の両面にそれぞれ貼り合わせて偏光板前駆体を作製した。その後、この偏光板前駆体の両面から、IRヒーターを用いて50℃に加温した。次いで、下記に示す活性エネルギー線を、偏光板前駆体の両面に照射して、上記活性エネルギー線硬化型接着剤組成物を硬化させた。その後、70℃で3分間熱風乾燥して、偏光板PL-4およびPL-8~PL-10を得た。
The laminates S-8 and S-28 to S-30 produced above were subjected to corona treatment on the adhesive polymer layer side. On the surface subjected to the corona treatment, the active energy ray-curable adhesive composition prepared above was applied to an MCD coater (manufactured by Fuji Machine Co., Ltd., cell shape: honeycomb, number of gravure roll wires: 1000 / INCH, rotation speed 140% The film was applied so as to have a thickness of 0.5 μm.
Separately, a cycloolefin film having a thickness of 40 μm (Arton G7810 manufactured by JSR) was prepared, and the surface thereof was subjected to corona treatment. The active energy ray-curable adhesive composition was applied to the corona-treated surface so as to have a thickness of 0.5 μm in the same manner as described above.
Subsequently, the surface on which the active energy ray-curable adhesive composition of laminates S-8 and S-28 to S-30 was applied, and the surface on which the active energy ray-curable adhesive composition of the cycloolefin film was applied Were bonded to both sides of the polarizer prepared above to prepare a polarizing plate precursor. Then, it heated at 50 degreeC using IR heater from both surfaces of this polarizing plate precursor. Subsequently, the active energy ray shown below was irradiated to both surfaces of the polarizing plate precursor, and the said active energy ray hardening-type adhesive composition was hardened. Thereafter, it was dried with hot air at 70 ° C. for 3 minutes to obtain polarizing plates PL-4 and PL-8 to PL-10.
(活性エネルギー線)
 活性エネルギー線として、紫外線(ガリウム封入メタルハライドランプ)、照射装置:Fusion UV Systems,Inc社製Light HAMMER10、バルブ:Vバルブ、ピーク照度:1600mW/cm、積算照射量1000/mJ/cm(波長380~440nm)を使用した。なお、紫外線の照度は、Solatell社製Sola-Checkシステムを使用して測定した。
(Active energy rays)
As active energy rays, ultraviolet rays (gallium filled metal halide lamp), irradiation apparatus: Fusion UV Systems, Inc. Light HAMMER10, bulb: V bulb, peak illuminance: 1600 mW / cm 2 , integrated irradiation amount 1000 / mJ / cm 2 (wavelength) 380-440 nm) was used. The illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell.
[試験例3: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-6、S-7、S-8、S-28、S-29、S-30、HS-1及びHS-2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 3: 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 a glass plate, and the laminates S-1, S-6, S-7, S-8, S-28, S-29, S-30, HS-1 and HS-2 are air interfaces. Two samples (about 5 cm × 5 cm) pasted so as to be on the side (on the side away from the glass plate) 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(%)=[上記保存後の偏光度(%)-上記保存前の偏光度(%)] Polarization degree change (%) = [Polarization degree after storage (%) − Polarization degree before storage (%)]
<偏光子耐久性評価基準>
偏光度変化量(%)
 A+:偏光度変化量が0.05%未満
 A :偏光度変化量が0.05%以上2.0%未満
 B :偏光度変化量が2.0%以上3.0%未満
 C :偏光度変化量が3.0%以上5.0%未満
 D :偏光度変化量が5.0%以上
 結果を下記表3に示す。
<Polarizer durability evaluation criteria>
Polarization degree change (%)
A +: Polarization degree change amount is less than 0.05% A: Polarization degree change amount is 0.05% or more and less than 2.0% B: Polarization degree change amount is 2.0% or more and less than 3.0% C: Polarization degree Change amount is 3.0% or more and less than 5.0% D: Polarization degree change amount is 5.0% or more The results are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000032
 上記表3に記載される通り、比較積層体HS-1を保護フィルムとして用いた比較偏光板HPL-1は、保護フィルムの層間密着性が不良でセルロースエステル樹脂層とポリマー層とが剥がれてしまい、耐久性の評価を実施可能な偏光板を得ることができなかった(比較例3)。
 また、比較積層体HS-2を保護フィルムとして用いた比較偏光板HPL-2は、偏光子耐久性に大きく劣る結果となった(比較例4)。
 これに対し、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-10は、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 comparative polarizing plate HPL-1 using the comparative laminate HS-1 as a protective film has a poor interlayer adhesion of the protective film, and the cellulose ester resin layer and the polymer layer are peeled off. A polarizing plate capable of evaluating durability could not be obtained (Comparative Example 3).
In addition, the comparative polarizing plate HPL-2 using the comparative laminate HS-2 as a protective film resulted in greatly inferior polarizer durability (Comparative Example 4).
In contrast, the polarizing plates PL-1 to PL-10 of the present invention using the laminate of the present invention as a protective film showed excellent polarizer durability. 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、2015年9月30日に日本国で特許出願された特願2015-195324及び2016年1月29日に日本国で特許出願された特願2016-016705に基づく優先権を主張するものであり、これらはいずれも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. 2015-195324 filed in Japan on September 30, 2015 and Japanese Patent Application No. 2016-016705 filed on January 29, 2016 in Japan. All of which are hereby incorporated herein by reference as if fully set forth herein.
10 積層体(積層板)
 11 セルロースエステル樹脂層
 12 密着性ポリマー層
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 Adhesive 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 polarization Direction of plate absorption axis

Claims (9)

  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られた密着性ポリマー層とを有し、上記密着性ポリマー層を構成する密着性ポリマーが下記〔a〕の繰り返し単位の少なくとも1種と下記〔b〕の繰り返し単位の少なくとも1種とを有する積層体。
    〔a〕:
     (メタ)アクリル酸エステル化合物、オレフィン化合物、ビニリデン化合物又は環状オレフィン化合物由来の繰り返し単位であって、Hoy法により算出される溶解度パラメータδtが13.5~19.5である繰り返し単位。
    〔b〕:
     (メタ)アクリル酸エステル化合物、(メタ)アクリル酸化合物、(メタ)アクリルアミド化合物、酢酸ビニル化合物、ビニルケトン化合物、無水マレイン酸化合物もしくはスチレン化合物由来の繰り返し単位又はこれらの繰り返し単位以外でエチレン性不飽和結合を有する化合物由来の繰り返し単位であって、Hoy法により算出される溶解度パラメータδtが20.0~26.0である繰り返し単位。
    It has a cellulose ester resin layer and an adhesive polymer layer provided directly on the cellulose ester resin layer, and the adhesive polymer constituting the adhesive polymer layer is at least one repeating unit of the following [a]: The laminated body which has at least 1 sort (s) of the repeating unit of following [b].
    [A]:
    A repeating unit derived from a (meth) acrylic ester compound, an olefin compound, a vinylidene compound or a cyclic olefin compound and having a solubility parameter δt calculated by the Hoy method of 13.5 to 19.5.
    [B]:
    (Meth) acrylic acid ester compounds, (meth) acrylic acid compounds, (meth) acrylamide compounds, vinyl acetate compounds, vinyl ketone compounds, maleic anhydride compounds or repeating units derived from styrene compounds or ethylenically unsaturated other than these repeating units A repeating unit derived from a compound having a bond and having a solubility parameter δt calculated by the Hoy method of 20.0 to 26.0.
  2.  上記密着性ポリマーが、上記〔b〕の繰り返し単位として下記一般式1で表される繰り返し単位を有する、請求項1に記載の積層体。
    一般式1:
    Figure JPOXMLDOC01-appb-C000001
     一般式1中、
    は水素原子又はアルキル基を示す。
    及びR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。
    L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(R)-から選ばれる2価の連結基もしくはこれらの連結基の2種以上を組合せてなる2価の連結基を示す。
    は水素原子又はアルキル基を示す。
    The laminate according to claim 1, wherein the adhesive polymer has a repeating unit represented by the following general formula 1 as the repeating unit [b].
    General formula 1:
    Figure JPOXMLDOC01-appb-C000001
    In general formula 1,
    R 1 represents a hydrogen atom or an alkyl group.
    R 2 and R 3 represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
    L is a single bond, or a divalent linking group selected from an alkylene group, an arylene group, —C (═O) —, —O— and —N (R 4 ) —, or 2 of these linking groups. A divalent linking group formed by combining more than one species is shown.
    R 4 represents a hydrogen atom or an alkyl group.
  3.  上記密着性ポリマーが、上記〔a〕の繰り返し単位として下記一般式2で表される繰り返し単位を有する、請求項1又は2に記載の積層体。
    一般式2:
    Figure JPOXMLDOC01-appb-C000002
     一般式2中、
    は水素原子又はアルキル基を示す。
    及びR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。
    は炭素数1~20のアルキル基又は炭素数3~10のシクロアルキル基を示す。
    The laminate according to claim 1 or 2, wherein the adhesive polymer has a repeating unit represented by the following general formula 2 as the repeating unit of [a].
    General formula 2:
    Figure JPOXMLDOC01-appb-C000002
    In general formula 2,
    R 5 represents a hydrogen atom or an alkyl group.
    R 6 and R 7 represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
    R 8 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms.
  4.  上記密着性ポリマーを構成するモノマー成分の総モル量中に占める上記〔b〕の繰り返し単位のモル量が5モル%以上90モル%以下である、請求項1~3のいずれか1項に記載の積層体。 The molar amount of the repeating unit (b) occupying in the total molar amount of the monomer component constituting the adhesive polymer is 5 mol% or more and 90 mol% or less, according to any one of claims 1 to 3. Laminated body.
  5.  上記密着性ポリマーが、上記〔b〕の繰り返し単位として下記一般式1-1で表される繰り返し単位を有する、請求項1~4のいずれか1項に記載の積層体。
    一般式1-1:
    Figure JPOXMLDOC01-appb-C000003
     一般式1-1中、R及びLは、それぞれ上記一般式1におけるR及びLと同義である。
    The laminate according to any one of claims 1 to 4, wherein the adhesive polymer has a repeating unit represented by the following general formula 1-1 as the repeating unit [b].
    Formula 1-1:
    Figure JPOXMLDOC01-appb-C000003
    In the Formula 1-1, R 1 and L are respectively the same meanings as R 1 and L in the above general formula 1.
  6.  上記密着性ポリマーが、上記〔a〕の繰り返し単位として下記一般式2-2で表される繰り返し単位を有する、請求項1~5のいずれか1項に記載の積層体。
    一般式2-2
    Figure JPOXMLDOC01-appb-C000004
     一般式2-2中、R及びRは、それぞれ上記一般式2におけるR及びRと同義である。
    The laminate according to any one of claims 1 to 5, wherein the adhesive polymer has a repeating unit represented by the following general formula 2-2 as the repeating unit of [a].
    Formula 2-2
    Figure JPOXMLDOC01-appb-C000004
    In the Formula 2-2, R 5 and R 8 are the same meanings as R 5 and R 8 in the general formula 2.
  7.  上記セルロースエステル樹脂層を構成するセルロースエステルがセルロースアシレートである、請求項1~6のいずれか1項に記載の積層体。 The laminate according to any one of claims 1 to 6, wherein the cellulose ester constituting the cellulose ester resin layer is cellulose acylate.
  8.  請求項1~7のいずれか1項に記載の積層体と、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 7 and a polarizer.
  9.  請求項8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 8.
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