WO2019004042A1 - Optical film - Google Patents

Optical film Download PDF

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Publication number
WO2019004042A1
WO2019004042A1 PCT/JP2018/023583 JP2018023583W WO2019004042A1 WO 2019004042 A1 WO2019004042 A1 WO 2019004042A1 JP 2018023583 W JP2018023583 W JP 2018023583W WO 2019004042 A1 WO2019004042 A1 WO 2019004042A1
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group
meth
film
optical film
compound
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PCT/JP2018/023583
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French (fr)
Japanese (ja)
Inventor
亜依 小橋
智恵 阪上
悠司 淺津
Original Assignee
住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to KR1020207001839A priority Critical patent/KR20200023392A/en
Priority to CN201880042836.4A priority patent/CN110799866B/en
Publication of WO2019004042A1 publication Critical patent/WO2019004042A1/en

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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/22Absorbing filters
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363Birefringent elements, e.g. for optical compensation
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/02Details
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Definitions

  • the present invention relates to an optical film.
  • Patent Document 1 describes a polarizing plate in which an ultraviolet light absorber excellent in ultraviolet light absorbing ability in a wavelength range of 370 nm or less is added to a protective film of the polarizing plate.
  • the present invention provides an optical film having a good suppression function for deterioration of a retardation film or an organic EL light emitting device due to visible light of short wavelength by showing high absorption selectivity to visible light of short wavelength around 405 nm. It is to be.
  • the present invention includes the following inventions.
  • the resin (A) is at least one resin selected from the group consisting of cellulose resins, (meth) acrylic resins, polyester resins, polyamide resins, polyimide resins and cycloolefin resins,
  • a (405) 0.5 0.5 (1)
  • a (405) represents the absorbance at a wavelength of 405 nm.
  • (epsilon) (405) represents the gram absorption coefficient of the compound in wavelength 405 nm
  • (epsilon) (440) represents the gram absorption coefficient in wavelength 440 nm.
  • [8] The optical film as described in [1] to [7], wherein the photoselective absorption compound (B) is a compound having a merocyanine structure in the molecule.
  • the display apparatus which has an optical film as described in [10] [9].
  • the optical film of the present invention exhibits a high absorption selectivity for visible light of a short wavelength near 405 nm, and thus has a good suppression function for deterioration of the retardation film or the organic EL light emitting element due to visible light of a short wavelength.
  • the optical film of the present invention exhibits high absorption selectivity for visible light of short wavelength near 405 nm even after weathering test, and deterioration by visible light of short wavelength even after weathering test You can keep control.
  • the optical film of the present invention is used in a display device, good display characteristics and durability can be imparted.
  • the optical film of the present invention is an optical film formed from a resin composition containing a resin (A) and a light selective absorption compound (B),
  • the resin (A) is at least one resin selected from the group consisting of a cellulose resin, a (meth) acrylic resin, a polyester resin, a polyamide resin, a polyimide resin and a cycloolefin resin, and It is characterized by satisfying 1).
  • a (405) 0.5 0.5 (1)
  • a (405) represents the absorbance at a wavelength of 405 nm. ]
  • the value of A (405) is preferably 0.6 or more, more preferably 0.8 or more, and particularly preferably 1.0 or more. There is no particular upper limit, but it is usually 10 or less.
  • the optical film of the present invention preferably further satisfies the following formula (2).
  • a (440) ⁇ 0.1 (2) [In Formula (2), A (440) represents the light absorbency in wavelength 440nm. ] The smaller the value of A (440), the lower the absorption at a wavelength of 440 nm. When the value of A (440) exceeds 0.1, there is a tendency to impair good color expression in the display device. In addition, since the light emission of the display device is inhibited, the luminance is also reduced.
  • the value of A (440) is preferably 0.05 or less, more preferably 0.04 or less, and particularly preferably 0.03. The lower limit is not particularly limited, but is usually 0.00001 or more.
  • the optical film of the present invention preferably further satisfies the following formula (3).
  • a (405) / A (440) ⁇ 5 (3) [In Formula (3), A (405) represents the absorbance at a wavelength of 405 nm, and A (440) represents the absorbance at a wavelength of 440 nm. ]
  • the value of A (405) / A (440) represents the magnitude of absorption at a wavelength of 405 nm with respect to the magnitude of absorption at a wavelength of 440 nm. The larger the value, the specific absorption in a wavelength range near 405 nm. Represent.
  • the value of A (405) / A (440) is preferably 10 or more, more preferably 30 or more, and particularly preferably 60 or more.
  • the storage elastic modulus E ′ at 23 ° C. is usually 100 MPa or more, preferably 300 MPa or more, more preferably 500 MPa or more, still more preferably 1000 MPa or more, particularly preferably 3500 MPa It is above. Although the lower limit is not limited, it is usually 100000 MPa or less.
  • the storage elastic modulus at 23 ° C. of the optical film of the present invention can be measured by the method described in the examples.
  • the optical film of the present invention is formed from a resin composition containing a resin (A) and a light selective absorption compound (B) (hereinafter sometimes referred to as "resin composition (1)").
  • the resin (A) is at least one resin selected from the group consisting of cellulose resins, (meth) acrylic resins, polyester resins, polyamide resins, polyimide resins, and cycloolefin resins.
  • the cellulose-based resin is preferably a cellulose ester-based resin, that is, a resin in which at least a part of hydroxyl groups in cellulose is acetate-esterified, a part is acetate-esterified, and a part is esterified with another acid It may be a mixed ester.
  • the cellulose ester resin is preferably an acetyl cellulose resin. Specific examples of the acetyl cellulose-based resin include triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, and cellulose acetate butyrate.
  • acetylcellulose As a raw material cotton of acetyl cellulose, cellulose raw materials such as wood pulp and cotton linters which are known according to Inventive Society of Japan published technology 2001-1745 etc. can be used.
  • acetylcellulose can be synthesized by the method described in Wood Chemistry, pp. 180-190 (Kyoritsu Shuppan, Akita et al., 1968).
  • trade names "UV-50”, “UV-80", “SH-80”, “TD-80U”, “TD-TAC”, “UZ-TAC” manufactured by Fuji Film Co., Ltd. Etc. are mentioned.
  • Examples of (meth) acrylic resins include homopolymers of methacrylic acid alkyl esters or acrylic acid alkyl esters, and copolymers of methacrylic acid alkyl esters and acrylic acid alkyl esters.
  • Specific examples of the methacrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate and propyl methacrylate.
  • Specific examples of the acrylic acid alkyl ester include methyl acrylate, ethyl acrylate and propyl acrylate.
  • As such (meth) acrylic resins those commercially available as general-purpose (meth) acrylic resins can be used.
  • As the (meth) acrylic resin one called an impact resistant (meth) acrylic resin may be used.
  • "acrypet VH" of Mitsubishi Rayon Co., Ltd. and "acrypet VRL 20A” etc. are mentioned as a specific example of (meth) acrylic-type resin.
  • the polyester resin is a polymer resin having a repeating unit of an ester bond in the main chain, and is generally obtained by condensation polymerization of a polyvalent carboxylic acid or a derivative thereof and a polyalcohol or a derivative thereof.
  • polyvalent carboxylic acids or derivatives thereof which give polyesters include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenoxy ethane dicarboxylic acid, 5-sodium sulfone dicarboxylic acid
  • Aliphatic dicarboxylic acids such as acids, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acids, aliphatic dicarboxylic acids such as maleic acid and fumaric acid, and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicar
  • Examples of derivatives of dicarboxylic acid include dimethyl terephthalate, diethyl terephthalate, 2-hydroxyethyl methyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, dimethyl adipate, diethyl maleate, dimethyl dimer acid, etc. Esterified products can be mentioned. Among them, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and their esterified products are preferably used in view of moldability and handleability.
  • polyhydric alcohols or derivatives thereof which give polyesters ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Aliphatic dihydroxy compounds such as diol, 1,6-hexanediol, neopentyl glycol etc., polyoxyalkylene glycols such as diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol etc., 1,4-cyclohexanedimethanol, spiro glycol etc.
  • Alicyclic dihydroxy compounds aromatic dihydroxy compounds such as bisphenol A and bisphenol S, and derivatives thereof can be mentioned.
  • ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol and 1,4-cyclohexanedimethanol are preferably used in terms of moldability and handleability.
  • polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethyl terephthalate, and polycyclohexanedimethyl naphthalate.
  • polyethylene terephthalate or polyethylene naphthalate is preferable.
  • the polyamide resin is a polymer resin containing an amide bond in a repeating unit as a main chain, and for example, an aromatic polyamide (aramid) in which an aromatic ring skeleton is bonded by an amide bond or a fat in which an aliphatic skeleton is bonded by an amide bond Family polyamide and the like.
  • aromatic polyamide aromatic polyamide
  • it can be obtained by the polymerization reaction of a polyvalent carboxylic acid or a derivative thereof and a polyvalent amine.
  • polyvalent carboxylic acids which give polyamides or derivatives thereof include terephthalic acid chloride, 2-chloro-terephthalic acid chloride, isophthalic acid dichloride, naphthalene dicarbonyl chloride, biphenyl dicarbonyl chloride, terphenyl dicarbonyl chloride and the like.
  • polyhydric amines giving polyamides include 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,2'-ditriol.
  • a polyimide-based resin is a polymer resin containing an imide bond in a repeating unit as a main chain, and a condensation type polyimide obtained by polycondensation using a diamine and tetracarboxylic acid dianhydride as a starting material is generally used.
  • diamines aromatic diamines, alicyclic diamines, aliphatic diamines, etc. can be used.
  • tetracarboxylic acid dianhydride aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, acyclic aliphatic tetracarboxylic acid dianhydride, etc. can be used.
  • the diamines and the tetracarboxylic acid dianhydride may be used alone or in combination of two or more.
  • a tetracarboxylic acid compound selected from tetracarboxylic acid compound analogs such as an acid chloride compound may be used as a starting material.
  • the cycloolefin resin is, for example, a thermoplastic resin having a monomer unit composed of a cyclic olefin (cycloolefin) such as norbornene or polycyclic norbornene monomer, and is also referred to as a thermoplastic cycloolefin resin.
  • the cycloolefin resin may be a hydrogenated product of the above-mentioned ring-opening polymer of cycloolefin or ring-opening copolymer using two or more types of cyclo-olefin, and may be cycloolefin, chain olefin, vinyl It may be an addition polymer with an aromatic compound having a polymerizable double bond such as a group. A polar group may be introduced into the cycloolefin resin.
  • the first protective film is formed using a copolymer of a cycloolefin and an aromatic compound having a linear olefin and / or a vinyl group
  • linear olefin examples include ethylene and propylene
  • aromatic compound having a vinyl group examples include styrene, ⁇ -methylstyrene and nuclear alkyl-substituted styrene.
  • the unit of the cycloolefin monomer may be 50 mol% or less, preferably about 15 to 50 mol%.
  • the unit of the monomer composed of the cycloolefin is compared Amount can be reduced.
  • the unit of monomers consisting of chain olefins is usually 5 to 80 mol%
  • the unit of monomers consisting of aromatic compounds having a vinyl group is usually 5 to 80 mol%.
  • cycloolefin resin an appropriate commercially available product can be used.
  • TOPAS marketed by Polyplastics Co., Ltd.
  • Arton marketed by JSR Corporation
  • ZEONOR marketed by Nippon Zeon Co., Ltd.
  • ZEONEX And “Apple” (all trade names) sold by Mitsui Chemicals, Inc., and the like.
  • the storage elastic modulus E at 23 ° C. of the resin (A) is usually 100 MPa or more, preferably 300 MPa or more, more preferably 500 MPa or more, and particularly preferably 1000 MPa or more. Although the lower limit is not limited, it is usually 100000 MPa or less.
  • the light selective absorption compound (B) is a compound that selectively absorbs light of a wavelength of 405 nm, is preferably a compound that satisfies the following formula (4), and is further a compound that satisfies the formula (5) preferable.
  • [In Formula (4), (epsilon) (405) represents the gram absorption coefficient of a compound in wavelength 405 nm.
  • the unit of gram absorption coefficient is L / (g ⁇ cm).
  • (epsilon) (405) represents the gram absorption coefficient of the compound in wavelength 405 nm
  • (epsilon) (440) represents the gram absorption coefficient in wavelength 440 nm.
  • the gram absorbance coefficient is measured by the method described in the examples.
  • the resin composition of the present invention has the function of suppressing the deterioration of the retardation film or the organic EL light emitting device due to ultraviolet light or short wavelength visible light.
  • the content of the photoselective absorption compound (B) in the substance is increased.
  • the light selective absorption compound (B) may be bled out or dispersed unevenly, and the light absorption function may be insufficient.
  • ⁇ (405) is preferably 20 L / (g ⁇ cm) or more, more preferably 30 L / (g ⁇ cm) or more, and even more preferably 40 L / (g ⁇ cm) or more Preferably, it is usually 500 L / (g ⁇ cm) or less.
  • a compound having a larger value of ⁇ (405) / ⁇ (440) absorbs light in the vicinity of 405 nm and suppresses light degradation of a display device such as a retardation film or an organic EL element without inhibiting color expression of the display device. can do.
  • the value of ⁇ (405) / ⁇ (440) is preferably 20 or more, more preferably 40 or more, still more preferably 70 or more, and particularly preferably 80 or more.
  • the photoselective absorption compound (B) is preferably a compound containing a merocyanine structure in the molecule.
  • a compound, an indole compound, a benzotriazole compound, etc. are mentioned, It is preferable that they are a merocyanine compound, a cyanine compound, and a benzotriazole compound, More preferably, it is a compound represented by Formula (I).
  • R 1 and R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms which may have a substituent, or 7 to carbon atoms which may have a substituent; 15 represent an aralkyl group, an aryl group having a carbon number of 6 to 15, and a heterocyclic group, and -CH 2- contained in the alkyl group or the aralkyl group is -NR 1A- , -CO-, -SO 2- , -O It may be substituted by-or -S-.
  • R 1A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aromatic hydrocarbon group which may have a substituent Or an aromatic heterocyclic group which may have a substituent, and -CH 2- contained in the alkyl group is -NR 1B- , -CO-, -SO 2- , -O- or -S- And may be substituted.
  • R 1B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 6 and R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an electron-withdrawing group, or R 6 and R 7 may combine with each other to form a ring structure .
  • R 1 and R 2 may be linked to each other to form a ring structure
  • R 2 and R 3 may be linked to each other to form a ring structure
  • R 2 and R 4 are linked to each other to form a ring structure
  • R 3 and R 6 may be linked to each other to form a ring structure.
  • Examples of the alkyl group having 1 to 25 carbon atoms represented by R 1 and R 5 include methyl group, ethyl group, n-propyl group, isopropyl group, 2-cyanopropyl group, n-butyl group, tert-butyl group, and sec-butyl, n-pentyl, n-hexyl, 1-methylbutyl, 3-methylbutyl, n-octyl, n-decyl, 2-hexyl-octyl and the like.
  • Examples of the substituent which the alkyl group having 1 to 25 carbon atoms represented by R 1 and R 5 may have include the groups described in the following group A.
  • Group A nitro, hydroxy, carboxy, sulfo, cyano, amino, halogen, alkoxy having 1 to 6 carbons, alkylsilyl having 1 to 12 carbons, alkyl having 2 to 8 carbons carbonyl group, * - R a1 - (O -R a2) t1 -R a3 (R a1 and R a2 each independently represent an alkanediyl group having 1 to 6 carbon atoms, R a3 is a C1- 6 represents an alkyl group, and s 1 represents an integer of 1 to 3.) and the like.
  • alkylsilyl group having 1 to 12 carbon atoms examples include monoalkylsilyl groups such as methylsilyl group, ethylsilyl and propylsilyl groups; dialkylsilyl groups such as dimethylsilyl group, diethylsilyl group and methylethylsilyl group; trimethylsilyl and triethylsilyl, And trialkylsilyl groups such as tripropylsilyl group.
  • alkylcarbonyl group having 2 to 8 carbon atoms examples include a methylcarbonyl group and an ethylcarbonyl group.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom etc. are mentioned.
  • Examples of the aralkyl group having 7 to 15 carbon atoms represented by R 1 and R 5 include a benzyl group and a phenylethyl group. Examples of the group in which —CH 2 — contained in the aralkyl group is replaced by —SO 2 — or —COO— include a 2-phenylacetic acid ethyl group and the like. Examples of the substituent which the aralkyl group having 7 to 15 carbon atoms represented by R 1 and R 5 may have include the groups described in the following group A. Examples of the aryl group having 6 to 15 carbon atoms represented by R 1 and R 5 include a phenyl group, a naphthyl group and an anthracenyl group.
  • Examples of the substituent which the aryl group having 6 to 15 carbon atoms represented by R 1 and R 5 may have include the groups described in Group A above.
  • Examples of the heterocyclic group having 6 to 15 carbon atoms represented by R 1 and R 5 include carbons such as pyridyl, pyrrolidinyl, quinolyl, thiophene, imidazolyl, oxazolyl, pyrrole, thiazolyl and furanyl And 3 to 9 aromatic heterocyclic groups.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 1A and R 1B include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, n -Pentyl group, n-hexyl group and the like.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 2 , R 3 and R 4 include the same ones as the alkyl group having 1 to 6 carbon atoms represented by R 1B .
  • Examples of the substituent which the alkyl group having 1 to 6 carbon atoms represented by R 2 , R 3 and R 4 may have include the groups described in the above-mentioned group A.
  • the aromatic hydrocarbon group represented by R 2 , R 3 and R 4 includes aryl groups having 6 to 15 carbon atoms such as phenyl, naphthyl and anthracenyl; and 7 to 15 carbon atoms such as benzyl and phenylethyl. There may be mentioned 15 aralkyl groups.
  • Examples of the substituent which the aromatic hydrocarbon group represented by R 2 , R 3 and R 4 may have include the groups described in Group A above.
  • the aromatic heterocyclic ring represented by R 2 , R 3 and R 4 has 3 carbon atoms such as pyridyl, pyrrolidinyl, quinolyl, thiophene, imidazolyl, oxazolyl, pyrrole, thiazolyl and furanyl.
  • aromatic heterocyclic groups of -9 As a substituent which the aromatic heterocyclic ring represented by R ⁇ 2 >, R ⁇ 3 > and R ⁇ 4 > may have, the group as described in the said group A is mentioned.
  • Examples of the alkyl group having 1 to 25 carbon atoms represented by R 6 and R 7 include the same ones as the alkyl group having 1 to 25 carbon atoms represented by R 1 and R 5 .
  • Examples of the substituent which the alkyl group having 1 to 25 carbon atoms represented by R 6 and R 7 may have include the groups described in Group A above.
  • Examples of the alkyl group having 1 to 25 carbon atoms represented by R 6 and R 7 include the same ones as the alkyl group having 1 to 25 carbon atoms represented by R 1 and R 5 .
  • Examples of the electron withdrawing group represented by R 6 and R 7 include a cyano group, a nitro group, a halogen atom, an alkyl group substituted with a halogen atom, and a group represented by formula (I-1) .
  • R 11 represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, and at least one of the methylene groups contained in the alkyl group may be substituted by an oxygen atom.
  • X 1 is, -CO -, - COO -, - OCO -, - CS -, - CSO -, - CSS -, - NR 12 CO- or CONR 13 - represents a.
  • R 12 and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • alkyl group substituted by a halogen atom include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, and the like
  • Perfluoroalkyl groups, such as perfluorohexyl group, etc. are mentioned.
  • the carbon number of the alkyl group substituted with a halogen atom is usually 1 to 25.
  • R 6 and R 7 may be linked to each other to form a ring structure, and examples of the ring structure formed of R 6 and R 7 include a Meldrum's acid structure, a barbituric acid structure, a dimedone structure, etc.
  • R 11 examples of the alkyl group having 1 to 25 carbon atoms represented by R 11 include the same as the alkyl groups represented by R 1 and R 5 .
  • the ring structure formed by bonding R 2 and R 3 to each other is a nitrogen-containing ring structure containing a nitrogen atom bonded to R 2, and is, for example, a 4- to 14-membered nitrogen-containing heterocyclic ring It can be mentioned.
  • the ring structure formed by linking R 2 and R 3 to each other may be monocyclic or polycyclic. Specifically, pyrrolidine ring, pyrroline ring, imidazolidine ring, imidazoline ring, oxazoline ring, thiazoline ring, piperidine ring, morpholine ring, piperazine ring, indole ring, isoindole ring and the like can be mentioned.
  • the ring structure formed by bonding R 1 and R 2 to each other is a nitrogen-containing ring structure containing a nitrogen atom to which R 1 and R 2 are bonded, and is, for example, a 4- to 14-membered ring (preferably And 4 to 8 membered rings).
  • the ring structure formed by linking R 1 and R 2 to each other may be monocyclic or polycyclic. Specifically, the same as the ring structure formed by linking R 2 and R 3 to each other can be mentioned.
  • the ring structure formed by combining R 2 and R 4 with one another includes a 4- to 14-membered nitrogen-containing ring structure, and a 5- to 9-membered nitrogen-containing ring structure is preferable.
  • the ring structure formed by bonding R 2 and R 4 to each other may be monocyclic or polycyclic. These rings may have a substituent, and as such a ring structure, the same one as exemplified as the ring structure formed by R 2 and R 3 may be mentioned.
  • a phenyl group etc. are mentioned.
  • Examples of the compound represented by formula (I) in which R 2 and R 3 are linked to each other to form a ring structure include compounds represented by formula (IA), and R 2 and R 4
  • Examples of the compound represented by the formula (I) which forms a ring structure by linking include a compound represented by the formula (IB) and the like.
  • R 1 , R 3 , R 4 , R 5 , R 6 and R 7 each represent the same meaning as described above.
  • Ring W 1 and ring W 2 each independently represent a nitrogen-containing ring.
  • Ring W 1 and ring W 2 represent a nitrogen-containing ring containing a nitrogen atom as a constituent unit of the ring.
  • the ring W 1 and the ring W 2 may be each independently a single ring or multiple rings, and may contain a heteroatom other than nitrogen as a constituent unit of the ring.
  • the ring W 1 and the ring W 2 are preferably each independently a 5- to 9-membered ring.
  • the compound represented by the formula (IA) is preferably a compound represented by the formula (IA-1).
  • R 1 , R 4 , R 5 , R 6 and R 7 each represent the same meaning as described above.
  • a 1 represents -CH 2- , -O-, -S- or -NR 1D- .
  • Each of R 14 and R 15 independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
  • R 1D represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the compound represented by the formula (IB) is preferably a compound represented by the formula (IB-1) and a compound represented by the formula (IB-2).
  • R 1 , R 6 and R 7 each represent the same meaning as described above.
  • Each R 16 independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group.
  • R 3 , R 5 , R 6 and R 7 each represent the same meaning as described above.
  • R 30 represents a hydrogen atom, a cyano group, a nitro group, a halogen atom, a mercapto group, an amino group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms And an acyl group having 2 to 13 carbon atoms, an acyloxy group having 2 to 13 carbon atoms, or an alkoxycarbonyl group having 2 to 13 carbon atoms.
  • R 31 represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a mercapto group, an alkylthio group having 1 to 12 carbon atoms, an amino group or heterocyclic group which may have a substituent, Represent. ]
  • the halogen atom represented by R 30, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom.
  • Examples of the acyloxy group having 2 to 13 carbon atoms represented by R 30 include a methyl carbonyloxy group, an ethyl carbonyloxy group, a propyl carbonyloxy group, and a butyl carbonyloxy group.
  • Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms represented by R 30 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group and the like.
  • Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R 30 include aryl groups having 6 to 18 carbon atoms such as phenyl group, naphthyl group and biphenyl group; 7 carbon atoms such as benzyl group and phenylethyl group There may be mentioned an aralkyl group of -18.
  • Examples of the alkyl group having 1 to 12 carbon atoms represented by R 30 include the same ones as the alkyl group having 1 to 12 carbon atoms represented by R 14 .
  • Examples of the alkyl group having 1 to 12 carbon atoms represented by R 30 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group.
  • R 30 is preferably an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an amino group or a mercapto group.
  • Examples of the alkyl group having 1 to 12 carbon atoms represented by R 31 include the same ones as the alkyl group having 1 to 12 carbon atoms represented by R 14 .
  • Examples of the C 1-12 alkoxy group represented by R 31 include the same as the C 1-12 alkoxy group represented by R 30 .
  • Examples of the alkylthio group having 1 to 12 carbon atoms represented by R 31 include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group and a hexylthio group.
  • the amino group which may have a substituent represented by R 31 is, for example, an amino group; one alkyl group having 1 to 8 carbon atoms such as N-methylamino group or N-ethylamino group Amino groups; amino groups substituted with two alkyl groups having 1 to 8 carbon atoms such as N, N-dimethylamino, N, N-diethylamino, N, N-methylethylamino and the like; and the like.
  • Examples of the heterocyclic ring represented by R 31 include nitrogen-containing heterocyclic groups having 4 to 9 carbon atoms such as pyrrolidinyl group, piperidinyl group and morpholinyl group.
  • R 1, R 6 and R 7 represent the same meaning as described above.
  • Each of R 21 and R 22 independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a hydroxy group.
  • R 25 represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group which may have a substituent.
  • Examples of the alkyl group having 1 to 25 carbon atoms represented by R 25 include the same ones as the alkyl group having 1 to 25 carbon atoms represented by R 1 .
  • Examples of the aromatic hydrocarbon group represented by R 25 include aryl groups such as phenyl group and naphthyl group: aralkyl groups such as benzyl group and phenylethyl group: biphenyl group and the like, and aromatics having 6 to 20 carbon atoms It is preferably a hydrocarbon group.
  • Examples of the substituent which the aromatic hydrocarbon group represented by R 25 may have include a hydroxy group and the like.
  • R 3 and R 6 are each independently an electron withdrawing group.
  • Examples of the compound represented by the formula (I) in which R 1 and R 2 are linked to each other to form a ring structure and R 3 and R 6 are linked to each other to form a ring structure include a compound represented by formula (ID) And the like.
  • R 4 , R 5 and R 7 represent the same meaning as described above.
  • R 25 , R 26 , R 27 and R 28 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, a hydroxy group or an aralkyl group.
  • Examples of the alkyl group having 1 to 12 carbon atoms represented by R 25 , R 26 , R 27 and R 28 include the same ones as the alkyl group having 1 to 12 carbon atoms represented by R 1A and R 1B .
  • Examples of the substituent which the alkyl group having 1 to 12 carbon atoms represented by R 25 , R 26 , R 27 and R 28 may have include a hydroxy group.
  • Examples of the aralkyl group represented by R 25 , R 26 , R 27 and R 28 include aralkyl groups having 7 to 15 carbon atoms such as benzyl group and phenylethyl group.
  • Examples of the compound (I) in which R 6 and R 7 are linked to each other to form a ring structure include compounds represented by the formula (IE) and the like.
  • IE formula (IE)
  • R 1 , R 3 , R 4 and R 5 each represent the same meaning as described above.
  • Ring W 3 represents a cyclic compound
  • the ring W 3 is a 5- to 9-membered ring, and may contain a heteroatom such as a nitrogen atom, an oxygen atom or a sulfur atom as a constituent unit of the ring.
  • the compound represented by the formula (IE) is preferably a compound represented by the formula (IE-1).
  • R 1 , R 2 , R 3 and R 5 each represent the same meaning as described above.
  • R 17 , R 18 , R 19 and R q each independently represent a hydrogen atom or an alkyl, aralkyl or aryl group having 1 to 12 carbon atoms which may have a substituent, and the alkyl or
  • R 17 and R 18 may be linked to each other to form a ring structure
  • R 18 and R 19 may be linked to each other to form a ring structure
  • R 19 and R q are linked to each other to form a ring structure
  • Examples of the compound represented by the formula (I) include the following compounds.
  • the content of the light selective absorption compound (B) is usually 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, more preferably 0 based on 100 parts by mass of the resin (A). 1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.
  • the resin composition (1) may further contain a plasticizer, an organic acid, a dye, an antistatic agent, a surfactant, a lubricant, a flame retardant, a filler, a rubber particle, a phase difference adjuster, an ultraviolet absorber and the like. Good.
  • any appropriate forming method may be employed as a method of producing the optical film of the present invention. Specifically, compression molding method, transfer molding method, injection molding method, extrusion molding method, blow molding method, powder molding method, FRP molding method, cast coating method (for example, casting method), calendar molding method, heat press Law etc. are mentioned.
  • the extrusion molding method or the cast coating method is preferred because the smoothness of the resulting film can be enhanced and good optical uniformity can be obtained.
  • the molding conditions may be appropriately set according to the composition and type of the resin to be used, the characteristics desired for the retardation film, and the like.
  • the thickness of the optical film of the present invention is usually 1 to 500 ⁇ m, preferably 5 to 300 ⁇ m, more preferably 10 to 150 ⁇ m, and particularly preferably 10 to 75 ⁇ m.
  • the optical film of the present invention may be unstretched or stretched. When the optical film of the present invention is stretched, it may be uniaxially stretched or biaxially stretched.
  • the stretching ratio is usually 1.01 to 10 times, preferably 1.01 to 6 times.
  • the stretching direction can also be performed in various directions and dimensions, such as the length direction, the width direction, the thickness direction, and the oblique direction.
  • the pressure-sensitive adhesive layer-carrying optical film of the present invention is a film having a pressure-sensitive adhesive layer on at least one surface of the optical film of the present invention.
  • the pressure-sensitive adhesive layer is formed of a known pressure-sensitive adhesive.
  • the known pressure-sensitive adhesive may be any pressure-sensitive adhesive having a base polymer such as acrylic, rubber, urethane, silicone, and polyvinyl ether, but the (meth) acrylic resin (A) is a base polymer It is preferable that it is an acrylic adhesive composition included as
  • the (meth) acrylic resin (A) is preferably a polymer as a main component (preferably containing 50% by mass or more) of a structural unit derived from a (meth) acrylic acid ester.
  • the structural unit derived from (meth) acrylic acid ester is a structural unit derived from a monomer other than one or more (meth) acrylic acid esters (for example, a structural unit derived from a monomer having a polar functional group) May be included.
  • (meth) acrylic acid means that either acrylic acid or methacrylic acid may be used, and in the case of (meth) acrylate etc., “(meth)” also has the same meaning. .
  • Examples of the (meth) acrylic acid ester include (meth) acrylic acid esters represented by the following formula (I) [In formula (I), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkyl group having 1 to 14 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and hydrogen of the alkyl group or the aralkyl group The atom may be replaced by an alkoxy group having 1 to 10 carbon atoms. ]
  • R 2 is preferably an alkyl group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.
  • (meth) acrylic acid ester represented by the formula (I), Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, (Meth) acrylic acid n-heptyl, (meth) acrylic acid n-octyl, (meth) acrylic acid n-nonyl, (meth) acrylic acid n-decyl, (meth) acrylic acid n-dodecyl, (meth) acrylic acid Linear alkyl esters of (meth) acrylic acid such as lauryl, stearyl (meth) acrylate, etc .; (Meth) acrylic acid i-propyl, (meth) acrylic acid i-butyl, (meth) acrylic acid t-butyl, (Met
  • Alkyl esters (Meth) acrylic acid cyclohexyl, isoboronyl (meth) acrylic acid, adamantyl (meth) acrylic acid, dicyclopentanyl (meth) acrylic acid, cyclododecyl (meth) acrylic acid, methyl cyclohexyl (meth) acrylic acid, ( Alicyclic skeleton-containing alkyl ester of (meth) acrylic acid such as trimethylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, cyclohexyl ⁇ -ethoxyacrylate, etc .; Aromatic ring skeleton-containing ester of (meth) acrylic acid such as phenyl (meth) acrylate; Etc.
  • transduced into the alkyl group in (meth) acrylic acid alkyl ester can also be mentioned.
  • the substituent of the substituent-containing (meth) acrylic acid alkyl ester is a group that substitutes the hydrogen atom of the alkyl group, and specific examples thereof include a phenyl group, an alkoxy group, and a phenoxy group.
  • substituent-containing (meth) acrylic acid alkyl ester examples include 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2- (meth) acrylate Examples thereof include (2-phenoxyethoxy) ethyl, phenoxydiethylene glycol (meth) acrylate, and phenoxypoly (ethylene glycol) (meth) acrylate.
  • acrylic acid esters can be used alone or in combination of two or more different ones.
  • the (meth) acrylic resin (A) has a structural unit derived from a (meth) acrylic acid alkyl ester (a1) whose homopolymer has a glass transition temperature Tg of less than 0 ° C., and a homopolymer Tg of 0 ° C. or more It is preferable to contain the structural unit derived from (meth) acrylic acid alkyl ester (a2). Containing the structural unit derived from the acrylic acid alkyl ester (a1) and the structural unit derived from the acrylic acid alkyl ester (a2) is advantageous for enhancing the high temperature durability of the pressure-sensitive adhesive layer.
  • Tg of the homopolymer of (meth) acrylic acid alkyl ester literature values such as, for example, POLYMER HANDBOOK (Wiley-Interscience) can be adopted.
  • (meth) acrylic acid alkyl ester (a1) examples include ethyl acrylate, n- and i-propyl acrylate, n- and i-butyl acrylate, n-pentyl acrylate, n- and acrylate acrylic acid -Hexyl, n-heptyl acrylate, n- and i-octyl acrylate, 2-ethylhexyl acrylate, n- and i-nonyl acrylate, n- and i-decyl acrylate, n-dodecyl acrylate And the like.
  • examples thereof include (meth) acrylic acid alkyl esters having about 2 to 12 carbon atoms in the alkyl group.
  • the (meth) acrylic acid alkyl ester (a1) may be used alone or in combination of two or more. Among them, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate and the like are preferable from the viewpoint of followability and rework when laminated on an optical film.
  • the (meth) acrylic acid alkyl ester (a2) is a (meth) acrylic acid alkyl ester other than the (meth) acrylic acid alkyl ester (a1).
  • Specific examples of the (meth) acrylic acid alkyl ester (a2) include methyl acrylate, cyclohexyl acrylate, isoboronyl acrylate, stearyl acrylate, t-butyl acrylate and the like.
  • the (meth) acrylic acid alkyl ester (a2) may be used alone or in combination of two or more. Among them, from the viewpoint of high temperature durability, the (meth) acrylic acid alkyl ester (a2) preferably contains methyl acrylate, cyclohexyl acrylate, isoboronyl acrylate and the like, and more preferably methyl acrylate.
  • the structural unit derived from the (meth) acrylic acid ester represented by the formula (I) is preferably 50% by mass or more, and more preferably 60 to 95% by mass in the total structural units contained in the (meth) acrylic resin.
  • the content is preferably 65 to 95% by mass or more.
  • a structural unit derived from monomers other than (meth) acrylic acid ester a structural unit derived from a monomer having a polar functional group is preferable, and a structure derived from a (meth) acrylic acid ester having a polar functional group Units are more preferred.
  • polar functional groups include hydroxy groups, carboxyl groups, substituted or unsubstituted amino groups, and heterocyclic groups such as epoxy groups.
  • a monomer having a hydroxy group or a monomer having a carboxyl group is preferable in view of the reactivity between the (meth) acrylic acid ester polymer and the crosslinking agent, and a monomer having a hydroxy group and a carboxyl group It is more preferable to include any of monomers having a group.
  • a monomer having a hydroxy group 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate are preferable. In particular, good durability can be obtained by using 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and 5-hydroxypentyl acrylate.
  • acrylic acid is preferably used as a monomer having a carboxyl group.
  • not to substantially contain the monomer which has an amino group from a viewpoint of preventing peeling force enhancement of the separate film which can be laminated
  • “not substantially contained” means that it is 0.1 parts by weight or less in 100 parts by weight of all the constituent units constituting the (meth) acrylic resin (A).
  • the content of the structural unit derived from the monomer having a polar functional group is preferably 20 parts by mass or less, more preferably 0 based on 100 parts by mass of all structural units of the (meth) acrylic resin (A). 0.5 parts by weight or more and 15 parts by weight or less, more preferably 0.5 parts by weight or more and 10 parts by weight or less, particularly preferably 1 parts by weight or more and 7 parts by weight or less.
  • the content of the structural unit derived from the monomer having an aromatic group is preferably 20 parts by mass or less, more preferably 4 parts by mass with respect to 100 parts by mass of the total structural units of the (meth) acrylic resin (A).
  • the content is not less than 20 parts by mass and preferably not less than 4 parts by mass and not more than 16 parts by mass.
  • structural units derived from monomers other than (meth) acrylic acid esters structural units derived from styrenic monomers, structural units derived from vinyl monomers, plural (meth) acryloyl groups in the molecule Examples include structural units derived from monomers having a group, and structural units derived from (meth) acrylamide type monomers.
  • styrene-based monomers styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene, etc .; fluorostyrene, Halogenated styrenes such as chlorostyrene, bromostyrene, dibromostyrene, iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; and divinylbenzene.
  • alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylsty
  • vinyl monomers include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene chloride and the like And vinylidene halides; nitrogen-containing heteroaromatic vinyls such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; conjugated dienes such as butadiene, isoprene and chloroprene; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.
  • fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate
  • vinyl halides such as vinyl chloride and vinyl bromide
  • vinylidene halides nitrogen-containing heteroaromatic vinyls such as vinylpyridine, vinylpyrrolidone and vinylcarbazol
  • monomers having a plurality of (meth) acryloyl groups in the molecule 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di ( Two (meth) acryloyl groups in the molecule such as meta) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate and tripropylene glycol di (meth) acrylate Monomers having; monomers having three (meth) acryloyl groups in a molecule such as trimethylolpropane tri (meth) acrylate.
  • Examples of (meth) acrylamide monomers include N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N- (4-) Hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- (6-hydroxyhexyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide Meta) acrylamide, N-isopropyl (meth) acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamide, N- [2- (2-) 2-Oxo-1-imidazolidinyl) ethyl] (meth) acrylamide 2-acryloylamin
  • N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) acrylamide and N- (2-methylpropoxymethyl) acrylamide are preferable.
  • the weight average molecular weight (Mw) of the (meth) acrylic resin (A) is preferably 500,000 to 2,500,000.
  • the weight average molecular weight is 500,000 or more, the durability of the pressure-sensitive adhesive layer in a high temperature environment is improved, and defects such as peeling between adherends and the pressure-sensitive adhesive layer, cohesive failure of the pressure-sensitive adhesive layer, etc. It is easy to control.
  • the weight average molecular weight is 2,500,000 or less, it is advantageous from the viewpoint of coatability when processing the pressure-sensitive adhesive composition into, for example, a sheet (coating on a substrate).
  • the weight-average molecular weight is preferably 600,000 to 1,800,000, more preferably 700,000 to 1,700,000, and particularly preferably 100, from the viewpoint of achieving both the durability of the pressure-sensitive adhesive layer and the coatability of the pressure-sensitive adhesive composition. It is 10,000 to 1.6 million.
  • the molecular weight distribution (Mw / Mn) represented by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) is usually 2 to 10, preferably 3 to 8, and more preferably 3 to 6 .
  • the weight average molecular weight can be analyzed by gel permeation chromatography and is a value in terms of standard polystyrene.
  • the viscosity at 25 ° C. is preferably 20 Pa ⁇ s or less, preferably 0.1 to 15 Pa ⁇ s. It is more preferable that It is advantageous from the viewpoint of the coatability at the time of applying an adhesive constituent to a substrate as it is a viscosity of this range.
  • the viscosity can be measured by a Brookfield viscometer.
  • the glass transition temperature (Tg) of the (meth) acrylic resin (A) is, for example, -60 to 20 ° C, preferably -50 to 15 ° C, more preferably -45 to 10 ° C, particularly -40 to 0 ° C. May be It is advantageous for the wettability improvement with respect to the adherend base material of an adhesive layer that Tg is below an upper limit, and it is advantageous for the durable improvement of an adhesive layer to be more than a lower limit.
  • the glass transition temperature can be measured by a differential scanning calorimeter (DSC).
  • the (meth) acrylic resin (A) can be produced by a known method such as, for example, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and the solution polymerization method is particularly preferable.
  • a solution polymerization method for example, a monomer and an organic solvent are mixed, a thermal polymerization initiator is added under a nitrogen atmosphere, and a temperature condition of about 40 to 90 ° C., preferably about 50 to 80 ° C., 3 to 15 The method of stirring for about time is mentioned.
  • monomers or a thermal polymerization initiator may be added continuously or intermittently during the polymerization.
  • the monomer and thermal initiator may be in the state of being added to an organic solvent.
  • a polymerization initiator As a polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, etc. are used.
  • a photopolymerization initiator 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone and the like can be mentioned.
  • the proportion of the polymerization initiator is about 0.001 to 5 parts by mass with respect to 100 parts by mass of the total of the monomers constituting the (meth) acrylic resin.
  • the polymerization of the (meth) acrylic resin may be carried out by a polymerization method using active energy rays (for example, ultraviolet rays and the like).
  • Organic solvents include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propyl alcohol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone Can be mentioned.
  • the content of the (meth) acrylic resin (A) is usually 60% by mass to 99.9% by mass, preferably 70% by mass to 99.5% by mass in 100% by mass of the pressure-sensitive adhesive composition. More preferably, it is 80% by mass to 99% by mass.
  • the pressure-sensitive adhesive composition can contain a crosslinking agent (b).
  • the crosslinking agent (b) reacts with polar functional groups (for example, hydroxy group, amino group, carboxyl group, heterocyclic group, etc.) in the (meth) acrylic resin (A).
  • the crosslinking agent (B) forms a crosslinked structure with a (meth) acrylic resin or the like, and forms a crosslinked structure that is advantageous for durability and reworkability.
  • crosslinking agent (b) examples include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, metal chelate-based crosslinking agents and the like, and in particular the pot life of the pressure-sensitive adhesive composition and the durability of the pressure-sensitive adhesive layer, crosslinking It is preferable that it is an isocyanate type crosslinking agent from a viewpoint of speed etc.
  • the isocyanate compound a compound having at least two isocyanato groups (-NCO) in the molecule is preferable.
  • aliphatic isocyanate compounds for example, hexamethylene diisocyanate etc.
  • alicyclic isocyanate compounds for example isophorone diisocyanate
  • aromatic isocyanate compounds eg, tolylene diisocyanate, xylylene diisocyanate diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.
  • the crosslinking agent (B) may be an adduct of the above-mentioned isocyanate compound with a polyhydric alcohol compound (adduct) [for example, an adduct of glycerol, trimethylolpropane etc.], isocyanurate, burette type compound, polyether polyol, polyester It may be a derivative such as a urethane prepolymer type isocyanate compound which is addition-reacted with a polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol or the like.
  • the crosslinking agents (B) can be used alone or in combination of two or more.
  • aromatic isocyanate compounds eg, tolylene diisocyanate, xylylene diisocyanate
  • aliphatic isocyanate compounds eg, hexamethylene diisocyanate
  • polyhydric alcohol compounds thereof eg, glycerol, trimethylolpropane
  • adducts thereof, or isocyanurates e.g, glycerol, trimethylolpropane
  • the content of the crosslinking agent (b) is usually 0.01 to 15 parts by mass, preferably 0.05 to 10 parts by mass, relative to 100 parts by mass of the (meth) acrylic resin (A). Preferably, it is 0.1 to 5 parts by weight.
  • the resin composition may further contain a silane compound (D).
  • silane compound (D) examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, Examples thereof include 3-methacryloyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.
  • the silane compound (D) may be a silicone oligomer.
  • the specific example of the silicone oligomer is as
  • 3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer 3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetraethoxysilane Oligomers containing mercaptopropyl group-containing oligomers; mercaptomethyltrimethoxysilane-tetramethoxysilane oligomers, mercaptomethyltrimethoxysilane-tetraethoxysilane oligomers, mercaptomethyltriethoxysilane-tetramethoxysilane oligomers, mercaptomethyltriethoxysilane-tetraethoxy Mercaptomethyl group-containing oligomers such as silane oligomers; 3-glycid
  • -Containing oligomers of vinyl 3-aminopropyltrimethoxysilane-tetramethoxysilane Polymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetra Amino group-containing such as methoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer, etc
  • the silane compound (D) may be a silane compound represented by the following formula (d1).
  • the adhesion (or adhesion) can be further improved, so that a pressure-sensitive adhesive layer having excellent peel resistance can be formed.
  • adhesion or adhesiveness
  • high durability can be exhibited.
  • B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group
  • -CH 2- may be substituted by -O- or -CO-
  • R d7 represents an alkyl group having 1 to 5 carbon atoms
  • R d8 , R d9 , R d10 , R d11 and R d12 respectively represent Independently represents an alkyl group of 1 to 5 carbon atoms or an alkoxy group of 1 to 5 carbon atoms
  • B represents an alkanediyl group having 1 to 20 carbon atoms such as methylene group, ethylene group, trimethylene group, tetramethylene group, tetramethylene group, hexamethylene group, heptamethylene group, octamethylene group, etc .; 1,2-cyclobutylene group), cyclopentylene group (eg, 1,2-cyclopentylene group), cyclohexylene group (eg, 1,2-cyclohexylene group), cyclooctylene group (eg, 1,2-cyclobutylene group)
  • a divalent alicyclic hydrocarbon group having a carbon number of 3 to 20, such as a cyclooctylene group), or an alkanediyl group thereof and -CH2- constituting the alicyclic hydrocarbon group is -O- or- The group substituted by CO- is shown.
  • R d7 represents an alkyl group having a carbon number of 1 to 5, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, pentyl group, etc.
  • R d8 , R d9 , R d10 , R d11 and R d12 are each independently an alkyl group having 1 to 5 carbon atoms exemplified for R d7 , or a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, a butoxy group or an s-butoxy group
  • an alkoxy group having 1 to 5 carbon atoms such as t-butoxy group.
  • Desirable R d8 , R d9 , R d10 , R d11 and R d12 are each independently an alkoxy group having 1 to 5 carbon atoms. These silane compounds (D) can be used alone or in combination of two or more.
  • silane compound represented by the above formula (d1) examples include (trimethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, and 1,2-bis (triethoxysilyl) ethane.
  • the content of the silane compound (D) is usually 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, per 100 parts by weight of the (meth) acrylic resin (A).
  • the amount is preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight. It is advantageous for suppression of the bleed-out of the silane compound (D) from an adhesive layer that it is below the said upper limit, and adhesion with an adhesive layer, a metal layer, a glass substrate, etc. being more than the said lower limit It is easy to improve the properties (or adhesion), which is advantageous for improving the peeling resistance and the like.
  • the pressure-sensitive adhesive composition may further contain an antistatic agent.
  • an antistatic agent surfactants, siloxane compounds, conductive polymers, ionic compounds and the like can be mentioned, with preference given to ionic compounds.
  • the ionic compound include conventional ones.
  • a cation component which comprises an ionic compound an organic cation, an inorganic cation, etc. are mentioned.
  • the organic cation include pyridinium cation, pyrrolidinium cation, piperidinium cation, imidazolium cation, ammonium cation, sulfonium cation, phosphonium cation and the like.
  • inorganic cations include lithium cations, potassium cations, sodium cations, alkali metal cations such as cesium cations, and alkaline earth metal cations such as magnesium cations and calcium cations.
  • pyridinium cation, imidazolium cation, pyrrolidinium cation, lithium cation and potassium cation are preferable from the viewpoint of compatibility with the (meth) acrylic resin.
  • the anion component constituting the ionic compound may be either an inorganic anion or an organic anion, but in terms of antistatic performance, an anion component containing a fluorine atom is preferred.
  • anion component containing a fluorine atom for example, hexafluorophosphate anion (PF 6- ), bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N-], bis (fluorosulfonyl) imide anion [(FSO) 2 ) 2 N-], tetra (pentafluorophenyl) borate anion [(C 6 F 5 ) 4 B-] and the like.
  • PF 6- hexafluorophosphate anion
  • bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N-]
  • bis (fluorosulfonyl) imide anion [(FSO) 2 ) 2 N-] bis (fluorosulfonyl) imide anion [(FSO) 2 ) 2 N-]
  • tetra (pentafluorophenyl) borate anion (C 6 F
  • bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N-]
  • tetra (pentafluorophenyl) borate anion [(C 6 F 5 ) 4 B-]
  • the ionic compound which is solid at room temperature is preferred in view of the temporal stability of the antistatic performance of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.
  • the content of the antistatic agent is, for example, 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 1 to 7 with respect to 100 parts by mass of the (meth) acrylic resin (A). It is mass.
  • the pressure-sensitive adhesive composition can contain one or more additives such as a solvent, a crosslinking catalyst, a tackifier, a plasticizer, a softener, a pigment, a rust inhibitor, an inorganic filler, and light scattering fine particles.
  • additives such as a solvent, a crosslinking catalyst, a tackifier, a plasticizer, a softener, a pigment, a rust inhibitor, an inorganic filler, and light scattering fine particles.
  • FIG. 1 An example of the pressure-sensitive adhesive layer-carrying optical film according to the present invention is shown in FIG.
  • the separate film (release film) 3 may be laminated on the side opposite to the above.
  • the separate film 3 is usually peeled and removed at the time of use of the pressure-sensitive adhesive layer-attached optical film (for example, at the time of lamination on a liquid crystal cell, retardation film, etc.).
  • the separate film is, for example, a film on which an adhesive layer of a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarete, etc. is subjected to release treatment such as silicone treatment. it can.
  • FIG. 1 to FIG. 2 An example of the layer configuration of the optical laminate including the optical film according to the present invention is shown in FIG. 1 to FIG.
  • An optical laminate 10A described in FIG. 2 is an optical laminate including a protective film 4, an adhesive layer 5, a polarizing film 6, an adhesive layer 5, an optical film 1 of the present invention, and an adhesive layer 7.
  • An optical laminate 10B described in FIG. 3 is an optical laminate including the optical film 1, the adhesive layer 5, the polarizing film 6, the adhesive layer 5, the protective film 4 and the pressure-sensitive adhesive layer 7 of the present invention.
  • a protective film 4 an adhesive layer 5, a polarizing film 6, an adhesive layer 5, an optical film 1 of the present invention, an adhesive layer 7, It is an optical laminate including the optical film 40, the pressure-sensitive adhesive layer 7a, and the light emitting element 30 (liquid crystal cell, OLED cell).
  • An optical film such as a retardation film, a polarizing film, or a window film may be laminated on the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive layer-attached optical film of the present invention.
  • the retardation film is an optical film showing optical anisotropy, and for example, polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, polycycloolefin, polystyrene, polysulfone, polyether sulfone, polyvinylidene fluoro,
  • An example is a stretched film obtained by stretching a polymer film composed of a ride / polymethyl methacrylate, acetyl cellulose, a saponified ethylene-vinyl acetate copolymer, polyvinyl chloride and the like by about 1.01 to 6 times.
  • the retardation film includes a zero retardation film, and also includes a film referred to as a uniaxial retardation film, a low photoelastic modulus retardation film, a wide viewing angle retardation film, or the like.
  • a film referred to as a temperature compensation type retardation film a film referred to as a temperature-compensated retardation film, a film in which optical anisotropy is expressed by application and orientation of a liquid crystal compound, and a film in which optical anisotropy is expressed by application of an inorganic layered compound.
  • “NH film” (trade name; film in which rod-like liquid crystals are inclined and aligned) sold by Nippon Mining & Energy Co., Ltd.
  • WV film sold by Fujifilm Co., Ltd.
  • VAC film (trade name; film of perfect biaxial orientation type) sold by Sumitomo Chemical Co., Ltd., "new VAC film” sold by Sumitomo Chemical Co., Ltd. Trade name; biaxially oriented film) and the like.
  • the zero retardation film is an optically isotropic film in which both the front retardation R e and the retardation R th in the thickness direction are -15 to 15 nm.
  • resin films made of cellulose resins, polyolefin resins (chain polyolefin resins, polycycloolefin resins, etc.) or polyethylene terephthalate resins can be mentioned. Cellulose-based resins or polyolefin-based resins are preferred in that they are easy.
  • the zero retardation film can also be used as a protective film.
  • Z-TAC As the zero retardation film, “Z-TAC” (trade name) sold by Fuji Film Co., Ltd., “Zero Tack (registered trademark)” sold by Konica Minolta Opto Co., Ltd., Nippon Zeon Co., Ltd. And “ZF-14” (trade name) sold by
  • the retardation film is preferably a retardation film obtained by curing a polymerizable liquid crystal compound.
  • the first form retardation film in which a rod-like liquid crystal compound is oriented in the horizontal direction with respect to a supporting substrate
  • second form rod-like Retardation film in which a liquid crystal compound is oriented in a direction perpendicular to a supporting substrate
  • Third embodiment Retardation film in which a rod-like liquid crystal compound has a helical orientation in the plane
  • fourth embodiment The retardation film in which the discotic liquid crystal compound is obliquely oriented
  • the fifth form a biaxial retardation film in which the discotic liquid crystal compound is oriented in the direction perpendicular to the supporting substrate.
  • the 1st form, the 2nd form, and the 5th form are used suitably. Or these may be laminated and used.
  • the retardation film When the retardation film is a layer composed of a polymer in the alignment state of the polymerizable liquid crystal compound (hereinafter sometimes referred to as "optically anisotropic layer"), the retardation film has reverse wavelength dispersion.
  • Reverse wavelength dispersion is an optical characteristic in which the in-plane retardation value at the short wavelength is smaller than the in-plane retardation value at the long wavelength, and preferably the retardation film has the following formula It is to satisfy (7) and equation (8).
  • Re ( ⁇ ) represents an in-plane retardation value for light of wavelength ⁇ nm.
  • the retardation film when the retardation film is in the first form and has reverse wavelength dispersion, it is preferable because the coloration at the time of black display in the display device is reduced, and 0.82 ⁇ in the formula (7). It is more preferable if Re (450) / Re (550) ⁇ 0.93. Furthermore, 120 ⁇ Re (550) ⁇ 150 is preferable.
  • Examples of the method for producing a retardation film from a polymer in the alignment state of the polymerizable liquid crystal compound include the method described in JP-A-2010-31223.
  • the front retardation value Re (550) may be adjusted in the range of 0 to 10 nm, preferably in the range of 0 to 5 nm, and the retardation value R th in the thickness direction is -10 to- It may be adjusted in the range of 300 nm, preferably in the range of -20 to -200 nm.
  • the retardation value R th in the thickness direction which means the refractive index anisotropy in the thickness direction, is an in-plane retardation difference from the retardation value R 50 measured by tilting 50 degrees with the in-plane fast axis as the tilt axis. It can be calculated from the value R 0 .
  • the phase difference value R th in the thickness direction retardation value R 0 in the plane retardation value R 50 measured by inclining 50 degrees inclination axis fast axis, thickness of the retardation film d, and positions the average refractive index n 0 of the retardation film obtains the n x, n y and n z by the following equation (10) to (12), these are substituted into equation (9) can be calculated.
  • R th [(n x + n y ) / 2-n z ] ⁇ d (9)
  • R 0 (n x -n y ) ⁇ d (10)
  • n y ' n y ⁇ n z / [ ny 2 ⁇ sin 2 ( ⁇ ) + n z 2 ⁇ cos 2 ( ⁇ )] 1/2
  • the retardation film may be a multilayer film having two or more layers.
  • stacked via the adhesive or the adhesive agent are mentioned.
  • the optical film 40 is a multilayer film in which two or more retardation films are laminated, as a configuration of an optical laminate including the optical film of the present invention, as shown in FIG.
  • a configuration including the laminated optical film 40 can be mentioned.
  • stacked the quarter wavelength phase difference layer 50a and the positive C layer 80 through the adhesive bond layer or the adhesive layer is also mentioned.
  • the first wavelength retardation layer 50 for giving a phase difference of 1 ⁇ 4 wavelength shown in FIG. 4 and the half wavelength retardation layer 70 for giving a phase difference of 1 ⁇ 2 wavelength to transmitted light The optical film of the fifth aspect may be used. In the case of the configuration of FIG. 4, it is more preferable that at least one is the fifth form.
  • the 1 ⁇ 4 wavelength retardation layer 50 a is preferably the optical film of the first embodiment, and more preferably satisfies the expressions (7) and (8).
  • a polarizing film is a film which has the property of absorbing linearly polarized light having a vibration plane parallel to its absorption axis and transmitting linearly polarized light having a vibration plane orthogonal to the absorption axis (parallel to the transmission axis), for example, polyvinyl A film in which a dichroic dye is adsorbed and oriented to an alcohol-based resin film can be used.
  • dichroic dyes include iodine and dichroic organic dyes.
  • the polyvinyl alcohol-based resin can be formed into a film by a known method.
  • the thickness of the raw film is usually 1 to 150 ⁇ m, and preferably 10 ⁇ m or more in consideration of the ease of stretching and the like.
  • the polarizing film may be, for example, uniaxially stretching a raw film, dyeing the film with a dichroic dye and adsorbing the dichroic dye, treating the film with an aqueous solution of boric acid, The film is subjected to a step of washing with water, and finally dried and manufactured.
  • the thickness of the polarizing film is usually 1 to 30 ⁇ m, preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, particularly 10 ⁇ m or less from the viewpoint of thinning.
  • a polarizing film obtained by adsorbing and orienting a dichroic dye to a polyvinyl alcohol-based resin film uses a single film of a polyvinyl alcohol-based resin film as a raw film, and uniaxial stretching and dyeing of the dichroic dye on this film
  • a base film having a polyvinyl alcohol-based resin layer by applying a coating solution (such as an aqueous solution) containing a polyvinyl alcohol-based resin to a base film and drying it, in addition to the method of treating (the method (1)) After uniaxial stretching for each base film, subjecting the stretched polyvinyl alcohol-based resin layer to a dyeing treatment of a dichroic dye, and then peeling and removing the base film (method (2 ) Can also be obtained.
  • a film made of a thermoplastic resin can be used, and preferably, polyester resins such as polyethylene terephthalate, polycarbonate resins, cellulose resins such as triacetyl cellulose, cyclic polyolefin resins such as norbornene resin It is a film made of a resin, a polystyrene resin, or the like.
  • the thin film polarizing film can be easily produced, and for example, the polarizing film 2 having a thickness of 7 ⁇ m or less can be easily produced.
  • the adhesive a known adhesive may be used, which may be a water-based adhesive or an active energy ray-curable adhesive.
  • a conventional water-based adhesive for example, an adhesive comprising a polyvinyl alcohol-based resin aqueous solution, a water-based two-component urethane-based emulsion adhesive, an aldehyde compound, an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, Amine compounds, crosslinking agents such as polyvalent metal salts, etc.
  • the water-based adhesive which consists of polyvinyl alcohol-type resin aqueous solution can be used suitably.
  • a water-based adhesive when using a water-based adhesive, after bonding a polarizing film and a protective film, it is preferable to implement the process to dry in order to remove the water contained in a water-based adhesive. After the drying step, there may be provided a curing step of curing at a temperature of about 20 to 45 ° C., for example.
  • the above-mentioned active energy ray-curable adhesive means an adhesive which is cured by irradiation with active energy rays such as ultraviolet rays and electron beams, and for example, a curable composition containing a polymerizable compound and a photopolymerization initiator, light
  • a curable composition containing a reactive resin, a curable composition containing a binder resin and a photoreactive crosslinking agent, and the like can be mentioned, with preference given to a UV curable adhesive.
  • an active energy ray-curable adhesive When using an active energy ray-curable adhesive, after bonding a polarizing film and a protective film, a drying process is performed if necessary, and then an active energy ray-curable adhesive is obtained by irradiating an active energy ray. A curing step to cure is performed.
  • the light source of the active energy ray is not particularly limited, ultraviolet light having a light emission distribution at a wavelength of 400 nm or less is preferable.
  • the method etc. of surface-activating processes such as a saponification process, a corona treatment, a plasma treatment, etc. are mentioned to these bonding surface of at least any one of these.
  • the adhesive for bonding these resin films may be either the same type of adhesive or different types of adhesives.
  • a preferable configuration of the polarizing plate is a polarizing plate in which a protective film is laminated on at least one surface of a polarizing film via an adhesive layer.
  • stacked on the visual recognition side is a protective film which consists of triacetyl-cellulose-type resin or cycloolefin type resin.
  • the protective film may be an unstretched film, or may be stretched in any direction and have a retardation.
  • a surface treatment layer such as a hard coat layer or an antiglare layer may be provided on the surface of the protective film laminated on the viewing side.
  • the protective film on the panel side is a protective film or a retardation film made of a triacetyl cellulose resin, a cycloolefin resin or an acrylic resin.
  • the retardation film may be a zero retardation film described later.
  • Another layer or film may be further laminated between the polarizing plate and the panel.
  • a retardation layer having a 1 ⁇ 4 wavelength retardation layer and a 1 ⁇ 2 wavelength retardation layer, and a 1 ⁇ 4 wavelength layer of reverse wavelength dispersion described later are laminated. Is preferred.
  • the retardation layer is preferably a liquid crystal retardation film from the viewpoint of thinning.
  • a condensing film is used for the purpose of light path control etc., and can be a prism array sheet, a lens array sheet, a dot attachment sheet, or the like.
  • the brightness enhancement film is used for the purpose of improving the brightness in a liquid crystal display device to which a polarizing plate is applied.
  • a reflection type polarization separation sheet designed to have anisotropy in reflectance by laminating a plurality of thin film films having mutually different anisotropy of refractive index, an alignment film of cholesteric liquid crystal polymer and its alignment
  • the circularly polarized light separation sheet etc. which supported the liquid crystal layer on the base film are mentioned.
  • the window film means a front plate in a flexible display such as a flexible display, and is generally disposed on the outermost surface of the display.
  • the window film is, for example, a resin film made of a polyimide resin.
  • the window film may be a hybrid film of an organic material and an inorganic material, such as a resin film containing, for example, polyimide and silica.
  • a hard coat layer may be disposed on the surface of the window film to impart surface hardness, stain resistance, and fingerprint resistance.
  • the film etc. of Unexamined-Japanese-Patent No. 2017-94488 are mentioned.
  • the optical film of the present invention may be used as a protective film of a polarizing plate.
  • the protective film is laminated on one side or both sides of the polarizing film via the adhesive layer.
  • the optical film of the present invention may be used as the protective film on one side of the polarizer, or the optical film of the present invention is used as the protective film on both sides.
  • a polarizing plate using the optical film of the present invention as a protective film of the polarizing plate may be laminated with another optical film through an adhesive layer or a pressure-sensitive adhesive layer, and an example of the laminate is shown in FIG. And shown in FIG.
  • the adhesive layer 5 is a layer formed of a known adhesive.
  • the known adhesive may be a water-based adhesive or an active energy ray-curable adhesive.
  • the pressure-sensitive adhesive layer 6 may be a layer formed of the above-described pressure-sensitive adhesive or may be a layer formed of another known pressure-sensitive adhesive.
  • the protective film 4 may be a known thermoplastic resin film.
  • the protective film 4 may be the optical film of the present invention.
  • the optical film of the present invention can be suitably used for a liquid crystal display device.
  • acetonitrile is removed using a vacuum evaporator and purified by column chromatography (silica gel) to purify the effluent containing the photoselective absorptive compound (1) represented by the formula (aa1).
  • the solvent was removed using to give yellow crystals.
  • the crystals were dried at 60 ° C. under reduced pressure to obtain 4.6 g of a photoselective absorptive compound (1) as a yellow powder.
  • the yield was 50%
  • ⁇ Gram absorption coefficient ⁇ measurement> In order to measure the gram absorption coefficient of the obtained photoselective absorptive compound (1), the photoselective absorptive compound (1) was dissolved in 2-butanone. The resulting solution (concentration: 0.007 g / L) is placed in a 1 cm quartz cell, and the quartz cell is set in a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation), and 1 nm steps 300 to 800 nm by double beam method. Absorbance was measured in the wavelength range of From the obtained absorbance value, the concentration of the light absorbing compound in the solution, and the optical path length of the quartz cell, the gram absorption coefficient for each wavelength was calculated using the following equation.
  • ⁇ ( ⁇ ) A ( ⁇ ) / CL
  • ⁇ ( ⁇ ) represents the gram absorption coefficient L / (g ⁇ cm) of the compound at the wavelength ⁇ nm
  • a ( ⁇ ) represents the absorbance at the wavelength ⁇ nm
  • C represents the concentration g / L
  • L is It represents the optical path length cm of the quartz cell.
  • the light selective absorption compound (1) gram absorbance coefficient has a value of ⁇ (405) of 47 L / (g ⁇ cm) and a value of ⁇ (440) of less than 0.1 L / (g ⁇ cm), The value of ⁇ (405) / ⁇ (440) was 80 or more.
  • Synthesis Example 2 Synthesis of Photoselective Absorption Compound (1) 10 g of a compound represented by the formula (aa) prepared by referring to JP-A-2014-194508 in a nitrogen atmosphere in a 200 mL four-necked flask provided with a Dimroth condenser and a thermometer, acetic anhydride (Wako Pure Chemical Industries, Ltd. 3.6 g of the product, Inc., 10 g of 2-butyloctyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 60 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) were charged, and stirred with a magnetic stirrer.
  • acetic anhydride (Wako Pure Chemical Industries, Ltd. 3.6 g of the product, Inc.
  • 10 g of 2-butyloctyl cyanoacetate manufactured by Tokyo Chemical Industry Co., Ltd.
  • 60 g of acetonitrile manufactured by Wa
  • the value of ⁇ (405) of the compound represented by formula (aa4) is 45 L / (g ⁇ cm), and the value of ⁇ (420) is 2.1 L / (G ⁇ cm).
  • Example 1 Preparation of Optical Film (1) Cellulose triacetate (Acetyl substitution degree: 2.87; Fuji Film Wako Pure Chemical Industries, Ltd., trade name “cellulose triacetate”), and a light selective absorption compound (1) (cellulose)
  • a cellulose acylate solution (solid content concentration: 10% by mass) consisting of 3 parts by mass per 100 parts by mass of triacetate and a solvent (mixture of methylene chloride and ethanol, mass ratio 87: 13) is charged into a mixing tank The components were dissolved by stirring.
  • the obtained lysate was uniformly cast on a glass support using an applicator, dried in an oven at 40 ° C. for 10 minutes, and further dried in an oven at 80 ° C. for 10 minutes.
  • the optical film (1) was peeled off from the glass support to obtain an optical film (1) having a light selective absorptivity.
  • the thickness of the dried optical film (1) was 30 ⁇ m.
  • the obtained optical film (1) was cut into a size of 5 mm ⁇ 30 mm.
  • a dynamic viscoelasticity measuring device “DVA-220” manufactured by IT Measurement & Control Co., Ltd. the long side of the cut light selective absorption layer (A-1) is in the tensile direction
  • the storage elastic modulus E 'at a temperature of 23.degree. C. to 200.degree. C. was determined by holding at an interval of 2 cm, setting the frequency of tension and contraction to 10 Hz, and the temperature rising rate to 10.degree. C./min.
  • the storage elastic modulus E ′ at 23 ° C. was 4100 MPa.
  • Example 2 Preparation of Optical Film (2) Cellulose triacetate (Acetyl substitution degree: 2.87; Fuji Film Wako Pure Chemical Industries, Ltd., trade name "cellulose triacetate"), and a light selective absorption compound (2) (cellulose A cellulose acylate solution (solid content concentration: 5% by mass) consisting of 2 parts by mass per 100 parts by mass of triacetate and a solvent (mixture of methylene chloride and ethanol, mass ratio 90:10) is charged into a mixing tank The components were dissolved by stirring. The obtained lysate was uniformly cast on a glass support using an applicator, dried in an oven at 40 ° C. for 10 minutes, and further dried in an oven at 80 ° C. for 10 minutes.
  • the optical film (2) was peeled off from the glass support to obtain an optical film (2) having a light selective absorptivity.
  • the thickness of the dried optical film (2) was 20 ⁇ m.
  • storage elastic modulus E 'in 23 degreeC was 3800 Mpa.
  • the measurement of a weight average molecular weight and a number average molecular weight uses four "TSK gel XL (made by Tosoh Corp.)" as a column in a GPC apparatus, and "Shodex GPC KF-802 (made by Showa Denko KK)" 1 piece, 5 pieces in total are connected in series, and using tetrahydrofuran as an eluent, the sample concentration is 5 mg / mL, the sample introduction amount is 100 ⁇ L, the temperature is 40 ° C, and the flow rate is 1 mL / min. Calculated by
  • crosslinking agent Ethyl acetate solution (75% solid concentration) of trimethylolpropane adduct of tolylene diisocyanate, trade name "Corronate L” obtained from Tosoh Corporation.
  • Silane compound 3-glycidoxypropyltrimethoxysilane, trade name "KBM403” obtained from Shin-Etsu Chemical Co., Ltd.
  • Production Example 2 The release treated surface of a separate film (trade name "PLR-382190” obtained from Lintec Co., Ltd.) consisting of a polyethylene terephthalate film subjected to release treatment, the pressure-sensitive adhesive composition (1) prepared in Production Example 1 The mixture was applied using an applicator so that the thickness after drying was 20 ⁇ m, and dried at 100 ° C. for 1 minute to prepare a pressure-sensitive adhesive layer (1).
  • a separate film trade name "PLR-382190” obtained from Lintec Co., Ltd.
  • the pressure-sensitive adhesive composition (2) prepared above was applied to the release-treated surface of a separate film (trade name “PLR-382190” obtained from Lintec Co., Ltd.) made of a polyethylene terephthalate film subjected to release treatment. It applied so that the thickness after drying might be set to 20 micrometers using an applicator, and it dried at 100 degreeC for 1 minute, and produced the adhesive layer (2).
  • a separate film trade name “PLR-382190” obtained from Lintec Co., Ltd.
  • Example 3 After corona discharge treatment is applied to one side of the optical film (1) obtained in Example 1, the acrylic pressure-sensitive adhesive produced in Production Example 1 is bonded by a laminator, and the conditions of temperature 23 ° C. and relative humidity 65% It was aged for 7 days to obtain an adhesive-coated optical film. Subsequently, the pressure-sensitive adhesive-attached optical film was cut into a size of 30 mm ⁇ 30 mm, and was bonded to non-alkali glass (trade name “EAGLE XG” manufactured by Corning Co., Ltd.) to prepare a sample.
  • non-alkali glass trade name “EAGLE XG” manufactured by Corning Co., Ltd.
  • Example 4 The optical film (2) was evaluated in the same manner as in Example 3 except that the optical film was replaced with the optical film (2) obtained in Example 2. The results are shown in Table 1.
  • Example 3 Comparative Example 1 Example 3 was repeated except that one surface of a 40 ⁇ m thick triacetyl cellulose film (trade name "KC4CW” obtained from Konica) was subjected to corona discharge treatment, and then the pressure-sensitive adhesive layer (2) was laminated by a laminator. Evaluation was performed in the same manner.
  • KC4CW triacetyl cellulose film
  • Example 2 A corona discharge treatment was applied to one side of a 40 ⁇ m thick triacetyl cellulose film (trade name "KC4CW” obtained from Konica), and then Example 3 and Example 3 were repeated except that the pressure-sensitive adhesive layer (3) was laminated by a laminator. Evaluation was performed in the same manner.
  • KC4CW triacetyl cellulose film
  • the optical film of the present invention has a good light absorption capacity (A (405)) in the vicinity of a wavelength of 405 nm of 2.0 or more. Therefore, when the optical film of the present invention is laminated on a retardation film or an organic EL element, the optical film of the present invention can block visible light of a short wavelength near 405 nm with respect to the retardation film or the organic EL element. Have a function of suppressing deterioration of a retardation film or an organic EL element from visible light of Furthermore, the optical film of the present invention has a good light absorbing function near a wavelength of 405 nm even after a weathering test, and has a good weathering resistance (durability). In addition, the optical film of the present invention has a low light absorption performance near a wavelength of 440 nm, and can provide a good color expression without inhibiting the light emission of the liquid crystal display device.
  • a (405) light absorption capacity
  • the optical film of the present invention is suitably used in liquid crystal panels and liquid crystal displays.

Abstract

In order to provide an optical film having a good deterioration suppression function for suppressing deterioration of a phase-difference film or an organic EL light-emitting element due to short-wavelength visible light, this optical film is formed from a resin composition containing a resin (A) and a selective light absorption compound (B), characterized in that the resin (A) is at least one type of resin selected from the group consisting of cellulose resin, a (meth)acrylic resin, a polyester resin, a polyamide resin, a polyimide resin and a cycloolefin resin, and satisfies the formula (1) below. (1) A(405) ≥ 0.5 [In formula (1), A(405) represents absorbance at the wavelength 405 nm.]

Description

光学フィルムOptical film
 本発明は、光学フィルムに関する。 The present invention relates to an optical film.
 有機EL表示装置や液晶表示装置等の表示装置(FPD:フラットパネルディスプレイ)には、有機EL素子、液晶セル等の表示素子や偏光板等の光学フィルムなど様々な部材が用いられている。これらの部材に用いられる有機EL化合物および液晶化合物等は有機物であるため、紫外線(UV)による劣化が問題となりやすい。このような問題を解決するため、例えば、特許文献1には370nm以下の波長域の紫外線吸収能が優れる紫外線吸収剤を偏光板の保護フィルムに添加した偏光板が記載されている。 Various members such as organic EL elements, display elements such as liquid crystal cells, and optical films such as polarizing plates are used in display devices (FPD: flat panel display) such as organic EL display devices and liquid crystal display devices. Since organic EL compounds and liquid crystal compounds used for these members are organic substances, deterioration by ultraviolet light (UV) tends to be a problem. In order to solve such a problem, for example, Patent Document 1 describes a polarizing plate in which an ultraviolet light absorber excellent in ultraviolet light absorbing ability in a wavelength range of 370 nm or less is added to a protective film of the polarizing plate.
特開2006-308936号公報Unexamined-Japanese-Patent No. 2006-308936
 また、近年の表示装置の薄型化が進む中、重合性液晶化合物を配向・光硬化させてなる液晶系位相差フィルムの開発が進められている。これらの液晶系位相差フィルムや有機EL発光素子は紫外線による劣化のみではなく、短波長の可視光においても劣化する傾向があることが明らかになってきた。しかしながら、特許文献1に記載の偏光板は、370nm以下の波長域の紫外線吸収能が優れていても、400nm付近の可視光の吸収性能が低く、液晶系位相差フィルムや有機EL発光素子の劣化抑制が十分ではない場合があった。さらに、近年の表示装置において、より良好な表示特性が求められていた。 Further, with the progress in thinning of display devices in recent years, development of a liquid crystal retardation film formed by aligning and photocuring a polymerizable liquid crystal compound has been advanced. It has become clear that these liquid crystal retardation films and organic EL light emitting devices tend not to deteriorate not only by ultraviolet light but also by visible light of short wavelength. However, the polarizing plate described in Patent Document 1 has a low ability to absorb visible light in the vicinity of 400 nm even if it has an excellent ability to absorb ultraviolet light in a wavelength range of 370 nm or less. There was a case where suppression was not enough. Furthermore, in display devices of recent years, better display characteristics have been required.
 本発明は、波長405nm付近の短波長の可視光に対する高い吸収選択性を示すことにより、位相差フィルムや有機EL発光素子の短波長の可視光による劣化について良好な抑制機能を有する光学フィルムを提供することである。 The present invention provides an optical film having a good suppression function for deterioration of a retardation film or an organic EL light emitting device due to visible light of short wavelength by showing high absorption selectivity to visible light of short wavelength around 405 nm. It is to be.
 本発明は、以下の発明を含む。
[1]樹脂(A)及び光選択吸収化合物(B)を含む樹脂組成物から形成される光学フィルムであって、
樹脂(A)は、セルロース系樹脂、(メタ)アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリイミド系樹脂及びシクロオレフィン系樹脂からなる群から選ばれる少なくとも1種の樹脂であり、
下記式(1)を満たすことを特徴とする光学フィルム。
   A(405)≧0.5      (1)
[式(1)中、A(405)は波長405nmにおける吸光度を表す。]
[2]下記式(2)を満たす[1]に記載の光学フィルム。
  A(440)≦0.1       (2)
[式(2)中、A(440)は波長440nmにおける吸光度を表す。]
[3]さらに、下記式(3)を満たす[1]又は[2]に記載の光学フィルム。
   A(405)/A(440)≧5      (3)
[式(3)中、A(405)は波長405nmにおける吸光度を表し、A(440)は波長440nmにおける吸光度を表す。]
[4]光選択吸収化合物(B)の含有量が、樹脂(A)100質量部に対して、0.01~20質量部である[1]~[3]のいずれかに記載の光学フィルム。
[5]樹脂(A)の23℃における貯蔵弾性率Eが、100MPa以上である[1]~[4]のいずれかに記載の光学フィルム。
[6]光選択吸収化合物(B)が、式(3)を満たす化合物である[1]~[5]に記載の光学フィルム。
 ε(405)≧20  (4)
〔式(4)中、ε(405)は波長405nmにおける化合物のグラム吸光係数を表す。グラム吸光係数の単位はL/(g・cm)である。〕
[7]光選択吸収化合物(B)は、式(5)を満たす化合物である[6]に記載の光学フィルム。
ε(405)/ε(440)≧20      (5)
[式(6)中、ε(405)は波長405nmにおける化合物のグラム吸光係数を表し、ε(440)は波長440nmにおけるグラム吸光度係数を表す。]
[8]光選択吸収化合物(B)が、分子内にメロシアニン構造を有する化合物である[1]~[7]に記載の光学フィルム。
[9][1]~[8]のいずれかに記載の光学フィルムの少なくとも一方の面に、粘着剤層を有する粘着剤付き光学フィルム。
[10][9]に記載の光学フィルムを有する表示装置。
The present invention includes the following inventions.
[1] An optical film formed from a resin composition containing a resin (A) and a photoselective absorption compound (B),
The resin (A) is at least one resin selected from the group consisting of cellulose resins, (meth) acrylic resins, polyester resins, polyamide resins, polyimide resins and cycloolefin resins,
An optical film characterized by satisfying the following formula (1).
A (405) 0.5 0.5 (1)
[In Formula (1), A (405) represents the absorbance at a wavelength of 405 nm. ]
[2] The optical film according to [1], which satisfies the following formula (2).
A (440) ≦ 0.1 (2)
[In Formula (2), A (440) represents the light absorbency in wavelength 440nm. ]
[3] The optical film according to [1] or [2], further satisfying the following formula (3).
A (405) / A (440) ≧ 5 (3)
[In Formula (3), A (405) represents the absorbance at a wavelength of 405 nm, and A (440) represents the absorbance at a wavelength of 440 nm. ]
[4] The optical film according to any one of [1] to [3], wherein the content of the light selective absorption compound (B) is 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin (A) .
[5] The optical film according to any one of [1] to [4], wherein the storage elastic modulus E at 23 ° C. of the resin (A) is 100 MPa or more.
[6] The optical film as described in [1] to [5], wherein the photoselective absorption compound (B) is a compound satisfying the formula (3).
ε (405) 20 20 (4)
[In Formula (4), (epsilon) (405) represents the gram absorption coefficient of a compound in wavelength 405 nm. The unit of gram absorption coefficient is L / (g · cm). ]
[7] The optical film according to [6], wherein the light selective absorption compound (B) is a compound satisfying the formula (5).
ε (405) / ε (440) ≧ 20 (5)
[In Formula (6), (epsilon) (405) represents the gram absorption coefficient of the compound in wavelength 405 nm, and (epsilon) (440) represents the gram absorption coefficient in wavelength 440 nm. ]
[8] The optical film as described in [1] to [7], wherein the photoselective absorption compound (B) is a compound having a merocyanine structure in the molecule.
[9] An optical film with an adhesive having an adhesive layer on at least one surface of the optical film according to any one of [1] to [8].
The display apparatus which has an optical film as described in [10] [9].
 本発明の光学フィルムは、405nm付近の短波長の可視光に対する高い吸収選択性を示すことにより、位相差フィルムや有機EL発光素子の短波長の可視光による劣化について良好な抑制機能を有する。また、本発明の光学フィルムは、耐候性試験後であっても波長405nm付近の短波長の可視光に対する高い吸収選択性を示し、耐候性試験後であっても短波長の可視光による劣化の抑制を保つことが出来る。本発明の光学フィルムを表示装置に用いた場合には良好な表示特性と耐久性とを付与することができる。 The optical film of the present invention exhibits a high absorption selectivity for visible light of a short wavelength near 405 nm, and thus has a good suppression function for deterioration of the retardation film or the organic EL light emitting element due to visible light of a short wavelength. In addition, the optical film of the present invention exhibits high absorption selectivity for visible light of short wavelength near 405 nm even after weathering test, and deterioration by visible light of short wavelength even after weathering test You can keep control. When the optical film of the present invention is used in a display device, good display characteristics and durability can be imparted.
本発明に係る粘着剤層付光学フィルムの一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the optical film with an adhesive layer which concerns on this invention. 本発明に係る光学フィルムを含む積層体の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the laminated body containing the optical film which concerns on this invention. 本発明に係る光学フィルムを含む積層体の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the laminated body containing the optical film which concerns on this invention. 本発明に係る光学フィルムを含む積層体の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the laminated body containing the optical film which concerns on this invention. 本発明に係る光学フィルムを含む積層体の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the laminated body containing the optical film which concerns on this invention.
 本発明の光学フィルムは、樹脂(A)及び光選択吸収化合物(B)を含む樹脂組成物から形成される光学フィルムであって、
樹脂(A)は、セルロース系樹脂、(メタ)アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリイミド系樹脂及びシクロオレフィン系樹脂からなる群から選ばれる少なくとも1種の樹脂であり、下記式(1)を満たすことを特徴とする。   A(405)≧0.5      (1)
[式(1)中、A(405)は波長405nmにおける吸光度を表す。]
The optical film of the present invention is an optical film formed from a resin composition containing a resin (A) and a light selective absorption compound (B),
The resin (A) is at least one resin selected from the group consisting of a cellulose resin, a (meth) acrylic resin, a polyester resin, a polyamide resin, a polyimide resin and a cycloolefin resin, and It is characterized by satisfying 1). A (405) 0.5 0.5 (1)
[In Formula (1), A (405) represents the absorbance at a wavelength of 405 nm. ]
 A(405)の値が大きいほど波長405nmにおける吸収が高いことを表し、A(405)の値が0.5未満であると、波長405nmにおける吸収が低く、紫外線における有機EL素子等の表示装置や位相差フィルムの劣化が起こりやすい。A(405)の値は、好ましくは0.6以上であり、より好ましくは0.8以上であり、特に好ましくは1.0以上である。上限は特にないが、通常は10以下である。 The larger the value of A (405), the higher the absorption at a wavelength of 405 nm. If the value of A (405) is less than 0.5, the absorption at a wavelength of 405 nm is low, and a display device such as an organic EL element in ultraviolet light And deterioration of the retardation film are likely to occur. The value of A (405) is preferably 0.6 or more, more preferably 0.8 or more, and particularly preferably 1.0 or more. There is no particular upper limit, but it is usually 10 or less.
 本発明の光学フィルムは、さらに下記式(2)を満たすことが好ましい。
  A(440)≦0.1        (2)
[式(2)中、A(440)は、波長440nmにおける吸光度を表す。]
 A(440)の値が小さいほど波長440nmにおける吸収が低いことを表し、A(440)の値が0.1を超えると、表示装置における良好な色彩表現を損なう傾向にある。また表示装置の発光を阻害するため、輝度も低下してしまう。A(440)の値は、好ましくは0.05以下であり、より好ましくは0.04以下であり、特に好ましくは0.03である。下限は特にないが、通常は0.00001以上である。
The optical film of the present invention preferably further satisfies the following formula (2).
A (440) ≦ 0.1 (2)
[In Formula (2), A (440) represents the light absorbency in wavelength 440nm. ]
The smaller the value of A (440), the lower the absorption at a wavelength of 440 nm. When the value of A (440) exceeds 0.1, there is a tendency to impair good color expression in the display device. In addition, since the light emission of the display device is inhibited, the luminance is also reduced. The value of A (440) is preferably 0.05 or less, more preferably 0.04 or less, and particularly preferably 0.03. The lower limit is not particularly limited, but is usually 0.00001 or more.
 本発明の光学フィルムは、さらに下記式(3)を満たすことが好ましい。
  A(405)/A(440)≧5         (3)
[式(3)中、A(405)は波長405nmにおける吸光度を表し、A(440)は波長440nmにおける吸光度を表す。]
 A(405)/A(440)の値は、波長440nmにおける吸収の大きさに対する波長405nmの吸収の大きさを表し、この値が大きいほど405nm付近の波長域に特異的な吸収があることを表す。A(405)/A(440)の値は10以上であることが好ましく、30以上であることがより好ましく、特に好ましくは60以上である。
The optical film of the present invention preferably further satisfies the following formula (3).
A (405) / A (440) ≧ 5 (3)
[In Formula (3), A (405) represents the absorbance at a wavelength of 405 nm, and A (440) represents the absorbance at a wavelength of 440 nm. ]
The value of A (405) / A (440) represents the magnitude of absorption at a wavelength of 405 nm with respect to the magnitude of absorption at a wavelength of 440 nm. The larger the value, the specific absorption in a wavelength range near 405 nm. Represent. The value of A (405) / A (440) is preferably 10 or more, more preferably 30 or more, and particularly preferably 60 or more.
 本発明の光学フィルムは、23℃における貯蔵弾性率E’は、通常100MPa以上であり、好ましくは300MPa以上であり、より好ましくは500MPa以上であり、さらに好ましくは1000MPa以上であり、特に好ましくは3500MPa以上である。下限は制限ないが、通常100000MPa以下である。
 本発明の光学フィルムの23℃における貯蔵弾性率は、実施例に記載の方法で測定できる。
In the optical film of the present invention, the storage elastic modulus E ′ at 23 ° C. is usually 100 MPa or more, preferably 300 MPa or more, more preferably 500 MPa or more, still more preferably 1000 MPa or more, particularly preferably 3500 MPa It is above. Although the lower limit is not limited, it is usually 100000 MPa or less.
The storage elastic modulus at 23 ° C. of the optical film of the present invention can be measured by the method described in the examples.
 本発明の光学フィルムは、樹脂(A)及び光選択吸収化合物(B)を含む樹脂組成物(以下「樹脂組成物(1)」という場合がある。)から形成される。
 樹脂(A)は、セルロース系樹脂、(メタ)アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリイミド系樹脂及びシクロオレフィン系樹脂からなる群から選ばれる少なくとも1種の樹脂である。
The optical film of the present invention is formed from a resin composition containing a resin (A) and a light selective absorption compound (B) (hereinafter sometimes referred to as "resin composition (1)").
The resin (A) is at least one resin selected from the group consisting of cellulose resins, (meth) acrylic resins, polyester resins, polyamide resins, polyimide resins, and cycloolefin resins.
 セルロース系樹脂としては、好ましくはセルロースエステル系樹脂、すなわち、セルロースにおける水酸基の少なくとも一部が酢酸エステル化されている樹脂であり、一部が酢酸エステル化され、一部が他の酸でエステル化されている混合エステルであってもよい。セルロースエステル系樹脂は、好ましくはアセチルセルロース系樹脂である。アセチルセルロース系樹脂の具体例として、トリアセチルセルロース、ジアセチルセルロース、セルロースアセテートプロピオネート、セルロースアセテートブチレート等を挙げることができる。
 アセチルセルロースの原料綿は発明協会公開技法2001-1745等で公知の木材
パルプや綿リンターなどのセルロース原料を用いることができる。また、アセチルセルロースは、木材化学180~190頁(共立出版、右田他、1968年)等に記載の方法
で合成することができる。
 トリアセチルセルロースの市販品としては、富士フィルム社製の商品名「UV-50」、「UV-80」、「SH-80」、「TD-80U」、「TD-TAC」、「UZ-TAC」等が挙げられる。
The cellulose-based resin is preferably a cellulose ester-based resin, that is, a resin in which at least a part of hydroxyl groups in cellulose is acetate-esterified, a part is acetate-esterified, and a part is esterified with another acid It may be a mixed ester. The cellulose ester resin is preferably an acetyl cellulose resin. Specific examples of the acetyl cellulose-based resin include triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, and cellulose acetate butyrate.
As a raw material cotton of acetyl cellulose, cellulose raw materials such as wood pulp and cotton linters which are known according to Inventive Society of Japan published technology 2001-1745 etc. can be used. In addition, acetylcellulose can be synthesized by the method described in Wood Chemistry, pp. 180-190 (Kyoritsu Shuppan, Akita et al., 1968).
As commercial products of triacetyl cellulose, trade names "UV-50", "UV-80", "SH-80", "TD-80U", "TD-TAC", "UZ-TAC" manufactured by Fuji Film Co., Ltd. Etc. are mentioned.
 (メタ)アクリル系樹脂としては、メタクリル酸アルキルエステル又はアクリル酸アルキルエステルの単独重合体や、メタクリル酸アルキルエステルとアクリル酸アルキルエステルとの共重合体などが挙げられる。メタクリル酸アルキルエステルとしては、具体的に、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレートなどが、またアクリル酸アルキルエステルとしては、具体的に、メチルアクリレート、エチルアクリレート、プロピルアクリレートなどがそれぞれ挙げられる。かかる(メタ)アクリル系樹脂には、汎用の(メタ)アクリル系樹脂として市販されているものが使用できる。(メタ)アクリル系樹脂として、耐衝撃(メタ)アクリル樹脂と呼ばれるものを使用してもよい。
 また、(メタ)アクリル系樹脂の具体例としては、三菱レイヨン株式会社の「アクリペットVH」、「アクリペットVRL20A」等も挙げられる。
Examples of (meth) acrylic resins include homopolymers of methacrylic acid alkyl esters or acrylic acid alkyl esters, and copolymers of methacrylic acid alkyl esters and acrylic acid alkyl esters. Specific examples of the methacrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate and propyl methacrylate. Specific examples of the acrylic acid alkyl ester include methyl acrylate, ethyl acrylate and propyl acrylate. As such (meth) acrylic resins, those commercially available as general-purpose (meth) acrylic resins can be used. As the (meth) acrylic resin, one called an impact resistant (meth) acrylic resin may be used.
Moreover, "acrypet VH" of Mitsubishi Rayon Co., Ltd. and "acrypet VRL 20A" etc. are mentioned as a specific example of (meth) acrylic-type resin.
 ポリエステル系樹脂は、主鎖にエステル結合の繰り返し単位を持つ重合体樹脂であり、一般的には多価カルボン酸またはその誘導体と多価アルコールまたはその誘導体との縮合重合によって得られる。
ポリエステルを与える多価カルボン酸またはその誘導体としては、テレフタル酸、イソフタル酸、フタル酸、2,6-ナフタレンジカルボン酸、ジフェニルジカルボン酸、ジフェニルスルホンジカルボン酸、ジフェノキシエタンジカルボン酸、5-ナトリウムスルホンジカルボン酸などの芳香族ジカルボン酸、シュウ酸、コハク酸、アジピン酸、セバシン酸、ダイマー酸、マレイン酸、フマル酸などの脂肪族ジカルボン酸、1,4-シクロヘキサンジカルボン酸などの脂環族ジカルボン酸、パラオキシ安息香酸などのオキシカルボン酸、並びに、それらの誘導体を挙げることができる。ジカルボン酸の誘導体としてはたとえばテレフタル酸ジメチル、テレフタル酸ジエチル、テレフタル酸2-ヒドロキシエチルメチルエステル、2,6-ナフタレンジカルボン酸ジメチル、イソフタル酸ジメチル、アジピン酸ジメチル、マレイン酸ジエチル、ダイマー酸ジメチルなどのエステル化物を挙げることができる。中でも、成型性、取り扱い性の点で、テレフタル酸、イソフタル酸、2,6-ナフタレンジカルボン酸、1,4-シクロヘキサンジカルボン酸、および、それらのエステル化物が好ましく用いられる。
ポリエステルを与える多価アルコールまたはその誘導体としては、エチレングリコール、ジエチレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、ネオペンチルグリコールなどの脂肪族ジヒドロキシ化合物、ジエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールなどのポリオキシアルキレングリコール、1,4-シクロヘキサンジメタノール、スピログリコールなどの脂環族ジヒドロキシ化合物、ビスフェノールA、ビスフェノールSなどの芳香族ジヒドロキシ化合物、並びに、それらの誘導体が挙げられる。中でも、成型性、取り扱い性の点で、エチレングリコール、ジエチレングリコール、1,3-プロパンジオール、1,4-ブタンジオール、ネオペンチルグリコール、1,4-シクロヘキサンジメタノールが好ましく用いられる。
ポリエステル系樹脂としては、例えばポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリトリメチレンテレフタレート、ポリトリメチレンナフタレート、ポリシクロへキサンジメチルテレフタレート、ポリシクロヘキサンジメチルナフタレートなどが挙げられる。これらのうち、ポリエチレンテレフタレートまたはポリエチレンナフタレートなどが好ましい。
The polyester resin is a polymer resin having a repeating unit of an ester bond in the main chain, and is generally obtained by condensation polymerization of a polyvalent carboxylic acid or a derivative thereof and a polyalcohol or a derivative thereof.
Examples of polyvalent carboxylic acids or derivatives thereof which give polyesters include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenoxy ethane dicarboxylic acid, 5-sodium sulfone dicarboxylic acid Aliphatic dicarboxylic acids such as acids, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acids, aliphatic dicarboxylic acids such as maleic acid and fumaric acid, and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid Mention may be made of oxycarboxylic acids such as parahydroxybenzoic acid, as well as their derivatives. Examples of derivatives of dicarboxylic acid include dimethyl terephthalate, diethyl terephthalate, 2-hydroxyethyl methyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, dimethyl adipate, diethyl maleate, dimethyl dimer acid, etc. Esterified products can be mentioned. Among them, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and their esterified products are preferably used in view of moldability and handleability.
As polyhydric alcohols or derivatives thereof which give polyesters, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Aliphatic dihydroxy compounds such as diol, 1,6-hexanediol, neopentyl glycol etc., polyoxyalkylene glycols such as diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol etc., 1,4-cyclohexanedimethanol, spiro glycol etc. Alicyclic dihydroxy compounds, aromatic dihydroxy compounds such as bisphenol A and bisphenol S, and derivatives thereof can be mentioned. Among them, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol and 1,4-cyclohexanedimethanol are preferably used in terms of moldability and handleability.
Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethyl terephthalate, and polycyclohexanedimethyl naphthalate. Among these, polyethylene terephthalate or polyethylene naphthalate is preferable.
 ポリアミド系樹脂は、主鎖として繰り返し単位にアミド結合を含む重合体樹脂であり、例えば芳香環骨格がアミド結合により結合された芳香族ポリアミド(アラミド)や脂肪族骨格がアミド結合により結合された脂肪族ポリアミド等が挙げられる。一般的には多価カルボン酸またはその誘導体と多価アミンとの重合反応等により得ることができる。
 ポリアミドを与える多価カルボン酸またはその誘導体としては、テレフタル酸クロライド、2-クロロ-テレフタル酸クロライド、イソフタル酸ジクロライド、ナフタレンジカルボニルクロライド、ビフェニルジカルボニルクロライド、ターフェニルジカルボニルクロライドなどが挙げられる。
 ポリアミドを与える多価アミンとしては、例えば4,4’-ジアミノジフェニルエーテル、3,4’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルスルホン、3,3’-ジアミノジフェニルスルホン、2,2’-ジトリフルオロメチル-4,4’-ジアミノビフェニル、9,9-ビス(4-アミノフェニル)フルオレン、9,9-ビス(4-アミノ-3-メチルフェニル)フルオレン、ビス[4-(4-アミノフェノキシ)フェニル]スルホン、ビス[4-(3-アミノフェノキシ)フェニル]スルホン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、2,2-ビス(4-アミノフェニル)ヘキサフルオロプロパンなどが挙げられるが、好ましくは4,4’-ジアミノジフェニルスルホン、3,3’-ジアミノジフェニルスルホン、2,2’-ジトリフルオロメチル-4,4’-ジアミノビフェニル、9,9-ビス(4-アミノフェニル)フルオレン、9,9-ビス(4-アミノ-3-メチルフェニル)フルオレン、1,4-シクロヘキサンジアミン、1,4-ノルボルネンジアミンが挙げられる。
The polyamide resin is a polymer resin containing an amide bond in a repeating unit as a main chain, and for example, an aromatic polyamide (aramid) in which an aromatic ring skeleton is bonded by an amide bond or a fat in which an aliphatic skeleton is bonded by an amide bond Family polyamide and the like. Generally, it can be obtained by the polymerization reaction of a polyvalent carboxylic acid or a derivative thereof and a polyvalent amine.
Examples of polyvalent carboxylic acids which give polyamides or derivatives thereof include terephthalic acid chloride, 2-chloro-terephthalic acid chloride, isophthalic acid dichloride, naphthalene dicarbonyl chloride, biphenyl dicarbonyl chloride, terphenyl dicarbonyl chloride and the like.
Examples of polyhydric amines giving polyamides include 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,2'-ditriol. Fluoromethyl-4,4'-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, bis [4- (4-aminophenoxy) ) Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis (4-aminophenyl) hexafluoro Examples thereof include propane and the like, preferably 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodi Phenylsulfone, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, It includes 1,4-cyclohexanediamine and 1,4-norbornene diamine.
 ポリイミド系樹脂は、主鎖として繰り返し単位にイミド結合を含む重合体樹脂であり、ジアミン類とテトラカルボン酸二無水物とを出発原料として、重縮合によって得られる縮合型ポリイミドが一般的である。ジアミン類としては、芳香族ジアミン類、脂環式ジアミン類、脂肪族ジアミン類等を用いることができる。テトラカルボン酸二無水物としては、芳香族テトラカルボン酸二無水物、脂環式テトラカルボン酸二無水物、非環式脂肪族テトラカルボン酸二無水物等を用いることができる。ジアミン類及びテトラカルボン酸二無水物はそれぞれ、単独で用いてもよいし、2種以上を併用して用いてもよい。テトラカルボン酸二無水物に代えて、酸クロライド化合物等のテトラカルボン酸化合物類縁体から選ばれるテトラカルボン酸化合物を出発原料として用いてもよい。 A polyimide-based resin is a polymer resin containing an imide bond in a repeating unit as a main chain, and a condensation type polyimide obtained by polycondensation using a diamine and tetracarboxylic acid dianhydride as a starting material is generally used. As diamines, aromatic diamines, alicyclic diamines, aliphatic diamines, etc. can be used. As tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, acyclic aliphatic tetracarboxylic acid dianhydride, etc. can be used. The diamines and the tetracarboxylic acid dianhydride may be used alone or in combination of two or more. Instead of tetracarboxylic acid dianhydride, a tetracarboxylic acid compound selected from tetracarboxylic acid compound analogs such as an acid chloride compound may be used as a starting material.
 シクロオレフィン系樹脂は、例えば、ノルボルネンや多環ノルボルネン系モノマーのような環状オレフィン(シクロオレフィン)からなるモノマーのユニットを有する熱可塑性の樹脂であり、熱可塑性シクロオレフィン系樹脂とも呼ばれる。このシクロオレフィン系樹脂は、上記シクロオレフィンの開環重合体や2種以上のシクロオレフィンを用いた開環共重合体の水素添加物であってもよく、シクロオレフィンと、鎖状オレフィンや、ビニル基の如き重合性二重結合を有する芳香族化合物などとの付加重合体であってもよい。シクロオレフィン系樹脂には、極性基が導入されていてもよい。 The cycloolefin resin is, for example, a thermoplastic resin having a monomer unit composed of a cyclic olefin (cycloolefin) such as norbornene or polycyclic norbornene monomer, and is also referred to as a thermoplastic cycloolefin resin. The cycloolefin resin may be a hydrogenated product of the above-mentioned ring-opening polymer of cycloolefin or ring-opening copolymer using two or more types of cyclo-olefin, and may be cycloolefin, chain olefin, vinyl It may be an addition polymer with an aromatic compound having a polymerizable double bond such as a group. A polar group may be introduced into the cycloolefin resin.
 シクロオレフィンと、鎖状オレフィン及び/又はビニル基を有する芳香族化合物との共重合体を用いて第一の保護フィルムを構成する場合、鎖状オレフィンとしては、エチレンやプロピレンなどが挙げられ、またビニル基を有する芳香族化合物としては、スチレン、α-メチルスチレン、核アルキル置換スチレンなどが挙げられる。このような共重合体においては、シクロオレフィンからなるモノマーのユニットが50モル%以下であってもよいが、好ましくは15~50モル%程度とされる。特に、シクロオレフィンと鎖状オレフィンとビニル基を有する芳香族化合物との三元共重合体を用いて第一の保護フィルムを構成する場合、シクロオレフィンからなるモノマーのユニットは、上述したように比較的少ない量とすることができる。かかる三元共重合体において、鎖状オレフィンからなるモノマーのユニットは、通常5~80モル%、ビニル基を有する芳香族化合物からなるモノマーのユニットは、通常5~80モル%である。 When the first protective film is formed using a copolymer of a cycloolefin and an aromatic compound having a linear olefin and / or a vinyl group, examples of the linear olefin include ethylene and propylene, and Examples of the aromatic compound having a vinyl group include styrene, α-methylstyrene and nuclear alkyl-substituted styrene. In such a copolymer, the unit of the cycloolefin monomer may be 50 mol% or less, preferably about 15 to 50 mol%. In particular, when a first protective film is formed using a ternary copolymer of a cycloolefin, a linear olefin, and an aromatic compound having a vinyl group, as described above, the unit of the monomer composed of the cycloolefin is compared Amount can be reduced. In such a ternary copolymer, the unit of monomers consisting of chain olefins is usually 5 to 80 mol%, and the unit of monomers consisting of aromatic compounds having a vinyl group is usually 5 to 80 mol%.
 シクロオレフィン系樹脂としては、適宜の市販品を用いることができる。例えば、ポリプラスチック株)から販売されている「TOPAS 」、JSR株式会社から販売されている「アートン」、日本ゼオン(株)から販売されている「ゼオノア(ZEONOR)」及び「ゼオネックス(ZEONEX)」、三井化学(株)から販売されている「アペル」(以上、いずれも商品名)などを挙げることができる。 As the cycloolefin resin, an appropriate commercially available product can be used. For example, "TOPAS" marketed by Polyplastics Co., Ltd., "Arton" marketed by JSR Corporation, "ZEONOR" marketed by Nippon Zeon Co., Ltd. and "ZEONEX" And “Apple” (all trade names) sold by Mitsui Chemicals, Inc., and the like.
 樹脂(A)の23℃における貯蔵弾性率Eは、通常100MPa以上であり、好ましくは300MPa以上であり、より好ましくは500MPa以上であり、特に好ましくは1000MPa以上である。下限は制限ないが、通常100000MPa以下である。 The storage elastic modulus E at 23 ° C. of the resin (A) is usually 100 MPa or more, preferably 300 MPa or more, more preferably 500 MPa or more, and particularly preferably 1000 MPa or more. Although the lower limit is not limited, it is usually 100000 MPa or less.
 光選択吸収化合物(B)は、波長405nmの光を選択的に吸収する化合物であり、下記式(4)を満たす化合物であることが好ましく、さらに式(5)を満たす化合物であることがより好ましい。
 ε(405)≧20  (4)
〔式(4)中、ε(405)は波長405nmにおける化合物のグラム吸光係数を表す。グラム吸光係数の単位はL/(g・cm)である。〕
ε(405)/ε(440)≧20      (5)
[式(6)中、ε(405)は波長405nmにおける化合物のグラム吸光係数を表し、ε(440)は波長440nmにおけるグラム吸光度係数を表す。]
 なお、グラム吸光度係数は、実施例に記載の方法で測定する。
The light selective absorption compound (B) is a compound that selectively absorbs light of a wavelength of 405 nm, is preferably a compound that satisfies the following formula (4), and is further a compound that satisfies the formula (5) preferable.
ε (405) 20 20 (4)
[In Formula (4), (epsilon) (405) represents the gram absorption coefficient of a compound in wavelength 405 nm. The unit of gram absorption coefficient is L / (g · cm). ]
ε (405) / ε (440) ≧ 20 (5)
[In Formula (6), (epsilon) (405) represents the gram absorption coefficient of the compound in wavelength 405 nm, and (epsilon) (440) represents the gram absorption coefficient in wavelength 440 nm. ]
The gram absorbance coefficient is measured by the method described in the examples.
 ε(405)の値が大きい化合物ほど波長405nmの光を吸収しやすく、紫外線や短波長の可視光による劣化抑制機能を発現しやすい。ε(405)の値が20L/(g・cm)未満であると、位相差フィルムや有機EL発光素子の紫外線や短波長の可視光による劣化抑制機能を発現するために、本発明の樹脂組成物中の光選択吸収化合物(B)の含有量が増大する。光選択吸収化合物(B)の含有量が増大すると、光選択吸収化合物(B)がブリードアウト又は不均一に分散してしまい、光吸収機能が不十分となることがある。ε(405)の値は20L/(g・cm)以上であることが好ましく、30L/(g・cm)以上であることがより好ましく、40L/(g・cm)以上であることがさらにより好ましく、通常500L/(g・cm)以下である。 The larger the value of ε (405) is, the easier it is to absorb light with a wavelength of 405 nm, and it is easy to exhibit the function of suppressing deterioration by ultraviolet light or visible light of short wavelength. When the value of ε (405) is less than 20 L / (g · cm), the resin composition of the present invention has the function of suppressing the deterioration of the retardation film or the organic EL light emitting device due to ultraviolet light or short wavelength visible light. The content of the photoselective absorption compound (B) in the substance is increased. When the content of the light selective absorption compound (B) is increased, the light selective absorption compound (B) may be bled out or dispersed unevenly, and the light absorption function may be insufficient. The value of ε (405) is preferably 20 L / (g · cm) or more, more preferably 30 L / (g · cm) or more, and even more preferably 40 L / (g · cm) or more Preferably, it is usually 500 L / (g · cm) or less.
 ε(405)/ε(440)の値が大きい化合物ほど、表示装置の色彩表現を阻害することなく、405nm付近の光を吸収し位相差フィルムや有機EL素子等の表示装置の光劣化を抑制することができる。ε(405)/ε(440)の値は20以上が好ましく、40以上がより好ましく、70以上がさらにより好ましく、80以上が特により好ましい。 A compound having a larger value of ε (405) / ε (440) absorbs light in the vicinity of 405 nm and suppresses light degradation of a display device such as a retardation film or an organic EL element without inhibiting color expression of the display device. can do. The value of ε (405) / ε (440) is preferably 20 or more, more preferably 40 or more, still more preferably 70 or more, and particularly preferably 80 or more.
 また、光選択吸収化合物(B)は、分子内にメロシアニン構造を含む化合物であることが好ましい。分子内にメロシアニン構造を含む化合物としては、-(N-C=C-C=C)-で示される部分構造を分子内に含有している化合物であって、例えば、メロシアニン系化合物、シアニン系化合物、インドール系化合物、ベンゾトリアゾール系化合物等が挙げられ、メロシアニン系化合物、シアニン系化合物及びベンゾトリアゾール系化合物であることが好ましく、より好ましくは式(I)で表される化合物である。
Figure JPOXMLDOC01-appb-I000001
[式中、R及びRは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数1~25のアルキル基、置換基を有していてもよい炭素数7~15のアラルキル基、炭素数6~15のアリール基、複素環基を表し、該アルキル基又はアラルキル基に含まれる-CH-は-NR1A-、-CO-、-SO-、-O-又は-S-に置換されていてもよい。
 R1Aは、水素原子又は炭素数1~6のアルキル基を表す。
 R、R及びRは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数1~6のアルキル基、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表し、該アルキル基に含まれる-CH-は-NR1B-、-CO-、-SO-、-O-又は-S-で置換されていてもよい。
 R1Bは、水素原子又は炭素数1~6のアルキル基を表す。
 R及びRは、それぞれ独立して、水素原子、炭素数1~25のアルキル基又は電子吸引性基を表すか、R及びRが互いに連結して環構造を形成してもよい。
 R及びRは互いに連結して環構造を形成してもよく、R及びRは互いに連結して環構造を形成してもよく、R及びRは互いに連結して環構造を形成してもよく、R及びRは、互いに連結して環構造を形成してもよい。]
Further, the photoselective absorption compound (B) is preferably a compound containing a merocyanine structure in the molecule. The compound having a merocyanine structure in the molecule is a compound having in its molecule a partial structure represented by-(N-C = C-C = C)-, and examples thereof include merocyanine compounds and cyanine compounds. A compound, an indole compound, a benzotriazole compound, etc. are mentioned, It is preferable that they are a merocyanine compound, a cyanine compound, and a benzotriazole compound, More preferably, it is a compound represented by Formula (I).
Figure JPOXMLDOC01-appb-I000001
[Wherein, R 1 and R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms which may have a substituent, or 7 to carbon atoms which may have a substituent; 15 represent an aralkyl group, an aryl group having a carbon number of 6 to 15, and a heterocyclic group, and -CH 2- contained in the alkyl group or the aralkyl group is -NR 1A- , -CO-, -SO 2- , -O It may be substituted by-or -S-.
R 1A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aromatic hydrocarbon group which may have a substituent Or an aromatic heterocyclic group which may have a substituent, and -CH 2- contained in the alkyl group is -NR 1B- , -CO-, -SO 2- , -O- or -S- And may be substituted.
R 1B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R 6 and R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an electron-withdrawing group, or R 6 and R 7 may combine with each other to form a ring structure .
R 1 and R 2 may be linked to each other to form a ring structure, and R 2 and R 3 may be linked to each other to form a ring structure, and R 2 and R 4 are linked to each other to form a ring structure And R 3 and R 6 may be linked to each other to form a ring structure. ]
 R及びRで表される炭素数1~25のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、2-シアノプロピル基、n-ブチル基、tert-ブチル基、sec-ブチル基、n-ペンチル基、n-ヘキシル基、1-メチルブチル基、3-メチルブチル基、n-オクチル基、n-デシル、2-へキシル-オクチル基等が挙げられる。
 R及びRで表される炭素数1~25のアルキル基が有していてもよい置換基としては、以下の群Aに記載の基が挙げられる。
群A:ニトロ基、ヒドロキシ基、カルボキシ基、スルホ基、シアノ基、アミノ基、ハロゲン原子、炭素数1~6のアルコキシ基、炭素数1~12のアルキルシリル基、炭素数2~8のアルキルカルボニル基、*-Ra1-(O-Ra2t1-Ra3(Ra1及びRa2は、それぞれ独立して、炭素数1~6のアルカンジイル基を表し、Ra3は炭素数1~6のアルキル基を表し、s1は1~3の整数を表す。)で表される基等が挙げられる。
 炭素数1~12のアルキルシリル基としては、メチルシリル基、エチルシリル、プロピルシリル基等のモノアルキルシリル基;ジメチルシリル基、ジエチルシリル基、メチルエチルシリル基等のジアルキルシリル基;トリメチルシリル、トリエチルシリル、トリプロピルシリル基等のトリアルキルシリル基が挙げられる。
 炭素数2~8のアルキルカルボニル基としては、メチルカルボニル基、エチルカルボニル基等が挙げられる。
 ハロゲン原子としては、フッ素原子、塩素原子、臭素原子等が挙げられる。
Examples of the alkyl group having 1 to 25 carbon atoms represented by R 1 and R 5 include methyl group, ethyl group, n-propyl group, isopropyl group, 2-cyanopropyl group, n-butyl group, tert-butyl group, and sec-butyl, n-pentyl, n-hexyl, 1-methylbutyl, 3-methylbutyl, n-octyl, n-decyl, 2-hexyl-octyl and the like.
Examples of the substituent which the alkyl group having 1 to 25 carbon atoms represented by R 1 and R 5 may have include the groups described in the following group A.
Group A: nitro, hydroxy, carboxy, sulfo, cyano, amino, halogen, alkoxy having 1 to 6 carbons, alkylsilyl having 1 to 12 carbons, alkyl having 2 to 8 carbons carbonyl group, * - R a1 - (O -R a2) t1 -R a3 (R a1 and R a2 each independently represent an alkanediyl group having 1 to 6 carbon atoms, R a3 is a C1- 6 represents an alkyl group, and s 1 represents an integer of 1 to 3.) and the like.
Examples of the alkylsilyl group having 1 to 12 carbon atoms include monoalkylsilyl groups such as methylsilyl group, ethylsilyl and propylsilyl groups; dialkylsilyl groups such as dimethylsilyl group, diethylsilyl group and methylethylsilyl group; trimethylsilyl and triethylsilyl, And trialkylsilyl groups such as tripropylsilyl group.
Examples of the alkylcarbonyl group having 2 to 8 carbon atoms include a methylcarbonyl group and an ethylcarbonyl group.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom etc. are mentioned.
 R及びRで表される炭素数7~15のアラルキル基としては、ベンジル基、フェニルエチル基等が挙げられる。アラルキル基に含まれる-CH-が、-SO-又は-COO-に置き換わった基としては2-フェニル酢酸エチル基等が挙げられる。
 R及びRで表される炭素数7~15のアラルキル基が有していてもよい置換基としては、以下の群Aに記載の基が挙げられる。
 R及びRで表される炭素数6~15のアリール基としては、フェニル基、ナフチル基、アントラセニル基等が挙げられる。
 R及びRで表される炭素数6~15のアリール基が有していてもよい置換基としては、上記群Aに記載の基が挙げられる。
 R及びRで表される炭素数6~15の複素環基としては、ピリジル基、ピロリジル基、キノリル基、チオフェン基、イミダゾリル基、オキサゾリル基、ピロール基、チアゾリル基及びフラニル基等の炭素数3~9の芳香族複素環基が挙げられる。
Examples of the aralkyl group having 7 to 15 carbon atoms represented by R 1 and R 5 include a benzyl group and a phenylethyl group. Examples of the group in which —CH 2 — contained in the aralkyl group is replaced by —SO 2 — or —COO— include a 2-phenylacetic acid ethyl group and the like.
Examples of the substituent which the aralkyl group having 7 to 15 carbon atoms represented by R 1 and R 5 may have include the groups described in the following group A.
Examples of the aryl group having 6 to 15 carbon atoms represented by R 1 and R 5 include a phenyl group, a naphthyl group and an anthracenyl group.
Examples of the substituent which the aryl group having 6 to 15 carbon atoms represented by R 1 and R 5 may have include the groups described in Group A above.
Examples of the heterocyclic group having 6 to 15 carbon atoms represented by R 1 and R 5 include carbons such as pyridyl, pyrrolidinyl, quinolyl, thiophene, imidazolyl, oxazolyl, pyrrole, thiazolyl and furanyl And 3 to 9 aromatic heterocyclic groups.
 R1A及びR1Bで表される炭素数1~6のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、tert-ブチル基、sec-ブチル基、n-ペンチル基、n-ヘキシル基等が挙げられる。 Examples of the alkyl group having 1 to 6 carbon atoms represented by R 1A and R 1B include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, n -Pentyl group, n-hexyl group and the like.
 R、R及びRで表される炭素数1~6のアルキル基としては、R1Bで表される炭素数1~6のアルキル基と同じものが挙げられる。
 R、R及びRで表される炭素数1~6のアルキル基が有していてもよい置換基としては、上記群Aに記載の基が挙げられる。
 R、R及びRで表される芳香族炭化水素基としては、フェニル基、ナフチル基、アントラセニル基等炭素数6~15のアリール基;ベンジル基、フェニルエチル基等の炭素数7~15のアラルキル基が挙げられる。
 R、R及びRで表される芳香族炭化水素基が有していてもよい置換基としては上記群Aに記載の基が挙げられる。
 R、R及びRで表される芳香族複素環としては、ピリジル基、ピロリジル基、キノリル基、チオフェン基、イミダゾリル基、オキサゾリル基、ピロール基、チアゾリル基及びフラニル基等の炭素数3~9の芳香族複素環基が挙げられる。
 R、R及びRで表される芳香族複素環が有していてもよい置換基としては、上記群Aに記載の基が挙げられる。
Examples of the alkyl group having 1 to 6 carbon atoms represented by R 2 , R 3 and R 4 include the same ones as the alkyl group having 1 to 6 carbon atoms represented by R 1B .
Examples of the substituent which the alkyl group having 1 to 6 carbon atoms represented by R 2 , R 3 and R 4 may have include the groups described in the above-mentioned group A.
The aromatic hydrocarbon group represented by R 2 , R 3 and R 4 includes aryl groups having 6 to 15 carbon atoms such as phenyl, naphthyl and anthracenyl; and 7 to 15 carbon atoms such as benzyl and phenylethyl. There may be mentioned 15 aralkyl groups.
Examples of the substituent which the aromatic hydrocarbon group represented by R 2 , R 3 and R 4 may have include the groups described in Group A above.
The aromatic heterocyclic ring represented by R 2 , R 3 and R 4 has 3 carbon atoms such as pyridyl, pyrrolidinyl, quinolyl, thiophene, imidazolyl, oxazolyl, pyrrole, thiazolyl and furanyl. And aromatic heterocyclic groups of -9.
As a substituent which the aromatic heterocyclic ring represented by R < 2 >, R < 3 > and R < 4 > may have, the group as described in the said group A is mentioned.
 R及びRで表される炭素数1~25のアルキル基としては、R及びRで表される炭素数1~25のアルキル基と同じものが挙げられる。
 R及びRで表される炭素数1~25のアルキル基が有していてもよい置換基としては、上記群Aに記載の基が挙げられる。
Examples of the alkyl group having 1 to 25 carbon atoms represented by R 6 and R 7 include the same ones as the alkyl group having 1 to 25 carbon atoms represented by R 1 and R 5 .
Examples of the substituent which the alkyl group having 1 to 25 carbon atoms represented by R 6 and R 7 may have include the groups described in Group A above.
 R及びRで表される炭素数1~25のアルキル基としては、R及びRで表される炭素数1~25のアルキル基と同じものが挙げられる。
 R及びRで表される電子吸引性基としては、例えば、シアノ基、ニトロ基、ハロゲン原子、ハロゲン原子で置換されたアルキル基、式(I-1)で表される基が挙げられる。
Figure JPOXMLDOC01-appb-I000002
[式中、R11は、水素原子又は炭素数1~25のアルキル基を表し、該アルキル基に含まれるメチレン基の少なくとも1つは酸素原子に置換されていてもよい。
 Xは、-CO-、-COO-、-OCO-、-CS-、-CSO-、-CSS-、-NR12CO-又はCONR13-を表す。
 R12及びR13は、それぞれ独立して、水素原子、炭素数1~6のアルキル基又はフェニル基を表す。]
Examples of the alkyl group having 1 to 25 carbon atoms represented by R 6 and R 7 include the same ones as the alkyl group having 1 to 25 carbon atoms represented by R 1 and R 5 .
Examples of the electron withdrawing group represented by R 6 and R 7 include a cyano group, a nitro group, a halogen atom, an alkyl group substituted with a halogen atom, and a group represented by formula (I-1) .
Figure JPOXMLDOC01-appb-I000002
[Wherein, R 11 represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, and at least one of the methylene groups contained in the alkyl group may be substituted by an oxygen atom.
X 1 is, -CO -, - COO -, - OCO -, - CS -, - CSO -, - CSS -, - NR 12 CO- or CONR 13 - represents a.
R 12 and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. ]
 ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
 ハロゲン原子で置換されたアルキル基としては、例えば、トリフルオロメチル基、ペルフルオロエチル基、ペルフルオロプロピル基、ペルフルオロイソプロピル基、ペルフルオロブチル基、ペルフルオロsec-ブチル基、ペルフルオロtert-ブチル基、ペルフルオロペンチル基及びペルフルオロヘキシル基等のパーフルオロアルキル基等が挙げられる。ハロゲン原子で置換されたアルキル基の炭素数としては、通常1~25である。
The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group substituted by a halogen atom include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, and the like Perfluoroalkyl groups, such as perfluorohexyl group, etc. are mentioned. The carbon number of the alkyl group substituted with a halogen atom is usually 1 to 25.
 R及びRは互いに連結して環構造を形成していてもよく、R及びRより形成される環構造としては、例えば、メルドラム酸構造、バルビツール酸構造、ジメドン構造等が挙げられる。
 R11で表される炭素数1~25のアルキル基としては、R及びRで表されるアルキル基と同じものが挙げられる。
R 6 and R 7 may be linked to each other to form a ring structure, and examples of the ring structure formed of R 6 and R 7 include a Meldrum's acid structure, a barbituric acid structure, a dimedone structure, etc. Be
Examples of the alkyl group having 1 to 25 carbon atoms represented by R 11 include the same as the alkyl groups represented by R 1 and R 5 .
 R及びRが互いに結合して形成される環構造としては、Rと結合している窒素原子を含む含窒素環構造であって、例えば、4~14員環の含窒素複素環が挙げられる。R及びRが互いに連結して形成される環構造は、単環であってもよいし、多環であってもよい。具体的には、ピロリジン環、ピロリン環、イミダゾリジン環、イミダゾリン環、オキサゾリン環、チアゾリン環、ピペリジン環、モルホリン環、ピペラジン環、インドール環、イソインドール環等が挙げられる。 The ring structure formed by bonding R 2 and R 3 to each other is a nitrogen-containing ring structure containing a nitrogen atom bonded to R 2, and is, for example, a 4- to 14-membered nitrogen-containing heterocyclic ring It can be mentioned. The ring structure formed by linking R 2 and R 3 to each other may be monocyclic or polycyclic. Specifically, pyrrolidine ring, pyrroline ring, imidazolidine ring, imidazoline ring, oxazoline ring, thiazoline ring, piperidine ring, morpholine ring, piperazine ring, indole ring, isoindole ring and the like can be mentioned.
 R及びRが互いに結合して形成される環構造としては、R及びRが結合している窒素原子を含む含窒素環構造であって、例えば、4~14員環(好ましくは4~8員環)の含窒素複素環が挙げられる。R及びRが互いに連結して形成される環構造は、単環であってもよいし、多環であってもよい。具体的には、R及びRが互いに連結して形成される環構造と同じものが挙げられる。 The ring structure formed by bonding R 1 and R 2 to each other is a nitrogen-containing ring structure containing a nitrogen atom to which R 1 and R 2 are bonded, and is, for example, a 4- to 14-membered ring (preferably And 4 to 8 membered rings). The ring structure formed by linking R 1 and R 2 to each other may be monocyclic or polycyclic. Specifically, the same as the ring structure formed by linking R 2 and R 3 to each other can be mentioned.
 R及びRが互いに結合して形成される環構造としては、4~14員環の含窒素環構造が挙げられ、5員環~9員環の含窒素環構造が好ましい。R及びRが互いに結合して形成される環構造は、単環であってもよいし、多環であってもよい。これらの環は置換基を有していてもよく、このような環構造としては、前記RとRにより形成される環構造として例示したものと同じものが挙げられる。 The ring structure formed by combining R 2 and R 4 with one another includes a 4- to 14-membered nitrogen-containing ring structure, and a 5- to 9-membered nitrogen-containing ring structure is preferable. The ring structure formed by bonding R 2 and R 4 to each other may be monocyclic or polycyclic. These rings may have a substituent, and as such a ring structure, the same one as exemplified as the ring structure formed by R 2 and R 3 may be mentioned.
 R及びRが互いに連結して形成される環構造としては、R-C=C-C=C-Rが環の骨格を形成する環構造である。例えば、フェニル基等が挙げられる。 The ring structure formed by linking R 3 and R 6 to each other is a ring structure in which R 3 -C = C-C = C-R 6 forms a ring skeleton. For example, a phenyl group etc. are mentioned.
 RとRが互いに連結して環構造を形成している式(I)で表される化合物としては式(I-A)で表される化合物が挙げられ、R及びRが互いに連結して環構造を形成している式(I)で表される化合物としては、式(I-B)で表される化合物等が挙げられる。
Figure JPOXMLDOC01-appb-I000003
[式(I-A)、式(I-B)中、R、R、R、R、R及びRは、それぞれ上記と同じ意味を表す。
 環W及び環Wは、それぞれ独立して、含窒素環を表す。]
Examples of the compound represented by formula (I) in which R 2 and R 3 are linked to each other to form a ring structure include compounds represented by formula (IA), and R 2 and R 4 Examples of the compound represented by the formula (I) which forms a ring structure by linking include a compound represented by the formula (IB) and the like.
Figure JPOXMLDOC01-appb-I000003
[In formula (IA) and formula (IB), R 1 , R 3 , R 4 , R 5 , R 6 and R 7 each represent the same meaning as described above.
Ring W 1 and ring W 2 each independently represent a nitrogen-containing ring. ]
 環W及び環Wは、環の構成単位として窒素原子を含有する含窒素環を表す。環W及び環Wは、それぞれ独立して、単環であってもよいし、多環であってもよく、窒素以外のヘテロ原子を環の構成単位として含んでいてもよい。環W及び環Wは、それぞれ独立して、5員環~9員環の環であることが好ましい。 Ring W 1 and ring W 2 represent a nitrogen-containing ring containing a nitrogen atom as a constituent unit of the ring. The ring W 1 and the ring W 2 may be each independently a single ring or multiple rings, and may contain a heteroatom other than nitrogen as a constituent unit of the ring. The ring W 1 and the ring W 2 are preferably each independently a 5- to 9-membered ring.
 式(I-A)で表される化合物は、式(I-A-1)で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-I000004
[式(I-A)中、R、R、R、R及びRは、それぞれ上記と同じ意味を表す。
 Aは、-CH-、-O-、-S-又は-NR1D-を表す。
 R14及びR15は、それぞれ独立して、水素原子又は炭素数1~12のアルキル基を表す。
 R1Dは、水素原子又は炭素数1~6のアルキル基を表す。]
The compound represented by the formula (IA) is preferably a compound represented by the formula (IA-1).
Figure JPOXMLDOC01-appb-I000004
[In formula (IA), R 1 , R 4 , R 5 , R 6 and R 7 each represent the same meaning as described above.
A 1 represents -CH 2- , -O-, -S- or -NR 1D- .
Each of R 14 and R 15 independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
R 1D represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]
 式(I-B)で表される化合物は、式(I-B-1)で表される化合物及び式(I-B-2)で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-I000005
[式(I-B-1)中、R、R及びRは、それぞれ上記と同じ意味を表す。
 R16は、それぞれ独立して、水素原子又は炭素数1~12のアルキル基、アリール基を表す。]
The compound represented by the formula (IB) is preferably a compound represented by the formula (IB-1) and a compound represented by the formula (IB-2).
Figure JPOXMLDOC01-appb-I000005
[In the formula (I-B-1), R 1 , R 6 and R 7 each represent the same meaning as described above.
Each R 16 independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group. ]
Figure JPOXMLDOC01-appb-I000006
[式(I-B-2)中、R、R、R及びRは、それぞれ上記と同じ意味を表す。
 R30は、水素原子、シアノ基、ニトロ基、ハロゲン原子、メルカプト基、アミノ基、炭素数1~12のアルキル基、炭素数1~12のアルコキシ基、炭素数6~18の芳香族炭化水素基、炭素数2~13のアシル基、炭素数2~13のアシルオキシ基又は炭素数2~13のアルコキシカルボニル基を表す。
 R31は、炭素数1~12のアルキル基、炭素数1~12のアルコキシ基、メルカプト基、炭素数1~12のアルキルチオ基、置換基を有していてもよいアミノ基又は複素環基を表す。]
Figure JPOXMLDOC01-appb-I000006
[In the formula (I-B-2), R 3 , R 5 , R 6 and R 7 each represent the same meaning as described above.
R 30 represents a hydrogen atom, a cyano group, a nitro group, a halogen atom, a mercapto group, an amino group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms And an acyl group having 2 to 13 carbon atoms, an acyloxy group having 2 to 13 carbon atoms, or an alkoxycarbonyl group having 2 to 13 carbon atoms.
R 31 represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a mercapto group, an alkylthio group having 1 to 12 carbon atoms, an amino group or heterocyclic group which may have a substituent, Represent. ]
 R30で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
 R30で表されるR30で表される炭素数2~13のアシル基としては、アセチル基、プロピオニル基及びブチリル基等が挙げられる。
 R30で表される炭素数2~13のアシルオキシ基としては、メチルカルボニルオキシ基、エチルカルボニルオキシ基、プロピルカルボニルオキシ基、ブチルカルボニルオキシ基等が挙げられる。
 R30で表される炭素数2~13のアルコキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ブトキシカルボニル基等が挙げられる。
 R30で表される炭素数6~18の芳香族炭化水素基としては、フェニル基、ナフチル基、ビフェニル基等の炭素数6~18のアリール基;ベンジル基、フェニルエチル基等の炭素数7~18のアラルキル基が挙げられる。
 R30で表される炭素数1~12のアルキル基としては、R14で表される炭素数1~12のアルキル基と同じものが挙げられる。
 R30で表される炭素数1~12のアルキル基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペントキシ基等が挙げられる。
 R30は、炭素数1~12のアルキル基、炭素数1~12のアルコキシ基、アミノ基又はメルカプト基であることが好ましい。
The halogen atom represented by R 30, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom.
The acyl group of 2 to 13 carbon atoms represented by R 30 represented by R 30, an acetyl group, and the like propionyl group and butyryl group.
Examples of the acyloxy group having 2 to 13 carbon atoms represented by R 30 include a methyl carbonyloxy group, an ethyl carbonyloxy group, a propyl carbonyloxy group, and a butyl carbonyloxy group.
Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms represented by R 30 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group and the like.
Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R 30 include aryl groups having 6 to 18 carbon atoms such as phenyl group, naphthyl group and biphenyl group; 7 carbon atoms such as benzyl group and phenylethyl group There may be mentioned an aralkyl group of -18.
Examples of the alkyl group having 1 to 12 carbon atoms represented by R 30 include the same ones as the alkyl group having 1 to 12 carbon atoms represented by R 14 .
Examples of the alkyl group having 1 to 12 carbon atoms represented by R 30 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group.
R 30 is preferably an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an amino group or a mercapto group.
 R31で表される炭素数1~12のアルキル基としては、R14で表される炭素数1~12のアルキル基と同じものが挙げられる。
 R31で表される炭素数1~12のアルコキシ基としては、R30で表される炭素数1~12のアルコキシ基と同じものが挙げられる。
 R31で表される炭素数1~12のアルキルチオ基としては、メチルチオ基、エチルチオ基、プロピルチオ基、ブチルチオ基、ペンチルチオ基、ヘキシルチオ基等が挙げられる。
 R31で表される置換基を有していてもよいアミノ基としては、アミノ基;N-メチルアミノ基、N-エチルアミノ基等の1つの炭素数1~8のアルキル基で置換されたアミノ基;N,N-ジメチルアミノ基、N,N-ジエチルアミノ基、N,N-メチルエチルアミノ基等の2つの炭素数1~8のアルキル基で置換されたアミノ基;等が挙げられる。
 R31で表される複素環としては、ピロリジニル基、ピペリジニル基、モルホリニル基等の炭素数4~9の含窒素複素環基等が挙げられる。
Examples of the alkyl group having 1 to 12 carbon atoms represented by R 31 include the same ones as the alkyl group having 1 to 12 carbon atoms represented by R 14 .
Examples of the C 1-12 alkoxy group represented by R 31 include the same as the C 1-12 alkoxy group represented by R 30 .
Examples of the alkylthio group having 1 to 12 carbon atoms represented by R 31 include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group and a hexylthio group.
The amino group which may have a substituent represented by R 31 is, for example, an amino group; one alkyl group having 1 to 8 carbon atoms such as N-methylamino group or N-ethylamino group Amino groups; amino groups substituted with two alkyl groups having 1 to 8 carbon atoms such as N, N-dimethylamino, N, N-diethylamino, N, N-methylethylamino and the like; and the like.
Examples of the heterocyclic ring represented by R 31 include nitrogen-containing heterocyclic groups having 4 to 9 carbon atoms such as pyrrolidinyl group, piperidinyl group and morpholinyl group.
 R及びRが互いに連結して環構造を形成し、かつR及びRが互いに結合して環構造を形成する式(I)で表される化合物としては、式(I-C)で表される化合物等が挙げられる。
Figure JPOXMLDOC01-appb-I000007
[式(I-C)中、R1、及びRは上記と同じ意味を表す。
 R21、R22は、それぞれ独立して、水素原子、炭素数1~12のアルキル基又はヒドロキシ基を表す。
 X及びXは、それぞれ独立して、-CH-又は-N(R25)=を表す。
 R25は、水素原子、炭素数1~25のアルキル基、置換基を有していてもよい芳香族炭化水素基を表す。]
As a compound represented by the formula (I) in which R 3 and R 6 are linked to each other to form a ring structure, and R 2 and R 4 are linked to each other to form a ring structure, a compound represented by formula (IC) And the like.
Figure JPOXMLDOC01-appb-I000007
[In formula (I-C), R 1, R 6 and R 7 represent the same meaning as described above.
Each of R 21 and R 22 independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a hydroxy group.
Each of X 2 and X 3 independently represents —CH 2 — or —N (R 25 ) =.
R 25 represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group which may have a substituent. ]
 R25で表される炭素数1~25のアルキル基としては、Rで表される炭素数1~25のアルキル基と同じものが挙げられる。
 R25で表される芳香族炭化水素基としては、フェニル基、ナフチル基等のアリール基:ベンジル基、フェニルエチル基等のアラルキル基:ビフェニル基等が挙げられ、炭素数6~20の芳香族炭化水素基であることが好ましい。R25で表される芳香族炭化水素基が有していてもよい置換基としては、ヒドロキシ基等が挙げられる。
Examples of the alkyl group having 1 to 25 carbon atoms represented by R 25 include the same ones as the alkyl group having 1 to 25 carbon atoms represented by R 1 .
Examples of the aromatic hydrocarbon group represented by R 25 include aryl groups such as phenyl group and naphthyl group: aralkyl groups such as benzyl group and phenylethyl group: biphenyl group and the like, and aromatics having 6 to 20 carbon atoms It is preferably a hydrocarbon group. Examples of the substituent which the aromatic hydrocarbon group represented by R 25 may have include a hydroxy group and the like.
 R及びRは、それぞれ独立して、電子吸引性基であることが好ましい。 Preferably, R 3 and R 6 are each independently an electron withdrawing group.
 R及びRが互いに連結して環構造を形成し、かつR及びRが互いに結合して環構造を形成する式(I)で表される化合物としては、式(I-D)で表される化合物等が挙げられる。
Figure JPOXMLDOC01-appb-I000008
 
[式(I-D)中、R、R5、R7は上記と同じ意味を表す。
 R25、R26、R27及びR28は、それぞれ独立して、水素原子、置換基を有してもよい炭素数1~12のアルキル基、ヒドロキシ基、アラルキル基を表す。]
Examples of the compound represented by the formula (I) in which R 1 and R 2 are linked to each other to form a ring structure and R 3 and R 6 are linked to each other to form a ring structure include a compound represented by formula (ID) And the like.
Figure JPOXMLDOC01-appb-I000008

[In the formula (I-D), R 4 , R 5 and R 7 represent the same meaning as described above.
R 25 , R 26 , R 27 and R 28 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, a hydroxy group or an aralkyl group. ]
 R25、R26、R27及びR28で表される炭素数1~12のアルキル基としては、R1A及びR1Bで表される炭素数1~12のアルキル基と同じものが挙げられる。R25、R26、R27及びR28で表される炭素数1~12のアルキル基が有していてもよい置換基としてはヒドロキシ基が挙げられる。
 R25、R26、R27及びR28で表されるアラルキル基としては、ベンジル基、フェニルエチル基等の炭素数7~15のアラルキル基が挙げられる。
Examples of the alkyl group having 1 to 12 carbon atoms represented by R 25 , R 26 , R 27 and R 28 include the same ones as the alkyl group having 1 to 12 carbon atoms represented by R 1A and R 1B . Examples of the substituent which the alkyl group having 1 to 12 carbon atoms represented by R 25 , R 26 , R 27 and R 28 may have include a hydroxy group.
Examples of the aralkyl group represented by R 25 , R 26 , R 27 and R 28 include aralkyl groups having 7 to 15 carbon atoms such as benzyl group and phenylethyl group.
 R及びRが互いに連結して環構造を形成している化合物(I)としては、式(I-E)で表される化合物等が挙げられる。
Figure JPOXMLDOC01-appb-I000009
[式(I-E)中、R、R、R、Rは、それぞれ上記と同じ意味を表す。
環Wは、環状化合物を表す]
 環Wは、5員環~9員環の環であり、窒素原子、酸素原子、硫黄原子等のヘテロ原子を環の構成単位として含んでいてもよい。
Examples of the compound (I) in which R 6 and R 7 are linked to each other to form a ring structure include compounds represented by the formula (IE) and the like.
Figure JPOXMLDOC01-appb-I000009
[In formula (IE), R 1 , R 3 , R 4 and R 5 each represent the same meaning as described above.
Ring W 3 represents a cyclic compound]
The ring W 3 is a 5- to 9-membered ring, and may contain a heteroatom such as a nitrogen atom, an oxygen atom or a sulfur atom as a constituent unit of the ring.
 式(I-E)で表される化合物は、式(IE-1)で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-I000010

[式(I-C-1)中、R、R、R及びRは、それぞれ上記と同じ意味を表す。
 R17、R18、R19、Rは、それぞれ独立して、水素原子又は置換基を有してもよい炭素数1~12のアルキル基、アラルキル基、アリール基を表し、該アルキル基又はアラルキル基に含まれる-CH-基は-NR1D-、-C(=O)-、-C(=S)-、-O-、-S-に置換されていてもよく、R17及びR18は互いに連結して環構造を形成してもよく、R18及びR19は互いに連結して環構造を形成してもよく、R19及びRは、互いに連結して環構造を形成してもよい。m、p、qはそれぞれ独立して0~3の整数を表す。]
The compound represented by the formula (IE) is preferably a compound represented by the formula (IE-1).
Figure JPOXMLDOC01-appb-I000010

[In formula (I-C-1), R 1 , R 2 , R 3 and R 5 each represent the same meaning as described above.
R 17 , R 18 , R 19 and R q each independently represent a hydrogen atom or an alkyl, aralkyl or aryl group having 1 to 12 carbon atoms which may have a substituent, and the alkyl or The -CH 2 -group contained in the aralkyl group may be substituted by -NR 1D- , -C (= O)-, -C (= S)-, -O-, -S-, R 17 and R 18 may be linked to each other to form a ring structure, R 18 and R 19 may be linked to each other to form a ring structure, and R 19 and R q are linked to each other to form a ring structure You may m, p and q each independently represent an integer of 0 to 3. ]
 式(I)で表される化合物としては、以下の化合物が挙げられる。
Figure JPOXMLDOC01-appb-I000011
Examples of the compound represented by the formula (I) include the following compounds.
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000014

Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000014

Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000016
Figure JPOXMLDOC01-appb-I000016
Figure JPOXMLDOC01-appb-I000017

Figure JPOXMLDOC01-appb-I000018
Figure JPOXMLDOC01-appb-I000017

Figure JPOXMLDOC01-appb-I000018
Figure JPOXMLDOC01-appb-I000019
Figure JPOXMLDOC01-appb-I000019
Figure JPOXMLDOC01-appb-I000020
Figure JPOXMLDOC01-appb-I000020
 光選択吸収化合物(B)の含有量は、樹脂(A)100質量部に対して、通常0.01~20質量部であり、好ましくは0.05~15質量部であり、より好ましくは0.1~10質量部であり、さらに好ましくは0.1~5質量部である。 The content of the light selective absorption compound (B) is usually 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, more preferably 0 based on 100 parts by mass of the resin (A). 1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.
 樹脂組成物(1)は、さらに、可塑剤、有機酸、色素、帯電防止剤、界面活性剤、滑剤、難燃剤、フィラー、ゴム粒子、位相差調整剤、紫外線吸収剤等を含んでいてもよい。 The resin composition (1) may further contain a plasticizer, an organic acid, a dye, an antistatic agent, a surfactant, a lubricant, a flame retardant, a filler, a rubber particle, a phase difference adjuster, an ultraviolet absorber and the like. Good.
 本発明の光学フィルムの製造方法としては、任意の適切な成形加工法が採用され得る。具体的には、圧縮成形法、トランスファー成形法、射出成形法、押出成形法、ブロー成形法、粉末成形法、FRP成形法、キャスト塗工法(例えば、流延法)、カレンダー成形法、熱プレス法等が挙げられる。得られるフィルムの平滑性を高め、良好な光学的均一性を得ることができることから、押出成形法またはキャスト塗工法が好ましい。成形条件は、使用される樹脂の組成や種類、位相差フィルムに所望される特性等に応じて適宜設定され得る。 Any appropriate forming method may be employed as a method of producing the optical film of the present invention. Specifically, compression molding method, transfer molding method, injection molding method, extrusion molding method, blow molding method, powder molding method, FRP molding method, cast coating method (for example, casting method), calendar molding method, heat press Law etc. are mentioned. The extrusion molding method or the cast coating method is preferred because the smoothness of the resulting film can be enhanced and good optical uniformity can be obtained. The molding conditions may be appropriately set according to the composition and type of the resin to be used, the characteristics desired for the retardation film, and the like.
 本発明の光学フィルムの厚みは、通常1~500μmであり、好ましくは5~300μmであり、より好ましくは10~150μmであり、特に好ましくは10~75μmである。
 本発明の光学フィルムは、未延伸であってもよいし、延伸されていてもよい。本発明の光学フィルムが延伸されている場合、一軸延伸であってもよいし、二軸延伸であってもよい。延伸倍率は、通常1.01~10倍、好ましくは1.01~6倍である。延伸方向に関しても、長さ方向、幅方向、厚さ方向、斜め方向等、様々な方向や次元に行なうことができる。
The thickness of the optical film of the present invention is usually 1 to 500 μm, preferably 5 to 300 μm, more preferably 10 to 150 μm, and particularly preferably 10 to 75 μm.
The optical film of the present invention may be unstretched or stretched. When the optical film of the present invention is stretched, it may be uniaxially stretched or biaxially stretched. The stretching ratio is usually 1.01 to 10 times, preferably 1.01 to 6 times. The stretching direction can also be performed in various directions and dimensions, such as the length direction, the width direction, the thickness direction, and the oblique direction.
 本発明の粘着剤層付光学フィルムは、本発明の光学フィルムの少なくとも一方の面に粘着剤層を有しているフィルムである。粘着剤層は、公知の粘着剤から形成される。公知の粘着剤としては、アクリル系、ゴム系、ウレタン系、シリコーン系、ポリビニルエーテル系などのベースポリマーを有する粘着剤のいずれであってもよいが、(メタ)アクリル樹脂(A)をベースポリマーとして含むアクリル系粘着剤組成物であることが好ましい。 The pressure-sensitive adhesive layer-carrying optical film of the present invention is a film having a pressure-sensitive adhesive layer on at least one surface of the optical film of the present invention. The pressure-sensitive adhesive layer is formed of a known pressure-sensitive adhesive. The known pressure-sensitive adhesive may be any pressure-sensitive adhesive having a base polymer such as acrylic, rubber, urethane, silicone, and polyvinyl ether, but the (meth) acrylic resin (A) is a base polymer It is preferable that it is an acrylic adhesive composition included as
 (メタ)アクリル系樹脂(A)は、(メタ)アクリル酸エステル由来の構成単位を主成分(好ましくは50質量%以上含む)重合体であることが好ましい。(メタ)アクリル酸エステルに由来する構造単位は、一種以上の(メタ)アクリル酸エステル以外の単量体に由来する構造単位(例えば、極性官能基を有する単量体に由来する構造単位)を含んでもよい。なお本明細書において、(メタ)アクリル酸とは、アクリル酸又はメタクリル酸のいずれでもよいことを意味し、他に、(メタ)アクリレートなどというときの「(メタ)」も同様の趣旨である。 The (meth) acrylic resin (A) is preferably a polymer as a main component (preferably containing 50% by mass or more) of a structural unit derived from a (meth) acrylic acid ester. The structural unit derived from (meth) acrylic acid ester is a structural unit derived from a monomer other than one or more (meth) acrylic acid esters (for example, a structural unit derived from a monomer having a polar functional group) May be included. In the present specification, (meth) acrylic acid means that either acrylic acid or methacrylic acid may be used, and in the case of (meth) acrylate etc., “(meth)” also has the same meaning. .
 (メタ)アクリル酸エステルとしては、下記式(I)で示される(メタ)アクリル酸エステルが挙げられる
Figure JPOXMLDOC01-appb-I000021
[式(I)中、R1 は水素原子又はメチル基で表し、R2 は炭素数1~14のアルキル基または炭素数7~20のアラルキル基を表し、該アルキル基または該アラルキル基の水素原子は、炭素数1~10のアルコキシ基で置き換わっていてもよい。]
Examples of the (meth) acrylic acid ester include (meth) acrylic acid esters represented by the following formula (I)
Figure JPOXMLDOC01-appb-I000021
[In formula (I), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkyl group having 1 to 14 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and hydrogen of the alkyl group or the aralkyl group The atom may be replaced by an alkoxy group having 1 to 10 carbon atoms. ]
 式(I)において、R2は、好ましくは、炭素数1~14のアルキル基であり、より好ましくは、炭素数1~8のアルキル基である。 In formula (I), R 2 is preferably an alkyl group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.
 式(I)で示される(メタ)アクリル酸エステルとしては、
(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸n-ペンチル、(メタ)アクリル酸n-ヘキシル、(メタ)アクリル酸n-ヘプチル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸n-ノニル、(メタ)アクリル酸n-デシル、(メタ)アクリル酸n-ドデシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ステアリル、等の(メタ)アクリル酸の直鎖状アルキルエステル;
(メタ)アクリル酸i-プロピル、(メタ)アクリル酸i-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸i-ペンチル、(メタ)アクリル酸i-ヘキシル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸i-オクチル、(メタ)アクリル酸i-ノニル、(メタ)アクリル酸i-ステアリル、(メタ)アクリル酸i-アミル、等の(メタ)アクリル酸の分枝状アルキルエステル;
(メタ)アクリル酸シクロへキシル、(メタ)アクリル酸イソボロニル、(メタ)アクリル酸アダマンチル、(メタ)アクリル酸ジシクロペンタニル、(メタ)アクリル酸シクロドデシル、(メタ)アクリル酸メチルシクロヘキシル、(メタ)アクリル酸トリメチルシクロヘキシル、(メタ)アクリル酸tert-ブチルシクロヘキシル、α-エトキシアクリル酸シクロヘキシル、等の(メタ)アクリル酸の脂環骨格含有アルキルエステル;
(メタ)アクリル酸フェニル等の(メタ)アクリル酸の芳香環骨格含有エステル;
等が挙げられる。
また、(メタ)アクリル酸アルキルエステルにおけるアルキル基に置換基が導入された置換基含有(メタ)アクリル酸アルキルエステルを挙げることもできる。置換基含有(メタ)アクリル酸アルキルエステルの置換基は、アルキル基の水素原子を置換する基であり、その具体例はフェニル基、アルコキシ基、フェノキシ基を含む。置換基含有(メタ)アクリル酸アルキルエステルとして、具体的には、(メタ)アクリル酸2-メトキシエチル、(メタ)アクリル酸エトキシメチル、(メタ)アクリル酸フェノキシエチル、(メタ)アクリル酸2-(2-フェノキシエトキシ)エチル、(メタ)アクリル酸フェノキシジエチレングリコール、(メタ)アクリル酸フェノキシポリ(エチレングリコール)等が挙げられる。
As the (meth) acrylic acid ester represented by the formula (I),
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, (Meth) acrylic acid n-heptyl, (meth) acrylic acid n-octyl, (meth) acrylic acid n-nonyl, (meth) acrylic acid n-decyl, (meth) acrylic acid n-dodecyl, (meth) acrylic acid Linear alkyl esters of (meth) acrylic acid such as lauryl, stearyl (meth) acrylate, etc .;
(Meth) acrylic acid i-propyl, (meth) acrylic acid i-butyl, (meth) acrylic acid t-butyl, (meth) acrylic acid i-pentyl, (meth) acrylic acid i-hexyl, (meth) acrylic acid Branching of (meth) acrylic acid such as 2-ethylhexyl, i-octyl (meth) acrylate, i-nonyl (meth) acrylate, i-stearyl (meth) acrylate, i-amyl (meth) acrylate, etc. Alkyl esters;
(Meth) acrylic acid cyclohexyl, isoboronyl (meth) acrylic acid, adamantyl (meth) acrylic acid, dicyclopentanyl (meth) acrylic acid, cyclododecyl (meth) acrylic acid, methyl cyclohexyl (meth) acrylic acid, ( Alicyclic skeleton-containing alkyl ester of (meth) acrylic acid such as trimethylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, cyclohexyl α-ethoxyacrylate, etc .;
Aromatic ring skeleton-containing ester of (meth) acrylic acid such as phenyl (meth) acrylate;
Etc.
Moreover, the substituent-containing (meth) acrylic acid alkyl ester in which the substituent was introduce | transduced into the alkyl group in (meth) acrylic acid alkyl ester can also be mentioned. The substituent of the substituent-containing (meth) acrylic acid alkyl ester is a group that substitutes the hydrogen atom of the alkyl group, and specific examples thereof include a phenyl group, an alkoxy group, and a phenoxy group. Specific examples of the substituent-containing (meth) acrylic acid alkyl ester include 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2- (meth) acrylate Examples thereof include (2-phenoxyethoxy) ethyl, phenoxydiethylene glycol (meth) acrylate, and phenoxypoly (ethylene glycol) (meth) acrylate.
 これらの(メタ)アクリル酸エステルは、それぞれ単独で用いることができるほか、異なる複数のものを用いてもよい。 These (meth) acrylic acid esters can be used alone or in combination of two or more different ones.
 (メタ)アクリル系樹脂(A)は、ホモポリマーのガラス転移温度Tgが0℃未満である(メタ)アクリル酸アルキルエステル(a1)由来の構成単位、及びホモポリマーのTgが0℃以上である(メタ)アクリル酸アルキルエステル(a2)由来の構成単位を含有することが好ましい。アクリル酸アルキルエステル(a1)由来の構成単位及びアクリル酸アルキルエステル(a2)由来の構成単位を含有することは、粘着剤層の高温耐久性を高めるうえで有利である。(メタ)アクリル酸アルキルエステルのホモポリマーのTgは、例えばPOLYMER HANDBOOK(Wiley-Interscience)などの文献値を採用することができる。 The (meth) acrylic resin (A) has a structural unit derived from a (meth) acrylic acid alkyl ester (a1) whose homopolymer has a glass transition temperature Tg of less than 0 ° C., and a homopolymer Tg of 0 ° C. or more It is preferable to contain the structural unit derived from (meth) acrylic acid alkyl ester (a2). Containing the structural unit derived from the acrylic acid alkyl ester (a1) and the structural unit derived from the acrylic acid alkyl ester (a2) is advantageous for enhancing the high temperature durability of the pressure-sensitive adhesive layer. As the Tg of the homopolymer of (meth) acrylic acid alkyl ester, literature values such as, for example, POLYMER HANDBOOK (Wiley-Interscience) can be adopted.
 (メタ)アクリル酸アルキルエステル(a1)の具体例としては、アクリル酸エチル、アクリル酸n-及びi-プロピル、アクリル酸n-及びi-ブチル、アクリル酸n-ペンチル、アクリル酸n-及びi-へキシル、アクリル酸n-ヘプチル、アクリル酸n-及びi-オクチル、アクリル酸2-エチルへキシル、アクリル酸n-及びi-ノニル、アクリル酸n-及びi-デシル、アクリル酸n-ドデシル等のアルキル基の炭素数が2~12程度の(メタ)アクリル酸アルキルエステル等が挙げられる。 Specific examples of the (meth) acrylic acid alkyl ester (a1) include ethyl acrylate, n- and i-propyl acrylate, n- and i-butyl acrylate, n-pentyl acrylate, n- and acrylate acrylic acid -Hexyl, n-heptyl acrylate, n- and i-octyl acrylate, 2-ethylhexyl acrylate, n- and i-nonyl acrylate, n- and i-decyl acrylate, n-dodecyl acrylate And the like. Examples thereof include (meth) acrylic acid alkyl esters having about 2 to 12 carbon atoms in the alkyl group.
 (メタ)アクリル酸アルキルエステル(a1)は、1種のみを用いてもよいし2種以上を併用してもよい。なかでも、光学フィルムに積層した際の追従性やリワーク性の観点から、アクリル酸n-ブチル、アクリル酸n-オクチル、アクリル酸2-エチルへキシルなどが好ましい。 The (meth) acrylic acid alkyl ester (a1) may be used alone or in combination of two or more. Among them, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate and the like are preferable from the viewpoint of followability and rework when laminated on an optical film.
 (メタ)アクリル酸アルキルエステル(a2)は、(メタ)アクリル酸アルキルエステル(a1)以外の(メタ)アクリル酸アルキルエステルである。(メタ)アクリル酸アルキルエステル(a2)の具体例は、アクリル酸メチル、アクリル酸シクロヘキシル、アクリル酸イソボロニル、アクリル酸ステアリル、アクリル酸t-ブチル等を含む。 The (meth) acrylic acid alkyl ester (a2) is a (meth) acrylic acid alkyl ester other than the (meth) acrylic acid alkyl ester (a1). Specific examples of the (meth) acrylic acid alkyl ester (a2) include methyl acrylate, cyclohexyl acrylate, isoboronyl acrylate, stearyl acrylate, t-butyl acrylate and the like.
 (メタ)アクリル酸アルキルエステル(a2)は、1種のみを用いてもよいし2種以上を併用してもよい。中でも、高温耐久性の観点から、(メタ)アクリル酸アルキルエステル(a2)は、アクリル酸メチル、アクリル酸シクロヘキシル、アクリル酸イソボロニル等を含むことが好ましく、アクリル酸メチルを含むことがより好ましい。 The (meth) acrylic acid alkyl ester (a2) may be used alone or in combination of two or more. Among them, from the viewpoint of high temperature durability, the (meth) acrylic acid alkyl ester (a2) preferably contains methyl acrylate, cyclohexyl acrylate, isoboronyl acrylate and the like, and more preferably methyl acrylate.
 式(I)で示される(メタ)アクリル酸エステルに由来する構造単位は、(メタ)アクリル系樹脂に含まれる全構造単位中、50質量%以上であることが好ましく、60~95質量%であることが好ましく、65~95質量%以上であることがより好ましい。 The structural unit derived from the (meth) acrylic acid ester represented by the formula (I) is preferably 50% by mass or more, and more preferably 60 to 95% by mass in the total structural units contained in the (meth) acrylic resin. The content is preferably 65 to 95% by mass or more.
 (メタ)アクリル酸エステル以外の単量体に由来する構造単位としては、極性官能基を有する単量体に由来する構造単位が好ましく、極性官能基を有する(メタ)アクリル酸エステルに由来する構造単位がより好ましい。極性官能基としては、ヒドロキシ基、カルボキシル基、置換もしくは無置換アミノ基、エポキシ基等の複素環基などが挙げられる。
極性官能基を有する単量体としては、
(メタ)アクリル酸1-ヒドロキシメチル、(メタ)アクリル酸1-ヒドロキシエチル、(メタ)アクリル酸1-ヒドロキシヘプチル、(メタ)アクリル酸1-ヒドロキシブチル、(メタ)アクリル酸1-ヒドロキシペンチル、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸2-ヒドロキシブチル、(メタ)アクリル酸2-ヒドロキシペンチル、(メタ)アクリル酸2-ヒドロキシヘキシル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸3-ヒドロキシブチル、(メタ)アクリル酸3-ヒドロキシペンチル、(メタ)アクリル酸3-ヒドロキシヘキシル、(メタ)アクリル酸3-ヒドロキシヘプチル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸4-ヒドロキシペンチル、(メタ)アクリル酸4-ヒドロキシヘキシル、(メタ)アクリル酸4-ヒドロキシヘプチル、(メタ)アクリル酸4-ヒドロキシオクチル、(メタ)アクリル酸2-クロロ-2-ヒドロキシプロピル、(メタ)アクリル酸3-クロロ-2-ヒドロキシプロピル、(メタ)アクリル酸2-ヒドロキシー3-フェノキシプロピル、(メタ)アクリル酸5-ヒドロキシペンチル、(メタ)アクリル酸5-ヒドロキシヘキシル、(メタ)アクリル酸5-ヒドロキシヘプチル、(メタ)アクリル酸5-ヒドロキシオクチル、(メタ)アクリル酸5-ヒドロキシノニル、(メタ)アクリル酸6-ヒドロキシヘキシル、(メタ)アクリル酸6-ヒドロキシヘプチル、(メタ)アクリル酸6-ヒドロキシオクチル、(メタ)アクリル酸6-ヒドロキシノニル、(メタ)アクリル酸6-ヒドロキシデシル、(メタ)アクリル酸7-ヒドロキシヘプチル、(メタ)アクリル酸7-ヒドロキシオクチル、(メタ)アクリル酸7-ヒドロキシノニル、(メタ)アクリル酸7-ヒドロキシデシル、(メタ)アクリル酸7-ヒドロキシウンデシル、(メタ)アクリル酸8-ヒドロキシオクチル、(メタ)アクリル酸8-ヒドロキシノニル、(メタ)アクリル酸8-ヒドロキシデシル、(メタ)アクリル酸8-ヒドロキシウンデシル、(メタ)アクリル酸8-ヒドロキシドデシル、(メタ)アクリル酸9-ヒドロキシノニル、(メタ)アクリル酸9-ヒドロキシデシル、(メタ)アクリル酸9-ヒドロキシウンデシル、(メタ)アクリル酸9-ヒドロキシドデシル、(メタ)アクリル酸9-ヒドロキシトリデシル、(メタ)アクリル酸10-ヒドロキシデシル、(メタ)アクリル酸10-ヒドロキシウンデシル、(メタ)アクリル酸10-ヒドロキシドデシル、アクリル酸10-ヒドロキシトリデシル、(メタ)アクリル酸10-ヒドロキシテトラデシル、(メタ)アクリル酸11-ヒドロキシウンデシル、(メタ)アクリル酸11-ヒドロキシドデシル、(メタ)アクリル酸11-ヒドロキシトリデシル、(メタ)アクリル酸11-ヒドロキシテトラデシル、(メタ)アクリル酸11-ヒドロキシペンタデシル、(メタ)アクリル酸12-ヒドロキシドデシル、(メタ)アクリル酸12-ヒドロキシトリデシル、(メタ)アクリル酸12-ヒドロキシテトラデシル、(メタ)アクリル酸13-ヒドロキシペンタデシル、(メタ)アクリル酸13-ヒドロキシテトラデシル、(メタ)アクリル酸13-ヒドロキシペンタデシル、(メタ)アクリル酸14-ヒドロキシテトラデシル、(メタ)アクリル酸14-ヒドロキシペンタデシル、(メタ)アクリル酸15-ヒドロキシペンタデシル、(メタ)アクリル酸15-ヒドロキシヘプタデシル等のヒドロキシ基を有する単量体;
(メタ)アクリル酸、カルボキシアルキル(メタ)アクリレート(例えば、カルボキシエチル(メタ)アクリレート、カルボキシペンチル(メタ)アクリレート)、マレイン酸、無水マレイン酸、フマル酸、クロトン酸等のカルボキシル基を有する単量体;
アクリロイルモルホリン、ビニルカプロラクタム、N-ビニル-2-ピロリドン、ビニルピリジン、テトラヒドロフルフリル(メタ)アクリレート、カプロラクトン変性テトラヒドロフルフリルアクリレート、3,4-エポキシシクロヘキシルメチル(メタ)アクリレート、グリシジル(メタ)アクリレート、2,5-ジヒドロフラン等の複素環基を有する単量体;
アミノエチル(メタ)アクリレート、N,N-ジメチルアミノエチル(メタ)アクリレート、ジメチルアミノプロピル(メタ)アクリレート等の置換もしくは無置換アミノ基を有する単量体が挙げられる。
なかでも、(メタ)アクリル酸エステル重合体と架橋剤との反応性の点で、ヒドロキシ基を有する単量体またはおよびカルボキシル基を有する単量体が好ましく、ヒドロキシ基を有する単量体およびカルボキシル基を有する単量体のいずれもを含むことがより好ましい。
As a structural unit derived from monomers other than (meth) acrylic acid ester, a structural unit derived from a monomer having a polar functional group is preferable, and a structure derived from a (meth) acrylic acid ester having a polar functional group Units are more preferred. Examples of polar functional groups include hydroxy groups, carboxyl groups, substituted or unsubstituted amino groups, and heterocyclic groups such as epoxy groups.
As a monomer having a polar functional group,
(Meth) acrylic acid 1-hydroxymethyl, (meth) acrylic acid 1-hydroxyethyl, (meth) acrylic acid 1-hydroxyheptyl, (meth) acrylic acid 1-hydroxybutyl, (meth) acrylic acid 1-hydroxypentyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypentyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, 3-hydroxyhexyl (meth) acrylate, 3-hydroxyheptyl (meth) acrylate, (Meth) acrylic acid 4-hydroxybutyl, (meth) 4-hydroxypentyl methacrylate, 4-hydroxyhexyl (meth) acrylate, 4-hydroxyheptyl (meth) acrylate, 4-hydroxyoctyl (meth) acrylate, 2-chloro-2-hydroxypropyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 5-hydroxyhexyl (meth) acrylate, (meth ) 5-hydroxyheptyl acrylate, 5-hydroxyoctyl (meth) acrylate, 5-hydroxynonyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 6-hydroxyheptyl (meth) acrylate, (meth) ) Acrylic acid 6-hydroxyoctyl, (meta Acrylic acid 6-hydroxynonyl, (meth) acrylic acid 6-hydroxydecyl, (meth) acrylic acid 7-hydroxyheptyl, (meth) acrylic acid 7-hydroxyoctyl, (meth) acrylic acid 7-hydroxynonyl, (meth) Acrylic acid 7-hydroxydecyl, (meth) acrylic acid 7-hydroxyundecyl, (meth) acrylic acid 8-hydroxyoctyl, (meth) acrylic acid 8-hydroxynonyl, (meth) acrylic acid 8-hydroxydecyl (meth ) 8-hydroxyundecyl acrylate, 8-hydroxydodecyl (meth) acrylate, 9-hydroxynonyl (meth) acrylate, 9-hydroxydecyl (meth) acrylate, 9-hydroxyundecyl (meth) acrylate, (Meth) acrylic acid 9-hydroxydodecyl, (meth) ac 9-hydroxytridecyl acrylate, 10-hydroxydecyl (meth) acrylate, 10-hydroxyundecyl (meth) acrylate, 10-hydroxydodecyl (meth) acrylate, 10-hydroxytridecyl acrylate, (meth) Acrylic acid 10-hydroxytetradecyl, (meth) acrylic acid 11-hydroxyundecyl, (meth) acrylic acid 11-hydroxydodecyl, (meth) acrylic acid 11-hydroxytridecyl, (meth) acrylic acid 11-hydroxytetradecyl 11-hydroxypentadecyl (meth) acrylic acid, 12-hydroxydodecyl (meth) acrylic acid, 12-hydroxytridecyl (meth) acrylic acid, 12-hydroxytetradecyl (meth) acrylic acid, (meth) acrylic acid 13 -Hydroxypentadecyl (Meth) acrylic acid 13-hydroxytetradecyl, (meth) acrylic acid 13-hydroxypentadecyl, (meth) acrylic acid 14-hydroxytetradecyl, (meth) acrylic acid 14-hydroxypentadecyl, (meth) acrylic acid 15 -A monomer having a hydroxy group such as hydroxypentadecyl, 15-hydroxyheptadecyl (meth) acrylic acid;
(Meth) acrylic acid, carboxyalkyl (meth) acrylate (eg, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate), maleic acid, maleic anhydride, fumaric acid, crotonic acid, etc. body;
Acryloyl morpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, A monomer having a heterocyclic group such as 2,5-dihydrofuran;
Monomers having a substituted or unsubstituted amino group such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate and the like can be mentioned.
Among them, a monomer having a hydroxy group or a monomer having a carboxyl group is preferable in view of the reactivity between the (meth) acrylic acid ester polymer and the crosslinking agent, and a monomer having a hydroxy group and a carboxyl group It is more preferable to include any of monomers having a group.
 ヒドロキシ基を有する単量体としては、アクリル酸2-ヒドロキシエチル、アクリル酸3-ヒドロキシプロピル、アクリル酸4-ヒドロキシブチル、アクリル酸5-ヒドロキシペンチル、アクリル酸6-ヒドロキシヘキシルが好ましい。特に、アクリル酸2-ヒドロキシエチル、アクリル酸4-ヒドロキシブチルおよびアクリル酸5-ヒドロキシペンチルを用いることで良好な耐久性を得ることができる。
カルボキシル基を有する単量体としては、アクリル酸を用いることが好ましい。
As a monomer having a hydroxy group, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate are preferable. In particular, good durability can be obtained by using 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and 5-hydroxypentyl acrylate.
As a monomer having a carboxyl group, acrylic acid is preferably used.
粘着剤層の外面に積層することができるセパレートフィルムの剥離力亢進を防ぐ観点から、アミノ基を有する単量体を実質的に含まないことが好ましい。ここで実質的に含まないとは、(メタ)アクリル系樹脂(A)を構成する全構成単位100重量部中、0.1重量部以下であることをいう。 It is preferable not to substantially contain the monomer which has an amino group from a viewpoint of preventing peeling force enhancement of the separate film which can be laminated | stacked on the outer surface of an adhesive layer. Here, “not substantially contained” means that it is 0.1 parts by weight or less in 100 parts by weight of all the constituent units constituting the (meth) acrylic resin (A).
 極性官能基を有する単量体に由来する構造単位の含有量は、(メタ)アクリル系樹脂(A)の全構造単位100質量部に対して、好ましくは20質量部以下、より好ましくは、0.5質量部以上15質量部以下、さらに好ましくは0.5質量部以上10質量部以下、特に好ましくは1質量部以上7質量部以下である。 The content of the structural unit derived from the monomer having a polar functional group is preferably 20 parts by mass or less, more preferably 0 based on 100 parts by mass of all structural units of the (meth) acrylic resin (A). 0.5 parts by weight or more and 15 parts by weight or less, more preferably 0.5 parts by weight or more and 10 parts by weight or less, particularly preferably 1 parts by weight or more and 7 parts by weight or less.
 芳香族基を有する単量体に由来する構造単位の含有量は、(メタ)アクリル系樹脂(A)の全構造単位100質量部に対して、好ましくは20質量部以下、より好ましくは4質量部以上20質量部以下、さらに好ましくは4質量部以上16質量部以下である。 The content of the structural unit derived from the monomer having an aromatic group is preferably 20 parts by mass or less, more preferably 4 parts by mass with respect to 100 parts by mass of the total structural units of the (meth) acrylic resin (A). The content is not less than 20 parts by mass and preferably not less than 4 parts by mass and not more than 16 parts by mass.
 (メタ)アクリル酸エステル以外の単量体に由来する構造単位としては、スチレン系単量体に由来する構造単位、ビニル系単量体に由来する構造単位、分子内に複数の(メタ)アクリロイル基を有する単量体に由来する構造単位、(メタ)アクリルアミド系単量体に由来する構造単位などが挙げられる。 As structural units derived from monomers other than (meth) acrylic acid esters, structural units derived from styrenic monomers, structural units derived from vinyl monomers, plural (meth) acryloyl groups in the molecule Examples include structural units derived from monomers having a group, and structural units derived from (meth) acrylamide type monomers.
 スチレン系単量体としては、スチレン;メチルスチレン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、ジエチルスチレン、トリエチルスチレン、プロピルスチレン、ブチルスチレン、ヘキシルスチレン、ヘプチルスチレン、オクチルスチレン等のアルキルスチレン;フルオロスチレン、クロロスチレン、ブロモスチレン、ジブロモスチレン、ヨードスチレン等のハロゲン化スチレン;ニトロスチレン;アセチルスチレン;メトキシスチレン;および、ジビニルベンゼンが挙げられる。 As styrene-based monomers, styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene, etc .; fluorostyrene, Halogenated styrenes such as chlorostyrene, bromostyrene, dibromostyrene, iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; and divinylbenzene.
 ビニル系単量体としては、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、2-エチルヘキサン酸ビニル、ラウリン酸ビニル等の脂肪酸ビニルエステル;塩化ビニル、臭化ビニル等のハロゲン化ビニル;塩化ビニリデン等のハロゲン化ビニリデン;ビニルピリジン、ビニルピロリドン、ビニルカルバゾール等の含窒素複素芳香族ビニル;ブタジエン、イソプレン、クロロプレン等の共役ジエン;および、アクリロニトリル、メタクリロニトリル等の不飽和ニトリルが挙げられる。 Examples of vinyl monomers include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene chloride and the like And vinylidene halides; nitrogen-containing heteroaromatic vinyls such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; conjugated dienes such as butadiene, isoprene and chloroprene; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.
 分子内に複数の(メタ)アクリロイル基を有する単量体としては、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート等の分子内に2個の(メタ)アクリロイル基を有する単量体;トリメチロールプロパントリ(メタ)アクリレート等の分子内に3個の(メタ)アクリロイル基を有する単量体が挙げられる。 As monomers having a plurality of (meth) acryloyl groups in the molecule, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di ( Two (meth) acryloyl groups in the molecule such as meta) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate and tripropylene glycol di (meth) acrylate Monomers having; monomers having three (meth) acryloyl groups in a molecule such as trimethylolpropane tri (meth) acrylate.
 (メタ)アクリルアミド系単量体としては、N-メチロール(メタ)アクリルアミド、N-(2-ヒドロキシエチル)(メタ)アクリルアミド、N-(3-ヒドロキシプロピル)(メタ)アクリルアミド、N-(4-ヒドロキシブチル)(メタ)アクリルアミド、N-(5-ヒドロキシペンチル)(メタ)アクリルアミド、N-(6-ヒドロキシヘキシル)(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-(3-ジメチルアミノプロピル)(メタ)アクリルアミド、N-(1,1-ジメチル-3-オキソブチル)(メタ)アクリルアミド、N-〔2-(2-オキソ-1-イミダゾリジニル)エチル〕(メタ)アクリルアミド、2-アクリロイルアミノ-2-メチル-1-プロパンスルホン酸、N-(メトキシメチル)アクリルアミド、N-(エトキシメチル)(メタ)アクリルアミド、N-(プロポキシメチル)(メタ)アクリルアミド、N-(1-メチルエトキシメチル)(メタ)アクリルアミド、N-(1-メチルプロポキシメチル)(メタ)アクリルアミド、N-(2-メチルプロポキシメチル)(メタ)アクリルアミド、N-(ブトキシメチル)(メタ)アクリルアミド、N-(1,1-ジメチルエトキシメチル)(メタ)アクリルアミド、N-(2-メトキシエチル)(メタ)アクリルアミド、N-(2-エトキシエチル)(メタ)アクリルアミド、N-(2-プロポキシエチル)(メタ)アクリルアミド、N-〔2-(1-メチルエトキシ)エチル〕(メタ)アクリルアミド、N-〔2-(1-メチルプロポキシ)エチル〕(メタ)アクリルアミド、N-〔2-(2-メチルプロポキシ)エチル〕(メタ)アクリルアミド、N-(2-ブトキシエチル)(メタ)アクリルアミド、N-〔2-(1,1-ジメチルエトキシ)エチル〕(メタ)アクリルアミドなどが挙げられる。なかでも、N-(メトキシメチル)アクリルアミド、N-(エトキシメチル)アクリルアミド、N-(プロポキシメチル)アクリルアミド、N-(ブトキシメチル)アクリルアミドおよびN-(2-メチルプロポキシメチル)アクリルアミドが好ましい。 Examples of (meth) acrylamide monomers include N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N- (4-) Hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- (6-hydroxyhexyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide Meta) acrylamide, N-isopropyl (meth) acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamide, N- [2- (2-) 2-Oxo-1-imidazolidinyl) ethyl] (meth) acrylamide 2-acryloylamino-2-methyl-1-propanesulfonic acid, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) (meth) acrylamide, N- (propoxymethyl) (meth) acrylamide, N- (1-) Methylethoxymethyl) (meth) acrylamide, N- (1-methylpropoxymethyl) (meth) acrylamide, N- (2-methylpropoxymethyl) (meth) acrylamide, N- (butoxymethyl) (meth) acrylamide, N- (1,1-Dimethylethoxymethyl) (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N- (2-ethoxyethyl) (meth) acrylamide, N- (2-propoxyethyl) (meth) ) Acrylamide, N- [2- (1-methylethoxy) ethyl] Meta) Acrylamide, N- [2- (1-Methylpropoxy) ethyl] (meth) acrylamide, N- [2- (2-Methylpropoxy) ethyl] (meth) acrylamide, N- (2-Butoxyethyl) (meth) acrylamide A) acrylamide, N- [2- (1,1-dimethylethoxy) ethyl] (meth) acrylamide and the like. Among them, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) acrylamide and N- (2-methylpropoxymethyl) acrylamide are preferable.
 (メタ)アクリル系樹脂(A)の重量平均分子量(Mw)は、好ましくは、50万~250万である。重量平均分子量が50万以上であると、高温環境における粘着剤層の耐久性が向上し、被着体と粘着剤層との間の浮き剥れや、粘着剤層の凝集破壊などの不具合を抑制しやすい。重量平均分子量が250万以下であると、粘着剤組成物を例えばシート状に加工(基材に塗工する)際の塗工性の観点で有利である。粘着剤層の耐久性及び粘着剤組成物の塗工性の両立の観点から、重量平均分子量は好ましくは60万~180万であり、よく好ましくは70万~170万であり、特に好ましくは100万~160万である。また、重量平均分子量(Mw)と数平均分子量(Mn)との比で表される分子量分布(Mw/Mn)は、通常2~10、好ましくは3~8、さらに好ましくは3~6である。 重量平均分子量は、ゲルパーミエーションクロマトグラフィにより分析でき、標準ポリスチレン換算の値である。 The weight average molecular weight (Mw) of the (meth) acrylic resin (A) is preferably 500,000 to 2,500,000. When the weight average molecular weight is 500,000 or more, the durability of the pressure-sensitive adhesive layer in a high temperature environment is improved, and defects such as peeling between adherends and the pressure-sensitive adhesive layer, cohesive failure of the pressure-sensitive adhesive layer, etc. It is easy to control. When the weight average molecular weight is 2,500,000 or less, it is advantageous from the viewpoint of coatability when processing the pressure-sensitive adhesive composition into, for example, a sheet (coating on a substrate). The weight-average molecular weight is preferably 600,000 to 1,800,000, more preferably 700,000 to 1,700,000, and particularly preferably 100, from the viewpoint of achieving both the durability of the pressure-sensitive adhesive layer and the coatability of the pressure-sensitive adhesive composition. It is 10,000 to 1.6 million. The molecular weight distribution (Mw / Mn) represented by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) is usually 2 to 10, preferably 3 to 8, and more preferably 3 to 6 . The weight average molecular weight can be analyzed by gel permeation chromatography and is a value in terms of standard polystyrene.
 (メタ)アクリル系樹脂(A)は、酢酸エチルに溶解させ、濃度20質量%の溶液としたとき、25℃における粘度が、20Pa・s以下であることが好ましく、0.1~15Pa・sであることがより好ましい。該範囲の粘度であると、粘着剤組成物を基材に塗工する際の塗工性の観点から有利である。なお、粘度は、ブルックフィールド粘度計により測定できる。 When the (meth) acrylic resin (A) is dissolved in ethyl acetate to form a solution having a concentration of 20% by mass, the viscosity at 25 ° C. is preferably 20 Pa · s or less, preferably 0.1 to 15 Pa · s. It is more preferable that It is advantageous from the viewpoint of the coatability at the time of applying an adhesive constituent to a substrate as it is a viscosity of this range. The viscosity can be measured by a Brookfield viscometer.
 (メタ)アクリル系樹脂(A)のガラス転移温度(Tg)は、例えば-60~20℃、好ましくは-50~15℃、さらに好ましくは-45~10℃、特に-40~0℃であってもよい。Tgが上限値以下であると粘着剤層の被着体基材に対するするぬれ性の向上に有利であり、下限値以上であると粘着剤層の耐久性の向上に有利である。なお、ガラス転移温度は示差走査熱量計(DSC)により測定できる。 The glass transition temperature (Tg) of the (meth) acrylic resin (A) is, for example, -60 to 20 ° C, preferably -50 to 15 ° C, more preferably -45 to 10 ° C, particularly -40 to 0 ° C. May be It is advantageous for the wettability improvement with respect to the adherend base material of an adhesive layer that Tg is below an upper limit, and it is advantageous for the durable improvement of an adhesive layer to be more than a lower limit. The glass transition temperature can be measured by a differential scanning calorimeter (DSC).
 (メタ)アクリル酸樹脂(A)は、例えば、溶液重合法、塊状重合法、懸濁重合法、乳化重合法などの公知の方法によって製造することができ、特に溶液重合法が好ましい。溶液重合法としては、例えば、単量体及び有機溶媒を混合し、窒素雰囲気下、熱重合開始剤を添加し、40~90℃、好ましくは50~80℃程度の温度条件下、3~15時間程度攪拌する方法が挙げられる。反応制御のため、重合中、連続的又は間歇的に単量体や熱重合開始剤を添加してもよい。該単量体や熱開始剤は有機溶媒に添加した状態であってもよい。 The (meth) acrylic resin (A) can be produced by a known method such as, for example, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and the solution polymerization method is particularly preferable. As the solution polymerization method, for example, a monomer and an organic solvent are mixed, a thermal polymerization initiator is added under a nitrogen atmosphere, and a temperature condition of about 40 to 90 ° C., preferably about 50 to 80 ° C., 3 to 15 The method of stirring for about time is mentioned. In order to control the reaction, monomers or a thermal polymerization initiator may be added continuously or intermittently during the polymerization. The monomer and thermal initiator may be in the state of being added to an organic solvent.
 重合開始剤としては、熱重合開始剤や光重合開始剤等が用いられる。光重合開始剤としては、4-(2-ヒドロキシエトキシ)フェニル(2-ヒドロキシ-2-プロピル)ケトンなどが挙げられる。熱重合開始剤としては、2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(2-メチルブチロニトリル)、1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、2,2’-アゾビス(2,4-ジメチル-4-メトキシバレロニトリル)、ジメチル-2,2’-アゾビス(2-メチルプロピオネート)、2,2’-アゾビス(2-ヒドロキシメチルプロピオニトリル)などのアゾ系化合物;ラウリルパーオキサイド、t-ブチルハイドロパーオキサイド、過酸化ベンゾイル、t-ブチルパーオキシベンゾエート、クメンハイドロパーオキサイド、ジイソプロピルパーオキシジカーボネート、ジプロピルパーオキシジカーボネート、t-ブチルパーオキシネオデカノエート、t-ブチルパーオキシピバレート、(3,5,5-トリメチルヘキサノイル)パーオキサイドなどの有機過酸化物;過硫酸カリウム、過硫酸アンモニウム、過酸化水素などの無機過酸化物などが挙げられる。また、過酸化物と還元剤とを併用したレドックス系開始剤なども使用できる。 As a polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, etc. are used. As the photopolymerization initiator, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone and the like can be mentioned. As a thermal polymerization initiator, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2'-azobis (2-methyl propionate) Azo compounds such as 2,2'-azobis (2-hydroxymethylpropionitrile); lauryl peroxide, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxybenzoate, cumene hydroperoxide, Diisopropyl peroxy dicarbonate, dipropyl peroxy dicarbonate, t-butyl peroxy neode Organic peroxides such as noates, t-butylperoxypivalate, (3,5,5-trimethylhexanoyl) peroxide; inorganic peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide and the like . In addition, a redox initiator in which a peroxide and a reducing agent are used in combination can also be used.
 重合開始剤の割合は、(メタ)アクリル系樹脂を構成する単量体の総量100質量部に対して、0.001~5質量部程度である。(メタ)アクリル系樹脂の重合は、活性エネルギー線(例えば紫外線など)による重合法を使用してもよい。 The proportion of the polymerization initiator is about 0.001 to 5 parts by mass with respect to 100 parts by mass of the total of the monomers constituting the (meth) acrylic resin. The polymerization of the (meth) acrylic resin may be carried out by a polymerization method using active energy rays (for example, ultraviolet rays and the like).
 有機溶媒としては、トルエン、キシレンなどの芳香族炭化水素類;酢酸エチル、酢酸ブチルなどのエステル類;プロピルアルコール、イソプロピルアルコールなどの脂肪族アルコール類;アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン類などが挙げられる。 Organic solvents include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propyl alcohol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone Can be mentioned.
 (メタ)アクリル系樹脂(A)の含有量は、粘着剤組成物100質量%中、通常60質量%~99.9質量%であり、好ましくは70質量%~99.5質量%であり、より好ましくは80質量%~99質量%である。 The content of the (meth) acrylic resin (A) is usually 60% by mass to 99.9% by mass, preferably 70% by mass to 99.5% by mass in 100% by mass of the pressure-sensitive adhesive composition. More preferably, it is 80% by mass to 99% by mass.
 粘着剤組成物は、架橋剤(b)を含むことができる。該架橋剤(b)は、(メタ)アクリル系樹脂(A)中の極性官能基(例えばヒドロキシ基、アミノ基、カルボキシル基、複素環基等)と反応する。架橋剤(B)は(メタ)アクリル系樹脂等と架橋構造を形成し、耐久性やリワーク性に有利な架橋構造を形成する。 The pressure-sensitive adhesive composition can contain a crosslinking agent (b). The crosslinking agent (b) reacts with polar functional groups (for example, hydroxy group, amino group, carboxyl group, heterocyclic group, etc.) in the (meth) acrylic resin (A). The crosslinking agent (B) forms a crosslinked structure with a (meth) acrylic resin or the like, and forms a crosslinked structure that is advantageous for durability and reworkability.
 架橋剤(b)としては、イソシアネート系架橋剤、エポキシ系架橋剤、アジリジン系架橋剤、金属キレート系架橋剤等が挙げられ、特に粘着剤組成物のポットライフ及び粘着剤層の耐久性、架橋速度などの観点から、イソシアネート系架橋剤であることが好ましい。 Examples of the crosslinking agent (b) include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, metal chelate-based crosslinking agents and the like, and in particular the pot life of the pressure-sensitive adhesive composition and the durability of the pressure-sensitive adhesive layer, crosslinking It is preferable that it is an isocyanate type crosslinking agent from a viewpoint of speed etc.
 イソシアネート系化合物としては、分子内に少なくとも2個のイソシアナト基(-NCO)を有する化合物が好ましく、例えば、脂肪族イソシアネート系化合物(例えばヘキサメチレンジイソシアネートなど)、脂環族イソシアネート系化合物(例えばイソホロンジイソシアネート、水添ジフェニルメタンジイソシアネート、水添キシリレンジイソシアネート)、芳香族イソシアネート系化合物(例えばトリレンジイソシアネート、キシリレンジイソシアネートジフェニルメタンジイソシアネート、ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート等)などが挙げられる。また架橋剤(B)は、前記イソシアネート化合物の多価アルコール化合物による付加体(アダクト体)[例えば、グリセロール、トリメチロールプロパンなどによる付加体]、イソシアヌレート化物、ビュレット型化合物、ポリエーテルポリオール、ポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオール等と付加反応させたウレタンプレポリマー型のイソシアネート化合物などの誘導体であってもよい。架橋剤(B)は単独又は二種以上組み合わせて使用できる。これらのうち、代表的には芳香族イソシアネート系化合物(例えばトリレンジイソシアネート、キシリレンジイソシアネート)、脂肪族イソシアネート系化合物(例えばヘキサメチレンジイソシアネート)又はこれらの多価アルコール化合物(例えば、グリセロール、トリメチロールプロパン)による付加体、又はイソシアヌレート体が挙げられる。架橋剤(B)が、芳香族イソシアネート系化合物及び/又はこれらの多価アルコール化合物、又はイソシアヌレート体による付加体であると、最適な架橋密度(又は架橋構造)の形成に有利なためか、粘着剤層の耐久性を向上できる。特に、トリレンジイソシアネート系化合物及び/又はこれらの多価アルコール化合物による付加体であると、例えば粘着剤層を偏光板に適用した場合等であっても耐久性を向上することができる。 As the isocyanate compound, a compound having at least two isocyanato groups (-NCO) in the molecule is preferable. For example, aliphatic isocyanate compounds (for example, hexamethylene diisocyanate etc.), alicyclic isocyanate compounds (for example isophorone diisocyanate) And hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate), aromatic isocyanate compounds (eg, tolylene diisocyanate, xylylene diisocyanate diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.) and the like. The crosslinking agent (B) may be an adduct of the above-mentioned isocyanate compound with a polyhydric alcohol compound (adduct) [for example, an adduct of glycerol, trimethylolpropane etc.], isocyanurate, burette type compound, polyether polyol, polyester It may be a derivative such as a urethane prepolymer type isocyanate compound which is addition-reacted with a polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol or the like. The crosslinking agents (B) can be used alone or in combination of two or more. Among these, typically, aromatic isocyanate compounds (eg, tolylene diisocyanate, xylylene diisocyanate), aliphatic isocyanate compounds (eg, hexamethylene diisocyanate) or polyhydric alcohol compounds thereof (eg, glycerol, trimethylolpropane) And adducts thereof, or isocyanurates. If the crosslinking agent (B) is an adduct of an aromatic isocyanate compound and / or a polyhydric alcohol compound thereof or an isocyanurate, it is advantageous for the formation of an optimal crosslinking density (or crosslinked structure), The durability of the pressure-sensitive adhesive layer can be improved. In particular, when it is an adduct of a tolylene diisocyanate compound and / or a polyhydric alcohol compound thereof, the durability can be improved even when, for example, the pressure-sensitive adhesive layer is applied to a polarizing plate.
 架橋剤(b)の含有量は、(メタ)アクリル系樹脂(A)100重量部に対して、通常0.01~15質量部であり、好ましくは0.05~10重量部であり、より好ましくは0.1~5重量部である。 The content of the crosslinking agent (b) is usually 0.01 to 15 parts by mass, preferably 0.05 to 10 parts by mass, relative to 100 parts by mass of the (meth) acrylic resin (A). Preferably, it is 0.1 to 5 parts by weight.
 樹脂組成物は、さらにシラン化合物(D)を含んでいてもよい。
 シラン化合物(D)としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(2-メトキシエトキシ)シラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルエトキシジメチルシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-クロロプロピルメチルジメトキシシラン、3-クロロプロピルトリメトキシシラン、3-メタクリロイルオキシプロピルトリメトキシシラン、3-メルカプトプロピルトリメトキシシラン等が挙げられる。
 シラン化合物(D)は、シリコーンオリゴマーであってもよい。シリコーンオリゴマーの具体例を、モノマー同士の組み合わせの形で表記すると次のとおりである。
The resin composition may further contain a silane compound (D).
Examples of the silane compound (D) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, Examples thereof include 3-methacryloyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.
The silane compound (D) may be a silicone oligomer. The specific example of the silicone oligomer is as follows, in the form of a combination of monomers.
 3-メルカプトプロピルトリメトキシシラン-テトラメトキシシランオリゴマー、3-メルカプトプロピルトリメトキシシラン-テトラエトキシシランオリゴマー、3-メルカプトプロピルトリエトキシシラン-テトラメトキシシランオリゴマー、3-メルカプトプロピルトリエトキシシラン-テトラエトキシシランオリゴマー等のメルカプトプロピル基含有オリゴマー;メルカプトメチルトリメトキシシラン-テトラメトキシシランオリゴマー、メルカプトメチルトリメトキシシラン-テトラエトキシシランオリゴマー、メルカプトメチルトリエトキシシラン-テトラメトキシシランオリゴマー、メルカプトメチルトリエトキシシラン-テトラエトキシシランオリゴマー等のメルカプトメチル基含有オリゴマー;3-グリジドキシプロピルトリメトキシシラン-テトラメトキシシランコポリマー、3-グリジドキシプロピルトリメトキシシラン-テトラエトキシシランコポリマー、3-グリジドキシプロピルトリエトキシシラン-テトラメトキシシランコポリマー、3-グリジドキシプロピルトリエトキシシラン-テトラエトキシシランコポリマー、3-グリジドキシプロピルメチルジメトキシシラン-テトラメトキシシランコポリマー、3-グリジドキシプロピルメチルジメトキシシラン-テトラエトキシシランコポリマー、3-グリジドキシプロピルメチルジエトキシシラン-テトラメトキシシランコポリマー、3-グリジドキシプロピルメチルジエトキシシラン-テトラエトキシシランコポリマー等の3-グリジドキシプロピル基含有のコポリマー;3-メタクリロイルオキシプロピルトリメトキシシラン-テトラメトキシシランオリゴマー、3-メタクリロイルオキシプロピルトリメトキシシラン-テトラエトキシシランオリゴマー、3-メタクリロイルオキシプロピルトリエトキシシラン-テトラメトキシシランオリゴマー、3-メタクリロイルオキシプロピルトリエトキシシラン-テトラエトキシシランオリゴマー、3-メタクリロイルオキシプロピルメチルジメトキシシラン-テトラメトキシシランオリゴマー、3-メタクリロイルオキシプロピルメチルジメトキシシラン-テトラエトキシシランオリゴマー、3-メタクリロイルオキシプロピルメチルジエトキシシラン-テトラメトキシシランオリゴマー、3-メタクリロイルオキシプロピルメチルジエトキシシラン-テトラエトキシシランオリゴマー等のメタクリロイルオキシプロピル基含有オリゴマー;3-アクリロイルオキシプロピルトリメトキシシラン-テトラメトキシシランオリゴマー、3-アクリロイルオキシプロピルトリメトキシシラン-テトラエトキシシランオリゴマー、3-アクリロイルオキシプロピルトリエトキシシラン-テトラメトキシシランオリゴマー、3-アクリロイルオキシプロピルトリエトキシシラン-テトラエトキシシランオリゴマー、3-アクリロイルオキシプロピルメチルジメトキシシラン-テトラメトキシシランオリゴマー、3-アクリロイルオキシプロピルメチルジメトキシシラン-テトラエトキシシランオリゴマー、3-アクリロイルオキシプロピルメチルジエトキシシラン-テトラメトキシシランオリゴマー、3-アクリロイルオキシプロピルメチルジエトキシシラン-テトラエトキシシランオリゴマー等のアクリロイルオキシプロピル基含有オリゴマー;ビニルトリメトキシシラン-テトラメトキシシランオリゴマー、ビニルトリメトキシシラン-テトラエトキシシランオリゴマー、ビニルトリエトキシシラン-テトラメトキシシランオリゴマー、ビニルトリエトキシシラン-テトラエトキシシランオリゴマー、ビニルメチルジメトキシシラン-テトラメトキシシランオリゴマー、ビニルメチルジメトキシシラン-テトラエトキシシランオリゴマー、ビニルメチルジエトキシシラン-テトラメトキシシランオリゴマー、ビニルメチルジエトキシシラン-テトラエトキシシランオリゴマー等のビニル基含有オリゴマー;3-アミノプロピルトリメトキシシラン-テトラメトキシシランコポリマー、3-アミノプロピルトリメトキシシラン-テトラエトキシシランコポリマー、3-アミノプロピルトリエトキシシラン-テトラメトキシシランコポリマー、3-アミノプロピルトリエトキシシラン-テトラエトキシシランコポリマー、3-アミノプロピルメチルジメトキシシラン-テトラメトキシシランコポリマー、3-アミノプロピルメチルジメトキシシラン-テトラエトキシシランコポリマー、3-アミノプロピルメチルジエトキシシラン-テトラメトキシシランコポリマー、3-アミノプロピルメチルジエトキシシラン-テトラエトキシシランコポリマー等のアミノ基含有のコポリマーなど。 3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetraethoxysilane Oligomers containing mercaptopropyl group-containing oligomers; mercaptomethyltrimethoxysilane-tetramethoxysilane oligomers, mercaptomethyltrimethoxysilane-tetraethoxysilane oligomers, mercaptomethyltriethoxysilane-tetramethoxysilane oligomers, mercaptomethyltriethoxysilane-tetraethoxy Mercaptomethyl group-containing oligomers such as silane oligomers; 3-glycidoxypropyl Trimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetra Ethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, Copolymers containing 3-glycidoxypropyl group such as 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer; 3-methacryloyl Xylpropyltrimethoxysilane-tetramethoxysilane oligomer, 3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxy Silane oligomers, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-methacryloyloxy Propylmethyldiethoxysilane-tetraethoxysilane oligomer Etc .; 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-acryloyloxypropyltriethoxysilane-tetramethoxysilane oligomer , 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane oligomer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-acryloyloxypropylmethyldi Ethoxysilane-tetramethoxysilane oligomer, 3-acryloyloxypropyl Acryloyloxypropyl group-containing oligomers such as chilldiethoxysilane-tetraethoxysilane oligomers; vinyltrimethoxysilane-tetramethoxysilane oligomers, vinyltrimethoxysilane-tetraethoxysilane oligomers, vinyltriethoxysilane-tetramethoxysilane oligomers, vinyltrimethoxysilane oligomers Ethoxysilane-tetraethoxysilane oligomer, vinylmethyldimethoxysilane-tetramethoxysilane oligomer, vinylmethyldimethoxysilane-tetraethoxysilane oligomer, vinylmethyldiethoxysilane-tetramethoxysilane oligomer, vinylmethyldiethoxysilane-tetraethoxysilane oligomer, etc. -Containing oligomers of vinyl; 3-aminopropyltrimethoxysilane-tetramethoxysilane Polymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetra Amino group-containing such as methoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer, etc. Copolymer etc.
 シラン化合物(D)は、下記式(d1)で表されるシラン化合物であってもよい。粘着剤組成物が下記式(d1)で表されるシラン化合物を含むと、密着性(又は接着性)をさらに向上できるため、耐剥がれ性に良好な粘着剤層を形成できる。特に、高温環境下で、粘着剤層を透明電極やガラスに適用(又は積層)した場合においても、密着性(又は接着性)を維持でき、高い耐久性を示すことができる。 The silane compound (D) may be a silane compound represented by the following formula (d1). When the pressure-sensitive adhesive composition contains a silane compound represented by the following formula (d1), the adhesion (or adhesion) can be further improved, so that a pressure-sensitive adhesive layer having excellent peel resistance can be formed. In particular, even when the pressure-sensitive adhesive layer is applied (or laminated) to a transparent electrode or glass under a high temperature environment, adhesion (or adhesiveness) can be maintained and high durability can be exhibited.
Figure JPOXMLDOC01-appb-I000022
(式中、Bは、炭素数1~20のアルカンジイル基又は炭素数3~20の二価の脂環式炭化水素基を示し、前記アルカンジイル基及び前記脂環式炭化水素基を構成する-CH-は、-O-又は-CO-に置換されてもよく、Rd7は炭素数1~5のアルキル基を示し、Rd8、Rd9、Rd10、Rd11及びRd12はそれぞれ独立して、炭素数1~5のアルキル基又は炭素数1~5のアルコキシ基を示す)
Figure JPOXMLDOC01-appb-I000022
(Wherein, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group) -CH 2- may be substituted by -O- or -CO-, and R d7 represents an alkyl group having 1 to 5 carbon atoms, and R d8 , R d9 , R d10 , R d11 and R d12 respectively represent Independently represents an alkyl group of 1 to 5 carbon atoms or an alkoxy group of 1 to 5 carbon atoms)
 式(d1)において、Bは、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基などの炭素数1~20のアルカンジイル基;シクロブチレン基(例えば1,2-シクロブチレン基)、シクロペンチレン基(例えば1,2-シクロペンチレン基)、シクロヘキシレン基(例えば1,2-シクロへキシレン基)、シクロオクチレン基(例えば1,2-シクロオクチレン基)などの炭素数3~20の二価の脂環式炭化水素基、又はこれらのアルカンジイル基及び前記脂環式炭化水素基を構成する-CH2-が、-O-又は-CO-に置換された基を示す。好ましいBは、炭素数1~10のアルカンジイル基である。Rd7はメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、s-ブチル基、t-ブチル基、ペンチル基などの炭素数1~5のアルキル基を示し、Rd8、Rd9、Rd10、Rd11及びRd12はそれぞれ独立して、前記Rd7に例示の炭素数1~5のアルキル基、又はメトキシ基、エトキシ基、プロポキシ基、i-プロポキシ基、ブトキシ基、s-ブトキシ基、t-ブトキシ基などの炭素数1~5のアルコキシ基を示す。好ましいRd8、Rd9、Rd10、Rd11及びRd12はそれぞれ独立して炭素数1~5のアルコキシ基である。これらのシラン化合物(D)は単独又は二種以上組み合わせて使用できる。 In the formula (d1), B represents an alkanediyl group having 1 to 20 carbon atoms such as methylene group, ethylene group, trimethylene group, tetramethylene group, tetramethylene group, hexamethylene group, heptamethylene group, octamethylene group, etc .; 1,2-cyclobutylene group), cyclopentylene group (eg, 1,2-cyclopentylene group), cyclohexylene group (eg, 1,2-cyclohexylene group), cyclooctylene group (eg, 1,2-cyclobutylene group) A divalent alicyclic hydrocarbon group having a carbon number of 3 to 20, such as a cyclooctylene group), or an alkanediyl group thereof and -CH2- constituting the alicyclic hydrocarbon group is -O- or- The group substituted by CO- is shown. Preferred B is a C 1-10 alkanediyl group. R d7 represents an alkyl group having a carbon number of 1 to 5, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, pentyl group, etc., and R d8 , R d9 , R d10 , R d11 and R d12 are each independently an alkyl group having 1 to 5 carbon atoms exemplified for R d7 , or a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, a butoxy group or an s-butoxy group And an alkoxy group having 1 to 5 carbon atoms such as t-butoxy group. Desirable R d8 , R d9 , R d10 , R d11 and R d12 are each independently an alkoxy group having 1 to 5 carbon atoms. These silane compounds (D) can be used alone or in combination of two or more.
 具体的な前記式(d1)で表されるシラン化合物としては、例えば、(トリメトキシシリル)メタン、1,2-ビス(トリメトキシシリル)エタン、1,2-ビス(トリエトキシシリル)エタン、1,3-ビス(トリメトキシシリル)プロパン、1,3-ビス(トリエトキシシリル)プロパン、1,4-ビス(トリメトキシシリル)ブタン、1,4-ビス(トリエトキシシリル)ブタン、1,5-ビス(トリメトキシシリル)ペンタン、1,5-ビス(トリエトキシシリル)ペンタン、1,6-ビス(トリメトキシシリル)ヘキサン、1,6-ビス(トリエトキシシリル)ヘキサン、1,6-ビス(トリプロポキシシリル)ヘキサン、1,8-ビス(トリメトキシシリル)オクタン、1,8-ビス(トリエトキシシリル)オクタン、1,8-ビス(トリプロポキシシリル)オクタンなどのビス(トリC1-5アルコキシシリル)C1-10アルカン;ビス(ジメトキシメチルシリル)メタン、1,2-ビス(ジメトキシメチルシリル)エタン、1,2-ビス(ジメトキシエチルシリル)エタン、1,4-ビス(ジメトキシメチルシリル)ブタン、1,4-ビス(ジメトキシエチルシリル)ブタン、1,6-ビス(ジメトキシメチルシリル)ヘキサン、1,6-ビス(ジメトキシエチルシリル)ヘキサン、1,8-ビス(ジメトキシメチルシリル)オクタン、1,8-ビス(ジメトキシエチルシリル)オクタンなどのビス(ジC1-5アルコキシC1-5アルキルシリル)C1-10アルカン;1,6-ビス(メトキシジメチルシリル)ヘキサン、1,8-ビス(メトキシジメチルシリル)オクタンなどのビス(モノC1-5アルコキシ-ジC1-5アルキルシリル)C1-10アルカンなどが挙げられる。これらのうち、1,2-ビス(トリメトキシシリル)エタン、1,3-ビス(トリメトキシシリル)プロパン、1,4-ビス(トリメトキシシリル)ブタン、1,5-ビス(トリメトキシシリル)ペンタン、1,6-ビス(トリメトキシシリル)ヘキサン、1,8-ビス(トリメトキシシリル)オクタンなどのビス(トリC1-3アルコキシシリル)C1-10アルカンが好ましく、特に、1,6-ビス(トリメトキシシリル)ヘキサン、1,8-ビス(トリメトキシシリル)オクタンが好ましい。 Specific examples of the silane compound represented by the above formula (d1) include (trimethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, and 1,2-bis (triethoxysilyl) ethane. 1,3-bis (trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 1,4-bis (trimethoxysilyl) butane, 1,4-bis (triethoxysilyl) butane, 1,1 5-bis (trimethoxysilyl) pentane, 1,5-bis (triethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,6-bis (triethoxysilyl) hexane, 1,6- Bis (tripropoxysilyl) hexane, 1,8-bis (trimethoxysilyl) octane, 1,8-bis (triethoxysilyl) octane, 1,8 Bis (triC1-5alkoxysilyl) C1-10 alkanes such as bis (tripropoxysilyl) octane; bis (dimethoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (dimethoxy) Ethylsilyl) ethane, 1,4-bis (dimethoxymethylsilyl) butane, 1,4-bis (dimethoxyethylsilyl) butane, 1,6-bis (dimethoxymethylsilyl) hexane, 1,6-bis (dimethoxyethylsilyl) ) Bis (di C1-5 alkoxy C1-5 alkyl silyl) C1-10 alkanes such as hexane, 1,8-bis (dimethoxymethylsilyl) octane, 1,8-bis (dimethoxyethylsilyl) octane and the like; 1,6- Bis (methoxydimethylsilyl) hexane, 1,8-bis (methoxydimethyl) Lil) bis octane (mono C1-5 alkoxy - di C1-5 alkylsilyl) such as C1-10 alkanes. Among these, 1,2-bis (trimethoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, 1,4-bis (trimethoxysilyl) butane, 1,5-bis (trimethoxysilyl) Bis (tri C 1-3 alkoxysilyl) C 1-10 alkanes such as pentane, 1,6-bis (trimethoxysilyl) hexane, 1,8-bis (trimethoxysilyl) octane, etc. are preferred, in particular 1,6-bis. (Trimethoxysilyl) hexane and 1,8-bis (trimethoxysilyl) octane are preferred.
 シラン化合物(D)の含有量は、(メタ)アクリル系樹脂(A)100重量部に対して、通常0.01~10重量部であり、好ましくは0.03~5重量部であり、より好ましくは0.05~2重量部であり、さらに好ましくは0.1~1重量部である。上記上限値以下であると、粘着剤層からのシラン化合物(D)のブリードアウトの抑制に有利であり、上記下限値以上であると、粘着剤層と、金属層やガラス基板等との密着性(又は接着性)を向上しやすくなり、耐剥がれ性などの向上に有利である。 The content of the silane compound (D) is usually 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, per 100 parts by weight of the (meth) acrylic resin (A). The amount is preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight. It is advantageous for suppression of the bleed-out of the silane compound (D) from an adhesive layer that it is below the said upper limit, and adhesion with an adhesive layer, a metal layer, a glass substrate, etc. being more than the said lower limit It is easy to improve the properties (or adhesion), which is advantageous for improving the peeling resistance and the like.
 粘着剤組成物は、さらに帯電防止剤を含有していてもよい。
 帯電防止剤としては、界面活性剤、シロキサン化合物、導電性高分子、イオン性化合物等が挙げられ、イオン性化合物であることが好ましい。イオン性化合物としては、慣用のものが挙げられる。イオン性化合物を構成するカチオン成分としては、有機カチオン、無機カチオンなどが挙げられる。有機カチオンとしては、例えばピリジニウムカチオン、ピロリジニウムカチオン、ピペリジニウムカチオン、イミダゾリウムカチオン、アンモニウムカチオン、スルホニウムカチオン、ホスホニウムカチオンなどが挙げられる。無機カチオンとしては、例えばリチウムカチオン、カリウムカチオン、ナトリウムカチオン、セシウムカチオンなどのアルカリ金属カチオン、マグネシウムカチオン、カルシウムカチオンなどのアルカリ土類金属カチオンなどが挙げられる。特に(メタ)アクリル系樹脂との相溶性の観点からピリジニウムカチオン、イミダゾリウムカチオン、ピロリジニウムカチオン、リチウムカチオン、カリウムカチオンが好ましい。イオン性化合物を構成するアニオン成分としては、無機アニオン及び有機アニオンのいずれでもよいが、帯電防止性能の点で、フッ素原子を含むアニオン成分が好ましい。フッ素原子を含むアニオン成分としては、例えばヘキサフルオロホスフェートアニオン(PF-)、ビス(トリフルオロメタンスルホニル)イミドアニオン[(CFSON-]、ビス(フルオロスルホニル)イミドアニオン[(FSON-]、テトラ(ペンタフルオロフェニル)ボレートアニオン[(CB-]などが挙げられる。これらのイオン性化合物は単独又は二種以上組み合わせて使用できる。特に、ビス(トリフルオロメタンスルホニル)イミドアニオン[(CFSON-]、ビス(フルオロスルホニル)イミドアニオン[(FSON-]、テトラ(ペンタフルオロフェニル)ボレートアニオン[(CB-]が好ましい。
 粘着剤組成物から形成される粘着剤層の帯電防止性能の経時安定性の点で、室温で固体であるイオン性化合物が好ましい。
The pressure-sensitive adhesive composition may further contain an antistatic agent.
As the antistatic agent, surfactants, siloxane compounds, conductive polymers, ionic compounds and the like can be mentioned, with preference given to ionic compounds. Examples of the ionic compound include conventional ones. As a cation component which comprises an ionic compound, an organic cation, an inorganic cation, etc. are mentioned. Examples of the organic cation include pyridinium cation, pyrrolidinium cation, piperidinium cation, imidazolium cation, ammonium cation, sulfonium cation, phosphonium cation and the like. Examples of inorganic cations include lithium cations, potassium cations, sodium cations, alkali metal cations such as cesium cations, and alkaline earth metal cations such as magnesium cations and calcium cations. In particular, pyridinium cation, imidazolium cation, pyrrolidinium cation, lithium cation and potassium cation are preferable from the viewpoint of compatibility with the (meth) acrylic resin. The anion component constituting the ionic compound may be either an inorganic anion or an organic anion, but in terms of antistatic performance, an anion component containing a fluorine atom is preferred. As an anion component containing a fluorine atom, for example, hexafluorophosphate anion (PF 6- ), bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N-], bis (fluorosulfonyl) imide anion [(FSO) 2 ) 2 N-], tetra (pentafluorophenyl) borate anion [(C 6 F 5 ) 4 B-] and the like. These ionic compounds can be used alone or in combination of two or more. In particular, bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N-], bis (fluorosulfonyl) imide anion [(FSO 2 ) 2 N-], tetra (pentafluorophenyl) borate anion [(C 6 F 5 ) 4 B-] is preferred.
The ionic compound which is solid at room temperature is preferred in view of the temporal stability of the antistatic performance of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.
 帯電防止剤の含有量は、(メタ)アクリル系樹脂(A)100質量部に対して、例えば、0.01~20質量部、好ましくは0.1~10質量部、さらに好ましくは1~7質量である。 The content of the antistatic agent is, for example, 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 1 to 7 with respect to 100 parts by mass of the (meth) acrylic resin (A). It is mass.
 粘着剤組成物は、溶剤、架橋触媒、タッキファイヤー、可塑剤、軟化剤、顔料、防錆剤、無機フィラー、光散乱性微粒子等の添加剤を1種又は2種以上含有することができる。 The pressure-sensitive adhesive composition can contain one or more additives such as a solvent, a crosslinking catalyst, a tackifier, a plasticizer, a softener, a pigment, a rust inhibitor, an inorganic filler, and light scattering fine particles.
 本発明に係る粘着剤層付光学フィルムの一例を図1に示した。
 図1に示すように、本発明の光学フィルム1の少なくとも一方の面に粘着剤層2を有している粘着剤層付光学フィルムは、光学フィルムと粘着剤層とが貼合している面と反対の面にセパレートフィルム(剥離フィルム)3を積層していてもよい。このセパレートフィルム3は通常、粘着剤層付光学フィルムの使用時(例えば液晶セルや位相差フィルム等への積層時)に剥離除去される。セパレートフィルムは、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート、ポリアレート等の各種樹脂からなるフィルムの粘着剤層が形成される面に、シリコーン処理等の離型処理が施されたものであることができる。
An example of the pressure-sensitive adhesive layer-carrying optical film according to the present invention is shown in FIG.
As shown in FIG. 1, in the pressure-sensitive adhesive layer-carrying optical film having the pressure-sensitive adhesive layer 2 on at least one surface of the optical film 1 of the present invention, the surface to which the optical film and the pressure-sensitive adhesive layer are bonded. The separate film (release film) 3 may be laminated on the side opposite to the above. The separate film 3 is usually peeled and removed at the time of use of the pressure-sensitive adhesive layer-attached optical film (for example, at the time of lamination on a liquid crystal cell, retardation film, etc.). The separate film is, for example, a film on which an adhesive layer of a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarete, etc. is subjected to release treatment such as silicone treatment. it can.
 図2~図5に本発明に係る光学フィルムを含む光学積層体の層構成の一例を図1に示した。
 図2に記載の光学積層体10Aは、保護フィルム4、接着剤層5、偏光フィルム6、接着剤層5、本発明の光学フィルム1、粘着剤層7を含む光学積層体である。
 図3に記載の光学積層体10Bは、本発明の光学フィルム1、接着剤層5、偏光フィルム6、接着剤層5、保護フィルム4、粘着剤層7を含む光学積層体である。
 図4に記載の光学フィルム10C及び図5に記載の光学積層体10Dは、保護フィルム4、接着剤層5、偏光フィルム6、接着剤層5、本発明の光学フィルム1、粘着剤層7、光学フィルム40、粘着剤層7a、発光素子30(液晶セル、OLEDセル)を含む光学積層体である。
An example of the layer configuration of the optical laminate including the optical film according to the present invention is shown in FIG. 1 to FIG.
An optical laminate 10A described in FIG. 2 is an optical laminate including a protective film 4, an adhesive layer 5, a polarizing film 6, an adhesive layer 5, an optical film 1 of the present invention, and an adhesive layer 7.
An optical laminate 10B described in FIG. 3 is an optical laminate including the optical film 1, the adhesive layer 5, the polarizing film 6, the adhesive layer 5, the protective film 4 and the pressure-sensitive adhesive layer 7 of the present invention.
The optical film 10C shown in FIG. 4 and the optical laminate 10D shown in FIG. 5 are a protective film 4, an adhesive layer 5, a polarizing film 6, an adhesive layer 5, an optical film 1 of the present invention, an adhesive layer 7, It is an optical laminate including the optical film 40, the pressure-sensitive adhesive layer 7a, and the light emitting element 30 (liquid crystal cell, OLED cell).
 本発明の粘着剤層付光学フィルムの粘着剤層面には、位相差フィルム、偏光フィルム、ウィンドフィルム等の光学フィルムが積層されていてもよい。 An optical film such as a retardation film, a polarizing film, or a window film may be laminated on the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive layer-attached optical film of the present invention.
 位相差フィルムとは、光学異方性を示す光学フィルムであって、例えば、ポリビニルアルコール、ポリカーボネート、ポリエステル、ポリアリレート、ポリイミド、ポリオレフィン、ポリシクロオレフィン、ポリスチレン、ポリサルホン、ポリエーテルサルホン、ポリビニリデンフルオライド/ポリメチルメタクリレート、アセチルセルロース、エチレン-酢酸ビニル共重合体ケン化物、ポリ塩化ビニルなどからなる高分子フィルムを1.01~6倍程度に延伸することにより得られる延伸フィルムなどが挙げられる。中でも、ポリカーボネートフィルムやシクロオレフィン系樹脂フィルムを一軸延伸または二軸延伸した高分子フィルムであることが好ましい。なお、本明細書において、位相差フィルムは、ゼロレタデーションフィルムを含み、一軸性位相差フィルム、低光弾性率位相差フィルム、広視野角位相差フィルムなどと称されるフィルムも含む。 The retardation film is an optical film showing optical anisotropy, and for example, polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, polycycloolefin, polystyrene, polysulfone, polyether sulfone, polyvinylidene fluoro, An example is a stretched film obtained by stretching a polymer film composed of a ride / polymethyl methacrylate, acetyl cellulose, a saponified ethylene-vinyl acetate copolymer, polyvinyl chloride and the like by about 1.01 to 6 times. Among them, a polymer film obtained by uniaxially or biaxially stretching a polycarbonate film or a cycloolefin resin film is preferable. In the present specification, the retardation film includes a zero retardation film, and also includes a film referred to as a uniaxial retardation film, a low photoelastic modulus retardation film, a wide viewing angle retardation film, or the like.
 液晶性化合物の塗布・配向によって光学異方性を発現させたフィルムや、無機層状化合物の塗布によって光学異方性を発現させたフィルムとしては、温度補償型位相差フィルムと称されるフィルム、JX日鉱日石エネルギー(株)から販売されている“NHフィルム”(商品名;棒状液晶が傾斜配向したフィルム)、富士フイルム(株)から販売されている“WVフィルム”(商品名;円盤状液晶が傾斜配向したフィルム)、住友化学(株)から販売されている“VACフィルム”(商品名;完全二軸配向型のフィルム)、住友化学(株)から販売されている“new VACフィルム”(商品名;二軸配向型のフィルム)などが挙げられる。 A film referred to as a temperature compensation type retardation film, a film referred to as a temperature-compensated retardation film, a film in which optical anisotropy is expressed by application and orientation of a liquid crystal compound, and a film in which optical anisotropy is expressed by application of an inorganic layered compound. “NH film” (trade name; film in which rod-like liquid crystals are inclined and aligned) sold by Nippon Mining & Energy Co., Ltd., “WV film” sold by Fujifilm Co., Ltd. (trade name; disc-like liquid crystal Is a film of which the orientation is inclined), "VAC film" (trade name; film of perfect biaxial orientation type) sold by Sumitomo Chemical Co., Ltd., "new VAC film" sold by Sumitomo Chemical Co., Ltd. Trade name; biaxially oriented film) and the like.
 ゼロレタデーションフィルムとは、正面レタデーションReと厚み方向のレタデーションRthとが、ともに-15~15nmであり、光学的に等方なフィルムをいう。ゼロレタデーションフィルムとしては、セルロース系樹脂、ポリオレフィン系樹脂(鎖状ポリオレフィン系樹脂、ポリシクロオレフィン系樹脂など)またはポリエチレンテレフタレート系樹脂からなる樹脂フィルムが挙げられ、レタデーション値の制御が容易で、入手も容易であるという点で、セルロース系樹脂またはポリオレフィン系樹脂が好ましい。ゼロレタデーションフィルムは、保護フィルムとしても用いることができる。ゼロレタデーションフィルムとしては、富士フイルム(株)から販売されている“Z-TAC”(商品名)、コニカミノルタオプト(株)から販売されている“ゼロタック(登録商標)”、日本ゼオン(株)から販売されている“ZF-14”(商品名)などが挙げられる。 The zero retardation film is an optically isotropic film in which both the front retardation R e and the retardation R th in the thickness direction are -15 to 15 nm. As a zero retardation film, resin films made of cellulose resins, polyolefin resins (chain polyolefin resins, polycycloolefin resins, etc.) or polyethylene terephthalate resins can be mentioned. Cellulose-based resins or polyolefin-based resins are preferred in that they are easy. The zero retardation film can also be used as a protective film. As the zero retardation film, “Z-TAC” (trade name) sold by Fuji Film Co., Ltd., “Zero Tack (registered trademark)” sold by Konica Minolta Opto Co., Ltd., Nippon Zeon Co., Ltd. And “ZF-14” (trade name) sold by
 本発明の光学フィルムにおいて、位相差フィルムは、重合性液晶化合物を硬化させてなる位相差フィルムが好ましい。 In the optical film of the present invention, the retardation film is preferably a retardation film obtained by curing a polymerizable liquid crystal compound.
 液晶性化合物の塗布・配向によって光学異方性を発現させたフィルムとしては、第一の形態:棒状液晶化合物が支持基材に対して水平方向に配向した位相差フィルム、第二の形態:棒状液晶化合物が支持基材に対して垂直方向に配向した位相差フィルム、第三の形態:棒状液晶化合物が面内で螺旋状に配向の方向が変化している位相差フィルム、第四の形態:円盤状液晶化合物が傾斜配向している位相差フィルム、第五の形態:円盤状液晶化合物が支持基材に対して垂直方向に配向した二軸性の位相差フィルムがあげられる。 As a film in which optical anisotropy is expressed by application and orientation of liquid crystalline compound, the first form: retardation film in which a rod-like liquid crystal compound is oriented in the horizontal direction with respect to a supporting substrate, second form: rod-like Retardation film in which a liquid crystal compound is oriented in a direction perpendicular to a supporting substrate, Third embodiment: Retardation film in which a rod-like liquid crystal compound has a helical orientation in the plane, and fourth embodiment: The retardation film in which the discotic liquid crystal compound is obliquely oriented, and the fifth form: a biaxial retardation film in which the discotic liquid crystal compound is oriented in the direction perpendicular to the supporting substrate.
 たとえば、有機エレクトロルミネッセンスディスプレイに用いられる光学フィルムとしては、第一の形態、第二の形態、第五の形態が好適に用いられる。またはこれらを積層させて用いてもよい。 For example, as an optical film used for an organic electroluminescent display, the 1st form, the 2nd form, and the 5th form are used suitably. Or these may be laminated and used.
 位相差フィルムが、重合性液晶化合物の配向状態における重合体からなる層(以下、「光学異方性層」と称する場合がある)である場合、位相差フィルムは逆波長分散性を有することが好ましい。逆波長分散性とは、短波長での液晶配向面内位相差値の方が長波長での液晶配向面内位相差値よりも小さくなる光学特性であり、好ましくは、位相差フィルムが下記式(7)および式(8)を満たすことである。なお、Re(λ)は波長λnmの光に対する面内位相差値を表す。
 Re(450)/Re(550)≦1   (7)
 1≦Re(630)/Re(550)   (8)
 本発明の光学フィルムにおいて、位相差フィルムが第一の形態でかつ逆波長分散性を有する場合、表示装置での黒表示時の着色が低減するため好ましく、前記式(7)において0.82≦Re(450)/Re(550)≦0.93であればより好ましい。さらに120≦Re(550)≦150が好ましい。
When the retardation film is a layer composed of a polymer in the alignment state of the polymerizable liquid crystal compound (hereinafter sometimes referred to as "optically anisotropic layer"), the retardation film has reverse wavelength dispersion. preferable. Reverse wavelength dispersion is an optical characteristic in which the in-plane retardation value at the short wavelength is smaller than the in-plane retardation value at the long wavelength, and preferably the retardation film has the following formula It is to satisfy (7) and equation (8). Re (λ) represents an in-plane retardation value for light of wavelength λ nm.
Re (450) / Re (550) ≦ 1 (7)
1 ≦ Re (630) / Re (550) (8)
In the optical film of the present invention, when the retardation film is in the first form and has reverse wavelength dispersion, it is preferable because the coloration at the time of black display in the display device is reduced, and 0.82 ≦ in the formula (7). It is more preferable if Re (450) / Re (550) ≦ 0.93. Furthermore, 120 ≦ Re (550) ≦ 150 is preferable.
 位相差フィルムが、光学異方性層を有するフィルムである場合の重合性液晶化合物としては、液晶便覧(液晶便覧編集委員会編、丸善(株)平成12年10月30日発行)の「3.8.6 ネットワーク(完全架橋型)」、「6.5.1 液晶材料 b.重合性ネマチック液晶材料」に記載された化合物の中で重合性基を有する化合物、並びに、特開2010-31223号公報、特開2010-270108号公報、特開2011-6360号公報、特開2011-207765号公報、特開2011-162678号、特開2016-81035号公報、国際公開2017/043438号公報及び特表2011-207765号公報に記載の重合性液晶化合物が挙げられる。 As a polymerizable liquid crystal compound when the retardation film is a film having an optically anisotropic layer, “3” of “Liquid Crystal Handbook” (edited by the LCD Handbook Editorial Board, Maruzen Co., Ltd., published on October 30, 2000). Of the compounds described in “8.6 Network (fully cross-linked type)”, “6.5.1 liquid crystal material b. Polymerizable nematic liquid crystal material”, compounds having a polymerizable group, and JP-A-2010-31223 Publication No. 2010-270108 Publication No. 2011-6360 Publication No. 2011-207765 Publication No. 2011-162678 Publication No. 2016-81035 Publication International Publication 2017/043438 Publication The polymerizable liquid crystal compound described in JP-A-2011-207765 can be mentioned.
 重合性液晶化合物の配向状態における重合体から位相差フィルムを製造する方法は、例えば、特開2010-31223号公報に記載の方法が挙げられる。 Examples of the method for producing a retardation film from a polymer in the alignment state of the polymerizable liquid crystal compound include the method described in JP-A-2010-31223.
 第2の形態の場合、正面位相差値Re(550)は0~10nmの範囲に、好ましくは0~5nmの範囲に調整すればよく、厚み方向の位相差値Rthは、-10~-300nmの範囲に、好ましくは-20~-200nmの範囲に調整すればよい。厚み方向の屈折率異方性を意味する厚み方向の位相差値Rthは、面内の進相軸を傾斜軸として50度傾斜させて測定される位相差値R50と面内の位相差値R0 とから算出できる。すなわち、厚み方向の位相差値Rthは、面内の位相差値R0、進相軸を傾斜軸として50度傾斜させて測定した位相差値R50、位相差フィルムの厚みd、及び位相差フィルムの平均屈折率n0から、以下の式 (10)~(12)によりnx、ny及びnz を求め、これらを式(9)に代入して、算出することができる。 In the case of the second embodiment, the front retardation value Re (550) may be adjusted in the range of 0 to 10 nm, preferably in the range of 0 to 5 nm, and the retardation value R th in the thickness direction is -10 to- It may be adjusted in the range of 300 nm, preferably in the range of -20 to -200 nm. The retardation value R th in the thickness direction, which means the refractive index anisotropy in the thickness direction, is an in-plane retardation difference from the retardation value R 50 measured by tilting 50 degrees with the in-plane fast axis as the tilt axis. It can be calculated from the value R 0 . That is, the phase difference value R th in the thickness direction retardation value R 0 in the plane retardation value R 50 measured by inclining 50 degrees inclination axis fast axis, thickness of the retardation film d, and positions the average refractive index n 0 of the retardation film, obtains the n x, n y and n z by the following equation (10) to (12), these are substituted into equation (9) can be calculated.
  Rth=[(n+n)/2-n]×d  (9)
  R =(n-n)×d          (10)
  R50=(n-n')×d/cos(φ)   (11)
  (n+n+n)/3=n        (12)
ここで、
  φ=sin-1〔sin(40°)/n
  n'=n×n/〔n ×sin(φ)+n ×cos(φ)〕1/2
R th = [(n x + n y ) / 2-n z ] × d (9)
R 0 = (n x -n y ) × d (10)
R 50 = (n x -n y ') × d / cos (φ) (11)
(n x + n y + n z ) / 3 = n 0 (12)
here,
φ = sin −1 (sin (40 °) / n 0 )
n y '= n y × n z / [ ny 2 × sin 2 (φ) + n z 2 × cos 2 (φ)] 1/2
 位相差フィルムは、二以上の層を有する多層フィルムであってもよい。例えば、位相差フィルムの片面又は両面に保護フィルムが積層されたものや、二以上の位相差フィルムが粘着剤又は接着剤を介して積層されたものが挙げられる。 The retardation film may be a multilayer film having two or more layers. For example, the thing by which the protective film was laminated | stacked on the single side | surface or both surfaces of retardation film, and the thing by which two or more retardation films were laminated | stacked via the adhesive or the adhesive agent are mentioned.
 光学フィルム40が二以上の位相差フィルムが積層された多層フィルムである場合、本発明の光学フィルムを含む光学積層体の構成としては、図4に示したように、透過光に1/4波長分の位相差を付与する1/4波長位相差層50と透過光に1/2波長分の位相差を付与する1/2波長位相差層70とを、接着剤又は粘着剤60を介して積層した光学フィルム40を含む構成が挙げられる。また、図5に示したように、1/4波長位相差層50aとポジティブC層80とを、接着剤層又は粘着剤層を介して積層した光学フィルム40を含む構成も挙げられる。 When the optical film 40 is a multilayer film in which two or more retardation films are laminated, as a configuration of an optical laminate including the optical film of the present invention, as shown in FIG. A quarter-wave retardation layer 50 for giving a retardation of a minute and a half-wave retardation layer 70 for giving a retardation of a 1⁄2 wavelength to transmitted light through an adhesive or a pressure-sensitive adhesive 60 A configuration including the laminated optical film 40 can be mentioned. Moreover, as shown in FIG. 5, the structure containing the optical film 40 which laminated | stacked the quarter wavelength phase difference layer 50a and the positive C layer 80 through the adhesive bond layer or the adhesive layer is also mentioned.
 図4の1/4波長分の位相差を付与する1/4波長位相差層50、および透過光に1/2波長分の位相差を付与する1/2波長位相差層70は上記第一の形態の光学フィルムであっても第五の形態の光学フィルムであってもよい。図4の構成の場合、少なくとも片方が第五の形態であることがより好ましい。 The first wavelength retardation layer 50 for giving a phase difference of 1⁄4 wavelength shown in FIG. 4 and the half wavelength retardation layer 70 for giving a phase difference of 1⁄2 wavelength to transmitted light The optical film of the fifth aspect may be used. In the case of the configuration of FIG. 4, it is more preferable that at least one is the fifth form.
 図5の構成の場合、1/4波長位相差層50aは上記第一の形態の光学フィルムであることが好ましく、さらに式(7)、式(8)を満たすことがより好ましい。 In the case of the configuration of FIG. 5, the 1⁄4 wavelength retardation layer 50 a is preferably the optical film of the first embodiment, and more preferably satisfies the expressions (7) and (8).
 偏光フィルムはその吸収軸に平行な振動面をもつ直線偏光を吸収し、吸収軸に直交する(透過軸と平行な)振動面をもつ直線偏光を透過する性質を有するフィルムであり、例えば、ポリビニルアルコール系樹脂フィルムに二色性色素を吸着配向させたフィルムを用いることができる。二色性色素としては、例えば、ヨウ素や二色性有機染料などが挙げられる。 A polarizing film is a film which has the property of absorbing linearly polarized light having a vibration plane parallel to its absorption axis and transmitting linearly polarized light having a vibration plane orthogonal to the absorption axis (parallel to the transmission axis), for example, polyvinyl A film in which a dichroic dye is adsorbed and oriented to an alcohol-based resin film can be used. Examples of dichroic dyes include iodine and dichroic organic dyes.
 通常、ポリビニルアルコール系樹脂を製膜したものを偏光フィルムの原反フィルムとして用いる。ポリビニルアルコール系樹脂は、公知の方法で製膜することができる。原反フィルムの厚みは、通常1~150μmであり、延伸のしやすさなどを考慮すれば、好ましくは10μm以上である。 Usually, what formed polyvinyl alcohol-type resin into a film is used as a raw film of a polarizing film. The polyvinyl alcohol-based resin can be formed into a film by a known method. The thickness of the raw film is usually 1 to 150 μm, and preferably 10 μm or more in consideration of the ease of stretching and the like.
 偏光フィルムは、例えば、原反フィルムに対して、一軸延伸する工程、二色性色素でフィルムを染色してその二色性色素を吸着させる工程、ホウ酸水溶液でフィルムを処理する工程、及び、フィルムを水洗する工程が施され、最後に乾燥して製造される。偏光フィルムの厚みは、通常1~30μmであり、薄膜化の観点から、好ましくは20μm以下、さらに好ましくは15μm以下、特に10μm以下である。 The polarizing film may be, for example, uniaxially stretching a raw film, dyeing the film with a dichroic dye and adsorbing the dichroic dye, treating the film with an aqueous solution of boric acid, The film is subjected to a step of washing with water, and finally dried and manufactured. The thickness of the polarizing film is usually 1 to 30 μm, preferably 20 μm or less, more preferably 15 μm or less, particularly 10 μm or less from the viewpoint of thinning.
 ポリビニルアルコール系樹脂フィルムに二色性色素を吸着配向させてなる偏光フィルムは、原反フィルムとしてポリビニルアルコール系樹脂フィルムの単独フィルムを用い、このフィルムに対して一軸延伸処理及び二色性色素の染色処理を施す方法(方法(1)とする)のほか、基材フィルムにポリビニルアルコール系樹脂を含有する塗工液(水溶液等)を塗工、乾燥させてポリビニルアルコール系樹脂層を有する基材フィルムを得た後、これを基材フィルムごとに一軸延伸し、延伸後のポリビニルアルコール系樹脂層に対して二色性色素の染色処理を施し、次いで基材フィルムを剥離除去する方法(方法(2)とする)によっても得ることができる。基材フィルムとしては、熱可塑性樹脂からなるフィルムを用いることができ、好ましくは、ポリエチレンテレフタレートなどのポリエステル系樹脂、ポリカーボネート系樹脂、トリアセチルセルロースなどのセルロース系樹脂、ノルボルネン系樹脂などの環状ポリオレフィン系樹脂、ポリスチレン系樹脂などからなるフィルムである。上記方法(2)を利用すると、薄膜の偏光フィルムの作製が容易となり、例えば厚み7μm以下の偏光子2の作製であっても容易に行うことができる。 A polarizing film obtained by adsorbing and orienting a dichroic dye to a polyvinyl alcohol-based resin film uses a single film of a polyvinyl alcohol-based resin film as a raw film, and uniaxial stretching and dyeing of the dichroic dye on this film A base film having a polyvinyl alcohol-based resin layer by applying a coating solution (such as an aqueous solution) containing a polyvinyl alcohol-based resin to a base film and drying it, in addition to the method of treating (the method (1)) After uniaxial stretching for each base film, subjecting the stretched polyvinyl alcohol-based resin layer to a dyeing treatment of a dichroic dye, and then peeling and removing the base film (method (2 ) Can also be obtained. As the substrate film, a film made of a thermoplastic resin can be used, and preferably, polyester resins such as polyethylene terephthalate, polycarbonate resins, cellulose resins such as triacetyl cellulose, cyclic polyolefin resins such as norbornene resin It is a film made of a resin, a polystyrene resin, or the like. By using the above method (2), the thin film polarizing film can be easily produced, and for example, the polarizing film 2 having a thickness of 7 μm or less can be easily produced.
 偏光フィルムの少なくとも一方の面は、接着剤を介して保護フィルムが設けられていることが好ましい。
 接着剤としては、公知の接着剤が用いられ、水系接着剤であってもよいし、活性エネルギー線硬化型接着剤であってもよい。
It is preferable that at least one surface of the polarizing film is provided with a protective film via an adhesive.
As the adhesive, a known adhesive may be used, which may be a water-based adhesive or an active energy ray-curable adhesive.
 水系接着剤としては、慣用の水系接着剤(例えば、ポリビニルアルコール系樹脂水溶液からなる接着剤、水系二液型ウレタン系エマルジョン接着剤、アルデヒド化合物、エポキシ化合物、メラミン系化合物、メチロール化合物、イソシアネート化合物、アミン化合物、多価金属塩等の架橋剤など)が挙げられる。これらのうち、ポリビニルアルコール系樹脂水溶液からなる水系接着剤を好適に用いることができる。なお、水系接着剤を使用する場合は、偏光フィルムと保護フィルムとを貼合した後、水系接着剤中に含まれる水を除去するために乾燥させる工程を実施することが好ましい。乾燥工程後、例えば20~45℃程度の温度で養生する養生工程を設けてもよい。 As a water-based adhesive, a conventional water-based adhesive (for example, an adhesive comprising a polyvinyl alcohol-based resin aqueous solution, a water-based two-component urethane-based emulsion adhesive, an aldehyde compound, an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, Amine compounds, crosslinking agents such as polyvalent metal salts, etc. may be mentioned. Among these, the water-based adhesive which consists of polyvinyl alcohol-type resin aqueous solution can be used suitably. In addition, when using a water-based adhesive, after bonding a polarizing film and a protective film, it is preferable to implement the process to dry in order to remove the water contained in a water-based adhesive. After the drying step, there may be provided a curing step of curing at a temperature of about 20 to 45 ° C., for example.
 上記活性エネルギー線硬化性接着剤とは、紫外線や電子線等の活性エネルギー線を照射することで硬化する接着剤をいい、例えば、重合性化合物及び光重合開始剤を含む硬化性組成物、光反応性樹脂を含む硬化性組成物、バインダー樹脂及び光反応性架橋剤を含む硬化性組成物等が挙げられ、好ましくは紫外線硬化性接着剤である。 The above-mentioned active energy ray-curable adhesive means an adhesive which is cured by irradiation with active energy rays such as ultraviolet rays and electron beams, and for example, a curable composition containing a polymerizable compound and a photopolymerization initiator, light A curable composition containing a reactive resin, a curable composition containing a binder resin and a photoreactive crosslinking agent, and the like can be mentioned, with preference given to a UV curable adhesive.
活性エネルギー線硬化性接着剤を用いる場合は、偏光フィルムと保護フィルムとを貼合した後、必要に応じて乾燥工程を行い、次いで活性エネルギー線を照射することにより活性エネルギー線硬化性接着剤を硬化させる硬化工程を行う。活性エネルギー線の光源は特に限定されないが、波長400nm以下に発光分布を有する紫外線が好ましい。 When using an active energy ray-curable adhesive, after bonding a polarizing film and a protective film, a drying process is performed if necessary, and then an active energy ray-curable adhesive is obtained by irradiating an active energy ray. A curing step to cure is performed. Although the light source of the active energy ray is not particularly limited, ultraviolet light having a light emission distribution at a wavelength of 400 nm or less is preferable.
 偏光フィルムと保護フィルムとを貼合する方法としては、これらの少なくともいずれか一方の貼合面にケン化処理、コロナ処理、プラズマ処理等の表面活性化処理を施す方法などが挙げられる。偏光フィルムの両面に樹脂フィルムが貼合される場合、これらの樹脂フィルムを貼合するための接着剤は、同種の接着剤あってもよいし異種の接着剤であってもよい。 As a method of bonding a polarizing film and a protective film, the method etc. of surface-activating processes, such as a saponification process, a corona treatment, a plasma treatment, etc. are mentioned to these bonding surface of at least any one of these. When resin films are bonded to both sides of a polarizing film, the adhesive for bonding these resin films may be either the same type of adhesive or different types of adhesives.
 偏光板の好ましい構成としては、偏光フィルムの少なくとも一方の面に接着剤層を介して保護フィルムが積層された偏光板である。保護フィルムが偏光フィルムの一方の面にしか積層されない場合、視認側に積層されることがより好ましい。視認側に積層された保護フィルムは、トリアセチルセルロース系樹脂又はシクロオレフィン系樹脂からなる保護フィルムであることが好ましい。保護フィルムは未延伸フィルムであってもよいし、任意の方向に延伸され位相差を有していてもよい。視認側に積層された保護フィルムの表面にはハードコート層やアンチグレア層などの表面処理層が設けられていてもよい。
 保護フィルムが偏光フィルムの両面に積層される場合、パネル側(視認側と反対側)の保護フィルムは、トリアセチルセルロース系樹脂、シクロオレフィン系樹脂又はアクリル系樹脂からなる保護フィルム又は位相差フィルムであることが好ましい。位相差フィルムは後述するゼロレタデーションフィルムであってもよい。
 偏光板とパネルとの間には、さらにその他の層又はフィルムが積層されていてもよい。有機ELディスプレイ用の円偏光板として用いる場合は、1/4波長位相差層と1/2波長位相差層とを有する位相差層、後述する逆波長分散性の1/4波長層が積層されていることが好ましい。位相差層は薄膜化の観点から液晶系位相差フィルムであることが好ましい。
 集光フィルムは、光路制御等を目的に用いられるもので、プリズムアレイシートやレンズアレイシート、ドット付設シート等であることができる。
A preferable configuration of the polarizing plate is a polarizing plate in which a protective film is laminated on at least one surface of a polarizing film via an adhesive layer. When the protective film is laminated on only one side of the polarizing film, it is more preferable to be laminated on the viewing side. It is preferable that the protective film laminated | stacked on the visual recognition side is a protective film which consists of triacetyl-cellulose-type resin or cycloolefin type resin. The protective film may be an unstretched film, or may be stretched in any direction and have a retardation. A surface treatment layer such as a hard coat layer or an antiglare layer may be provided on the surface of the protective film laminated on the viewing side.
When the protective film is laminated on both sides of the polarizing film, the protective film on the panel side (the opposite side to the visible side) is a protective film or a retardation film made of a triacetyl cellulose resin, a cycloolefin resin or an acrylic resin. Is preferred. The retardation film may be a zero retardation film described later.
Another layer or film may be further laminated between the polarizing plate and the panel. When used as a circularly polarizing plate for an organic EL display, a retardation layer having a 1⁄4 wavelength retardation layer and a 1⁄2 wavelength retardation layer, and a 1⁄4 wavelength layer of reverse wavelength dispersion described later are laminated. Is preferred. The retardation layer is preferably a liquid crystal retardation film from the viewpoint of thinning.
A condensing film is used for the purpose of light path control etc., and can be a prism array sheet, a lens array sheet, a dot attachment sheet, or the like.
 輝度向上フィルムは、偏光板を適用した液晶表示装置における輝度を向上させる目的で使用される。具体的には、屈折率の異方性が互いに異なる薄膜フィルムを複数枚積層して反射率に異方性が生じるように設計された反射型偏光分離シート、コレステリック液晶ポリマーの配向フィルムやその配向液晶層を基材フィルム上に支持した円偏光分離シート等が挙げられる。 The brightness enhancement film is used for the purpose of improving the brightness in a liquid crystal display device to which a polarizing plate is applied. Specifically, a reflection type polarization separation sheet designed to have anisotropy in reflectance by laminating a plurality of thin film films having mutually different anisotropy of refractive index, an alignment film of cholesteric liquid crystal polymer and its alignment The circularly polarized light separation sheet etc. which supported the liquid crystal layer on the base film are mentioned.
 ウィンドウフィルムとは、フレキシブルディスプレイ等のフレキシブル表示装置における前面板を意味し、一般的には表示装置の最表面に配置される。ウィンドウフィルムは、例えばポリイミド樹脂からなる樹脂フィルムが挙げられる。ウィンドウフィルムは、例えばポリイミド及びシリカを含む樹脂フィルムのような、有機材料と無機材料のハイブリッドフィルムであってもよい。また、ウィンドウフィルムはその表面に、表面硬度や防汚性、耐指紋性を機能付与するためのハードコート層が配置されていてもよい。たとえば、特開2017―94488号記載のフィルム等が挙げられる。 The window film means a front plate in a flexible display such as a flexible display, and is generally disposed on the outermost surface of the display. The window film is, for example, a resin film made of a polyimide resin. The window film may be a hybrid film of an organic material and an inorganic material, such as a resin film containing, for example, polyimide and silica. In addition, a hard coat layer may be disposed on the surface of the window film to impart surface hardness, stain resistance, and fingerprint resistance. For example, the film etc. of Unexamined-Japanese-Patent No. 2017-94488 are mentioned.
 本発明の光学フィルムは、偏光板の保護フィルムとして使用してもよい。
 偏光板は、上述のとおり、偏光フィルムの片面又は両面に接着剤層を介して保護フィルムが積層されている。偏光子の両面に保護フィルムが積層されている偏光板においては、偏光子の片面の保護フィルムに本発明の光学フィルムを使用してもよいし、両面の保護フィルムに本発明の光学フィルムを使用してもよい。また、本発明の光学フィルムを偏光板の保護フィルムとして使用した偏光板は、接着剤層又は粘着剤層を介して他の光学フィルムと積層されていてもよく、該積層体の一例を図2及び図3に示した。
The optical film of the present invention may be used as a protective film of a polarizing plate.
In the polarizing plate, as described above, the protective film is laminated on one side or both sides of the polarizing film via the adhesive layer. In the polarizing plate in which the protective film is laminated on both sides of the polarizer, the optical film of the present invention may be used as the protective film on one side of the polarizer, or the optical film of the present invention is used as the protective film on both sides. You may In addition, a polarizing plate using the optical film of the present invention as a protective film of the polarizing plate may be laminated with another optical film through an adhesive layer or a pressure-sensitive adhesive layer, and an example of the laminate is shown in FIG. And shown in FIG.
 接着剤層5は、公知の接着剤から形成される層である。公知の接着剤としては、水系接着剤であってもよいし、活性エネルギー線硬化型接着剤であってもよい。粘着剤層6は、上述した粘着剤から形成された層であってもよいし、他の公知の粘着剤から形成された層であってもよい。 The adhesive layer 5 is a layer formed of a known adhesive. The known adhesive may be a water-based adhesive or an active energy ray-curable adhesive. The pressure-sensitive adhesive layer 6 may be a layer formed of the above-described pressure-sensitive adhesive or may be a layer formed of another known pressure-sensitive adhesive.
 保護フィルム4は、公知の熱可塑性樹脂フィルムが挙げられる。保護フィルム4が本発明の光学フィルムであってもよい。 The protective film 4 may be a known thermoplastic resin film. The protective film 4 may be the optical film of the present invention.
 本発明の光学フィルムは、液晶表示装置に好適に用いることができる。 The optical film of the present invention can be suitably used for a liquid crystal display device.
 以下、実施例及び比較例を示して本発明をさらに具体的に説明するが、本発明はこれらの例によって限定されるものではない。例中、含有量ないし使用量を表す%及び部は、特に断りのない限り質量基準である。 EXAMPLES The present invention will be more specifically described below by showing Examples and Comparative Examples, but the present invention is not limited by these examples. In the examples,% and parts representing contents or amounts used are on a mass basis unless otherwise noted.
 <光選択吸収性化合物の合成>
[合成例1]光選択吸収化合物(1)の合成
Figure JPOXMLDOC01-appb-I000023

 ジムロート冷却管、温度計を設置した200mL-四ツ口フラスコ内を窒素雰囲気とし、特許文献(特開2014-194508)を参考に合成した式(aa)で表される化合物10g、無水酢酸(和光純薬工業株式会社製)3.6g、シアノ酢酸2-エチルヘキシル(東京化成工業株式会社製)6.9g、およびアセトニトリル(和光純薬工業株式会社製)60gを仕込み、マグネチックスターラーで撹拌した。内温25℃にてDIPEA(東京化成工業株式会社製)4.5gを滴下漏斗から1時間かけて滴下し、滴下終了後に内温25℃にてさらに2時間保温した。反応終了後、減圧エバポレーターを用いてアセトニトリルを除去し、カラムクロマトグラフィー(シリカゲル)に供して精製し、式(aa1)で表される光選択吸収性化合物(1)を含む流出液を、減圧エバポレーターを用いて溶媒を除去し、黄色結晶を得た。該結晶を60℃減圧乾燥することにより、黄色粉末として光選択吸収性化合物(1)を4.6g得た。収率は50%であった
<Synthesis of Photoselective Absorbent Compound>
Synthesis Example 1 Synthesis of Photoselective Absorption Compound (1)
Figure JPOXMLDOC01-appb-I000023

The inside of a 200 mL four-necked flask equipped with a Dimroth condenser and a thermometer is a nitrogen atmosphere, and 10 g of a compound represented by the formula (aa) synthesized with reference to patent document (Japanese Patent Laid-Open No. 2014-194508) 3.6 g of Kojun Pharmaceutical Co., Ltd., 6.9 g of 2-ethylhexyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 60 g of acetonitrile (Wako Pure Chemical Industries, Ltd.) were charged, and stirred with a magnetic stirrer. At an internal temperature of 25 ° C., 4.5 g of DIPEA (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dropped from the dropping funnel over 1 hour, and after completion of dropping, the temperature was kept at 25 ° C. for further 2 hours. After completion of the reaction, acetonitrile is removed using a vacuum evaporator and purified by column chromatography (silica gel) to purify the effluent containing the photoselective absorptive compound (1) represented by the formula (aa1). The solvent was removed using to give yellow crystals. The crystals were dried at 60 ° C. under reduced pressure to obtain 4.6 g of a photoselective absorptive compound (1) as a yellow powder. The yield was 50%
 H-NMR解析を行ったところ、以下のピークが観測されたことから、光選択吸収性化合物(1)が生成したことが確認された。
H-NMR(CDCl3)δ:0.87-0.94(m、6H)、1.32-1.67(m、8H)、1.59-1.66(m、2H)、2.09(quin、2H)、3.00(m、5H)、3.64(t、2H)、4.10(dd、2H)、5.52(d、2H)、7.87(d、2H)
When 1 H-NMR analysis was performed, the following peaks were observed, and thus, it was confirmed that the light selective absorption compound (1) was generated.
1 H-NMR (CDCl 3) δ: 0.87 to 0.94 (m, 6H), 1.32-1.67 (m, 8H), 1.59- 1.66 (m, 2H), 09 (quin, 2 H), 3.00 (m, 5 H), 3.64 (t, 2 H), 4. 10 (dd, 2 H), 5.52 (d, 2 H), 7.87 (d, 2 H) )
<グラム吸光係数ε測定>
 得られた光選択吸収性化合物(1)のグラム吸光係数を測定するために、光選択吸収性化合物(1)を2-ブタノンに溶解させた。得られた溶液(濃度;0.007g/L)を1cmの石英セルに入れ、石英セルを分光光度計UV-2450(株式会社島津製作所製)にセットし、ダブルビーム法により1nmステップ300~800nmの波長範囲で吸光度を測定した。得られた吸光度の値と、溶液中の光吸収性化合物濃度、石英セルの光路長から、波長ごとのグラム吸光係数を下記式を用いて算出した。
 ε(λ)=A(λ)/CL   
〔式中、ε(λ)は波長λnmにおける化合物のグラム吸光係数L/(g・cm)を表し、A(λ)は波長λnmにおける吸光度を表し、Cは濃度g/Lを表し、Lは石英セルの光路長cmを表す。〕
 光選択吸収性化合物(1)グラム吸光度係数は、ε(405)の値は47L/(g・cm)であり、ε(440)の値は0.1L/(g・cm)以下であり、ε(405)/ε(440)の値は80以上であった。
<Gram absorption coefficient ε measurement>
In order to measure the gram absorption coefficient of the obtained photoselective absorptive compound (1), the photoselective absorptive compound (1) was dissolved in 2-butanone. The resulting solution (concentration: 0.007 g / L) is placed in a 1 cm quartz cell, and the quartz cell is set in a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation), and 1 nm steps 300 to 800 nm by double beam method. Absorbance was measured in the wavelength range of From the obtained absorbance value, the concentration of the light absorbing compound in the solution, and the optical path length of the quartz cell, the gram absorption coefficient for each wavelength was calculated using the following equation.
ε (λ) = A (λ) / CL
[Wherein, ε (λ) represents the gram absorption coefficient L / (g · cm) of the compound at the wavelength λ nm, A (λ) represents the absorbance at the wavelength λ nm, C represents the concentration g / L, and L is It represents the optical path length cm of the quartz cell. ]
The light selective absorption compound (1) gram absorbance coefficient has a value of ε (405) of 47 L / (g · cm) and a value of ε (440) of less than 0.1 L / (g · cm), The value of ε (405) / ε (440) was 80 or more.
 [合成例2]光選択吸収化合物(1)の合成
Figure JPOXMLDOC01-appb-I000024
 ジムロート冷却管、温度計を設置した200mL-四ツ口フラスコ内に、窒素雰囲気において、特開2014-194508を参考に合成した式(aa)で表される化合物10g、無水酢酸(和光純薬工業株式会社製)3.6g、シアノ酢酸2-ブチルオクチル(東京化成工業株式会社製)10g、及びアセトニトリル(和光純薬工業株式会社製)60gを仕込み、マグネチックスターラーで撹拌した。内温25℃にてDIPEA(東京化成工業株式会社製)4.5gを、得られた混合物に1時間かけて滴下した後、内温25℃にてさらに2時間保温した。その後、減圧エバポレーターを用いてアセトニトリルを除去し、カラムクロマトグラフィー(シリカゲル)に供して精製し、式(aa2)で表される化合物を含む流出液を、減圧エバポレーターを用いて溶媒を除去し、黄色結晶を得た。該結晶を60℃減圧乾燥することにより、黄色粉末として式(aa2)で表される化合物(光選択吸収化合物(2))を4.6g得た。収率は56%であった。
 上記と同じ方法でグラム吸光度係数を求めると、式(aa4)で表される化合物のε(405)の値は45L/(g・cm)であり、ε(420)の値は2.1L/(g・cm)であった。
Synthesis Example 2 Synthesis of Photoselective Absorption Compound (1)
Figure JPOXMLDOC01-appb-I000024
10 g of a compound represented by the formula (aa) prepared by referring to JP-A-2014-194508 in a nitrogen atmosphere in a 200 mL four-necked flask provided with a Dimroth condenser and a thermometer, acetic anhydride (Wako Pure Chemical Industries, Ltd. 3.6 g of the product, Inc., 10 g of 2-butyloctyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 60 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) were charged, and stirred with a magnetic stirrer. After 4.5 g of DIPEA (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained mixture over 1 hour at an internal temperature of 25 ° C., the mixture was kept at an internal temperature of 25 ° C. for 2 hours. Thereafter, acetonitrile is removed using a vacuum evaporator and purified by column chromatography (silica gel), and the effluent containing the compound represented by the formula (aa2) is solvent-removed using a vacuum evaporator, yellow I got a crystal. The crystals were dried at 60 ° C. under reduced pressure to obtain 4.6 g of a compound represented by the formula (aa2) (a light selective absorption compound (2)) as a yellow powder. The yield was 56%.
When the gram absorbance coefficient is determined by the same method as described above, the value of ε (405) of the compound represented by formula (aa4) is 45 L / (g · cm), and the value of ε (420) is 2.1 L / (G · cm).
 <光学フィルムの作製>
[実施例1]光学フィルム(1)の作製
 セルローストリアセテート(アセチル置換度:2.87;富士フィルム和光純薬株式会社 商品名「三酢酸セルロース」)と、光選択吸収性化合物(1)(セルローストリアセテート100質量部に対して3質量部)、及び溶媒(メチレンクロライドとエタノールとの混合物、質量比87:13)とからなるセルロースアシレート溶液(固形分濃度:10質量%)をミキシングタンクに投入し、攪拌して各成分を溶解した。
得られた溶解物を、アプリケーターを用い、ガラス支持体に均一に流延し、40℃のオーブンで10分間乾燥させたあと、さらに80℃のオーブンで10分乾燥させた。乾燥後、ガラス支持体から光学フィルム(1)を剥離させ、光選択吸収能を有する光学フィルム(1)を得た。乾燥後の光学フィルム(1)の膜厚は30μmであった。
<Production of optical film>
Example 1 Preparation of Optical Film (1) Cellulose triacetate (Acetyl substitution degree: 2.87; Fuji Film Wako Pure Chemical Industries, Ltd., trade name “cellulose triacetate”), and a light selective absorption compound (1) (cellulose) A cellulose acylate solution (solid content concentration: 10% by mass) consisting of 3 parts by mass per 100 parts by mass of triacetate and a solvent (mixture of methylene chloride and ethanol, mass ratio 87: 13) is charged into a mixing tank The components were dissolved by stirring.
The obtained lysate was uniformly cast on a glass support using an applicator, dried in an oven at 40 ° C. for 10 minutes, and further dried in an oven at 80 ° C. for 10 minutes. After drying, the optical film (1) was peeled off from the glass support to obtain an optical film (1) having a light selective absorptivity. The thickness of the dried optical film (1) was 30 μm.
<貯蔵弾性率の測定>
 得られた光学フィルム(1)を5mm×30mmの大きさに裁断した。裁断された光選択吸収層(A-1)のその長辺が引張り方向となるように、アイティー計測制御(株)製の動的粘弾性測定装置「DVA-220」を用いてつかみ具の間隔2cmで把持し、引張りと収縮の周波数を10Hz、昇温速度を10℃/分に設定して、温度23℃~200℃における貯蔵弾性率E’を求めた。23℃における貯蔵弾性率E’は4100MPaであった。
<Measurement of storage modulus>
The obtained optical film (1) was cut into a size of 5 mm × 30 mm. Using a dynamic viscoelasticity measuring device “DVA-220” manufactured by IT Measurement & Control Co., Ltd., the long side of the cut light selective absorption layer (A-1) is in the tensile direction The storage elastic modulus E 'at a temperature of 23.degree. C. to 200.degree. C. was determined by holding at an interval of 2 cm, setting the frequency of tension and contraction to 10 Hz, and the temperature rising rate to 10.degree. C./min. The storage elastic modulus E ′ at 23 ° C. was 4100 MPa.
 [実施例2]光学フィルム(2)の作製
 セルローストリアセテート(アセチル置換度:2.87;富士フィルム和光純薬株式会社 商品名「三酢酸セルロース」)と、光選択吸収性化合物(2)(セルローストリアセテート100質量部に対して2質量部)、及び溶媒(メチレンクロライドとエタノールとの混合物、質量比90:10)とからなるセルロースアシレート溶液(固形分濃度:5質量%)をミキシングタンクに投入し、攪拌して各成分を溶解した。
 得られた溶解物を、アプリケーターを用い、ガラス支持体に均一に流延し、40℃のオーブンで10分間乾燥させたあと、さらに80℃のオーブンで10分乾燥させた。乾燥後、ガラス支持体から光学フィルム(2)を剥離させ、光選択吸収能を有する光学フィルム(2)を得た。乾燥後の光学フィルム(2)の膜厚は20μmであった。また、得られた光学フィルム(2)の貯蔵弾性率を上記と同様にして測定したところ、23℃における貯蔵弾性率E’は3800MPaであった。
Example 2 Preparation of Optical Film (2) Cellulose triacetate (Acetyl substitution degree: 2.87; Fuji Film Wako Pure Chemical Industries, Ltd., trade name "cellulose triacetate"), and a light selective absorption compound (2) (cellulose A cellulose acylate solution (solid content concentration: 5% by mass) consisting of 2 parts by mass per 100 parts by mass of triacetate and a solvent (mixture of methylene chloride and ethanol, mass ratio 90:10) is charged into a mixing tank The components were dissolved by stirring.
The obtained lysate was uniformly cast on a glass support using an applicator, dried in an oven at 40 ° C. for 10 minutes, and further dried in an oven at 80 ° C. for 10 minutes. After drying, the optical film (2) was peeled off from the glass support to obtain an optical film (2) having a light selective absorptivity. The thickness of the dried optical film (2) was 20 μm. Moreover, when the storage elastic modulus of the obtained optical film (2) was measured similarly to the above, storage elastic modulus E 'in 23 degreeC was 3800 Mpa.
 <(メタ)アクリル系樹脂の合成>
[合成例3]
 冷却管、窒素導入管、温度計及び攪拌機を備えた反応容器に、溶媒として酢酸エチル81.8部、単量体としてアクリル酸ブチル70.4部、アクリル酸メチル20.0部、およびアクリル酸2-フェノキシエチル8.0部、アクリル酸2-ヒドロキシエチル1.0部およびアクリル酸0.6部と混合して得られた溶液を仕込んだ。反応容器内の空気を窒素ガスで置換した後、内温を60℃にした。その後、アゾビスイソブチロニトリル0.12部を酢酸エチル10部に溶解させた溶液を添加した。1時間同温度で保持した後、内温を54~56℃に保ちながら、添加速度17.3部/Hrで酢酸エチルを、重合体の濃度がほぼ35%となるように反応容器内へ連続的に加えた。酢酸エチルの添加開始から12時間経過するまで内温を54~56℃に保持した後、酢酸エチルを加えて重合体の濃度が20%となるように調整して、(メタ)アクリル系樹脂の酢酸エチル溶液(1)を得た。(メタ)アクリル系樹脂の重量平均分子量Mwは139万、重量平均分子量Mwと数平均分子量Mnとの比Mw/Mnは5.32であった。
<Synthesis of (meth) acrylic resin>
Synthesis Example 3
In a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer and a stirrer, 81.8 parts of ethyl acetate as a solvent, 70.4 parts of butyl acrylate as a monomer, 20.0 parts of methyl acrylate, and acrylic acid A solution obtained by mixing 8.0 parts of 2-phenoxyethyl, 1.0 parts of 2-hydroxyethyl acrylate and 0.6 parts of acrylic acid was charged. After the air in the reaction vessel was replaced with nitrogen gas, the internal temperature was brought to 60.degree. Thereafter, a solution of 0.12 parts of azobisisobutyronitrile in 10 parts of ethyl acetate was added. After maintaining at the same temperature for 1 hour, while maintaining the internal temperature at 54 to 56 ° C., continuously add ethyl acetate at a rate of 17.3 parts / hr to the reaction vessel so that the concentration of the polymer is approximately 35%. Added. The internal temperature is kept at 54 to 56 ° C. until 12 hours have passed from the start of the addition of ethyl acetate, and then ethyl acetate is added to adjust the concentration of the polymer to 20%, and the (meth) acrylic resin An ethyl acetate solution (1) was obtained. The weight average molecular weight Mw of the (meth) acrylic resin was 1,390,000, and the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn was 5.32.
 なお、重量平均分子量および数平均分子量の測定は、GPC装置にカラムとして「TSK gel XL(東ソー(株)製)」を4本、および「Shodex GPC KF-802(昭和電工(株)製)」を1本、計5本を直列につないで配置し、溶出液としてテトラヒドロフランを用いて、試料濃度5mg/mL、試料導入量100μL、温度40℃、流速1mL/分の条件で行い、標準ポリスチレン換算により算出した。 In addition, the measurement of a weight average molecular weight and a number average molecular weight uses four "TSK gel XL (made by Tosoh Corp.)" as a column in a GPC apparatus, and "Shodex GPC KF-802 (made by Showa Denko KK)" 1 piece, 5 pieces in total are connected in series, and using tetrahydrofuran as an eluent, the sample concentration is 5 mg / mL, the sample introduction amount is 100 μL, the temperature is 40 ° C, and the flow rate is 1 mL / min. Calculated by
<(メタ)アクリル系樹脂粘着剤組成物(1)の合成>
〔製造例1〕
 上記で得られた(メタ)アクリル系樹脂の酢酸エチル溶液(1)(樹脂濃度:20%)に、該溶液の固形分100部に対して、架橋剤(コロネートL、固形分75%:東ソー(株式会社製)0.4部及びシラン化合物(信越化学工業製:KBM-403)0.4部を混合し、さらに固形分濃度が14%となるように酢酸エチルを添加して粘着剤組成物(1)を得た。なお、上記架橋剤の配合量は、有効成分としての質量部数である。
<Synthesis of (Meth) Acrylic Resin Adhesive Composition (1)>
Production Example 1
A cross-linking agent (Corronate L, solid content 75%: Tosoh) based on 100 parts of solid content of the solution obtained from the ethyl acetate solution (1) (resin concentration: 20%) of the (meth) acrylic resin obtained above 0.4 parts of (made by Co., Ltd.) and 0.4 parts of silane compound (made by Shin-Etsu Chemical Co., Ltd .: KBM-403) are mixed, and ethyl acetate is further added so that solid content concentration will be 14%, and adhesive composition In addition, the compounding quantity of the said crosslinking agent is a mass part as an active ingredient.
 製造例1で使用した架橋剤及びシラン化合物は以下の通りである。
 架橋剤:トリレンジイソシアネートのトリメチロールプロパンアダクト体の酢酸エチル溶液(固形分濃度75%)、東ソー株式会社から入手した商品名「コロネートL」。
 シラン化合物:3-グリシドキシプロピルトリメトキシシラン、信越化学工業株式会社から入手した商品名「KBM403」。
The crosslinking agent and silane compound used in Production Example 1 are as follows.
Crosslinking agent: Ethyl acetate solution (75% solid concentration) of trimethylolpropane adduct of tolylene diisocyanate, trade name "Corronate L" obtained from Tosoh Corporation.
Silane compound: 3-glycidoxypropyltrimethoxysilane, trade name "KBM403" obtained from Shin-Etsu Chemical Co., Ltd.
<粘着剤層の作製>
〔製造例2〕
製造例1で調製した粘着剤組成物(1)を、離型処理が施されたポリエチレンテレフタレートフィルムからなるセパレートフィルム〔リンテック(株)から入手した商品名「PLR-382190」〕の離型処理面に、アプリケーターを用いて乾燥後の厚みが20μmとなるように塗布し、100℃で1分間乾燥して粘着剤層(1)を作製した。
<Preparation of pressure-sensitive adhesive layer>
Production Example 2
The release treated surface of a separate film (trade name "PLR-382190" obtained from Lintec Co., Ltd.) consisting of a polyethylene terephthalate film subjected to release treatment, the pressure-sensitive adhesive composition (1) prepared in Production Example 1 The mixture was applied using an applicator so that the thickness after drying was 20 μm, and dried at 100 ° C. for 1 minute to prepare a pressure-sensitive adhesive layer (1).
 <(メタ)アクリル系粘着剤組成物(2)の合成>
〔製造例3〕
 合成例3で得られた(メタ)アクリル系樹脂の酢酸エチル溶液(1)(樹脂濃度:20%)に、該溶液の固形分100部に対して、架橋剤(コロネートL、固形分75%:東ソー製)0.4部、シラン化合物(信越化学工業製:KBM-403)0.4部、及び合成例1で合成した光選択吸収性化合物(1)2部を混合し、さらに固形分濃度が14%となるように酢酸エチルを添加して粘着剤組成物(2)を得た。なお、上記架橋剤(コロネートL)の配合量は、有効成分としての質量部数である。
<Synthesis of (meth) acrylic pressure-sensitive adhesive composition (2)>
Production Example 3
A crosslinking agent (CORONATE L, solid content 75%, based on 100 parts of solid content of the solution of (meth) acrylic resin obtained in Synthesis Example 3 in ethyl acetate solution (1) (resin concentration: 20%) : 0.4 parts of Tosoh Co., Ltd., 0.4 parts of silane compound (Shin-Etsu Chemical Co., Ltd .: KBM-403), and 2 parts of the photoselective absorptive compound (1) synthesized in Synthesis Example 1 are further mixed, Ethyl acetate was added to a concentration of 14% to obtain a pressure-sensitive adhesive composition (2). In addition, the compounding quantity of the said crosslinking agent (coronate L) is a mass part as an active ingredient.
<粘着剤層(2)の作製>
 上記で調製した粘着剤組成物(2)を、離型処理が施されたポリエチレンテレフタレートフィルムからなるセパレートフィルム〔リンテック(株)から入手した商品名「PLR-382190」〕の離型処理面に、アプリケーターを用いて乾燥後の厚みが20μmとなるように塗布し、100℃で1分間乾燥して粘着剤層(2)を作製した。
<Preparation of pressure-sensitive adhesive layer (2)>
The pressure-sensitive adhesive composition (2) prepared above was applied to the release-treated surface of a separate film (trade name “PLR-382190” obtained from Lintec Co., Ltd.) made of a polyethylene terephthalate film subjected to release treatment. It applied so that the thickness after drying might be set to 20 micrometers using an applicator, and it dried at 100 degreeC for 1 minute, and produced the adhesive layer (2).
<(メタ)アクリル系粘着剤組成物(3)の合成>
〔製造例4〕
 光選択吸収化合物を、光選択吸収化合物(2)に代えた以外は、合成例6と同様にして粘着剤組成物(3)を得た。
 得られた粘着剤組成物(3)を、離型処理が施されたポリエチレンテレフタレートフィルムからなるセパレートフィルム〔リンテック(株)から入手した商品名「PLR-382190」〕の離型処理面に、アプリケーターを用いて乾燥後の厚みが20μmとなるように塗布し、100℃で1分間乾燥して粘着剤層(3)を作製した。
<Synthesis of (meth) acrylic pressure-sensitive adhesive composition (3)>
Production Example 4
A pressure-sensitive adhesive composition (3) was obtained in the same manner as in Synthesis Example 6, except that the photoselective absorption compound was replaced with the photoselective absorption compound (2).
The adhesive composition (3) thus obtained was applied to the release-treated surface of a separate film (trade name "PLR-382190" obtained from Lintec Co., Ltd.) made of a polyethylene terephthalate film subjected to release treatment. It applied so that the thickness after drying might be set to 20 micrometers, and it dried at 100 degreeC for 1 minute, and produced the adhesive layer (3).
<評価>
(実施例3)
 実施例1で得た光学フィルム(1)の片面にコロナ放電処理を施した後、製造例1で製造したアクリル系粘着剤をラミネーターにより貼り合わせた後、温度23℃、相対湿度65%の条件で7日間養生し、粘着剤付き光学フィルムを得た。次いで、粘着剤つき付光学フィルムを30mm×30mmの大きさに裁断し、無アルカリガラス〔コーニング社製の商品名“EAGLE XG”〕に貼合し、サンプルを作製した。作成したサンプルの波長300~800nm範囲の吸光度を、分光光度計(UV-2450:株式会社島津製作所製)を用いて測定した。測定後のサンプルを、耐候性試験機(サンシャインウェザーメーター:スガ試験機株式会社製)に投入し、24時間の耐候性試験を実施した後、取り出したサンプルの吸光度を再度測定した。測定した吸光度から、下記式に基づき、405nmにおけるサンプルの吸光度保持率を求めた。結果を表1に示す。吸光度保持率が100に近い値ほど、光選択吸収機能の劣化がなく良好な耐候性を示す。なお、波長405nm及び波長440nmにおける無アルカリガラスの吸収は、ほぼ0である。
吸光度保持率=耐久試験後のA(405) / 耐久試験前のA(405)×100
<Evaluation>
(Example 3)
After corona discharge treatment is applied to one side of the optical film (1) obtained in Example 1, the acrylic pressure-sensitive adhesive produced in Production Example 1 is bonded by a laminator, and the conditions of temperature 23 ° C. and relative humidity 65% It was aged for 7 days to obtain an adhesive-coated optical film. Subsequently, the pressure-sensitive adhesive-attached optical film was cut into a size of 30 mm × 30 mm, and was bonded to non-alkali glass (trade name “EAGLE XG” manufactured by Corning Co., Ltd.) to prepare a sample. The absorbance of the prepared sample in the wavelength range of 300 to 800 nm was measured using a spectrophotometer (UV-2450: manufactured by Shimadzu Corporation). The sample after measurement was put into a weather resistance tester (Sunshine Weather Meter: manufactured by Suga Test Instruments Co., Ltd.), and after performing a 24 hour weather resistance test, the absorbance of the taken out sample was measured again. From the measured absorbance, the absorbance retention of the sample at 405 nm was determined based on the following equation. The results are shown in Table 1. As the absorbance retention rate approaches 100, there is no deterioration in the light selective absorption function and the better the weather resistance. The absorption of the alkali-free glass at a wavelength of 405 nm and a wavelength of 440 nm is approximately zero.
Absorbance retention rate = A (405) after endurance test / A (405) before endurance test x 100
(実施例4)
 光学フィルムを実施例2で得た光学フィルム(2)に代えた以外は、実施例3と同様にして光学フィルム(2)の評価を行った。結果を表1に示す。
(Example 4)
The optical film (2) was evaluated in the same manner as in Example 3 except that the optical film was replaced with the optical film (2) obtained in Example 2. The results are shown in Table 1.
<比較例1>
 厚さ40μmのトリアセチルセルロースフィルム(コニカから入手した商品名“KC4CW”)の片面にコロナ放電処理を施した後、粘着剤層(2)をラミネーターにより貼り合わせたこと以外は、実施例3と同様にして評価を行った。
Comparative Example 1
Example 3 was repeated except that one surface of a 40 μm thick triacetyl cellulose film (trade name "KC4CW" obtained from Konica) was subjected to corona discharge treatment, and then the pressure-sensitive adhesive layer (2) was laminated by a laminator. Evaluation was performed in the same manner.
<比較例2>
 厚さ40μmのトリアセチルセルロースフィルム(コニカから入手した商品名“KC4CW”)の片面にコロナ放電処理を施した後、粘着剤層(3)をラミネーターにより貼り合わせたこと以外は、実施例3と同様にして評価を行った。
Comparative Example 2
A corona discharge treatment was applied to one side of a 40 μm thick triacetyl cellulose film (trade name "KC4CW" obtained from Konica), and then Example 3 and Example 3 were repeated except that the pressure-sensitive adhesive layer (3) was laminated by a laminator. Evaluation was performed in the same manner.
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
 本発明の光学フィルムは、波長405nm付近の光吸収能(A(405))の値が2.0以上と良好である。そのため、本発明の光学フィルムを位相差フィルムや有機EL素子に積層すると、本発明の光学フィルムが位相差フィルムや有機EL素子に対する波長405nm付近の短波長の可視光を遮ることができ、短波長の可視光から位相差フィルムや有機EL素子の劣化抑制機能を有する。さらに、本発明の光学フィルムは耐候性試験後であっても波長405nm付近の光吸収機能が良好であり、良好な耐候性(耐久性)を有する。また、本発明の光学フィルムは、波長440nm付近における光吸収性能が低く、液晶表示装置の発光を阻害せず、良好な色彩表現をすることが可能である。 The optical film of the present invention has a good light absorption capacity (A (405)) in the vicinity of a wavelength of 405 nm of 2.0 or more. Therefore, when the optical film of the present invention is laminated on a retardation film or an organic EL element, the optical film of the present invention can block visible light of a short wavelength near 405 nm with respect to the retardation film or the organic EL element. Have a function of suppressing deterioration of a retardation film or an organic EL element from visible light of Furthermore, the optical film of the present invention has a good light absorbing function near a wavelength of 405 nm even after a weathering test, and has a good weathering resistance (durability). In addition, the optical film of the present invention has a low light absorption performance near a wavelength of 440 nm, and can provide a good color expression without inhibiting the light emission of the liquid crystal display device.
  本発明の光学フィルムは、液晶パネル及び液晶表示装置に好適に用いられる。 The optical film of the present invention is suitably used in liquid crystal panels and liquid crystal displays.
 1   本発明の光学フィルム
 2   粘着剤層
 3   セパレートフィルム
 4   保護フィルム
 5   接着剤層
 6   偏光フィルム
 7、7a   粘着剤層
 8   保護フィルム
 30  発光素子
 40  光学フィルム
 50、50a   1/4波長位相差層
 60   接着剤層
 70   1/2波長位相差層
 80   ポジティブC層
 10  粘着剤層付光学フィルム
 10A、10B、10C、10D   光学積層体
DESCRIPTION OF SYMBOLS 1 optical film of this invention 2 adhesive layer 3 separate film 4 protective film 5 adhesive layer 6 polarizing film 7 and 7a adhesive layer 8 protective film 30 light emitting element 40 optical film 50, 50 a 1⁄4 wavelength retardation layer 60 adhesion Agent layer 70 1/2 wavelength retardation layer 80 positive C layer 10 optical film with adhesive layer 10A, 10B, 10C, 10D optical laminate

Claims (10)

  1.  樹脂(A)及び光選択吸収化合物(B)を含む樹脂組成物から形成される光学フィルムであって、
    樹脂(A)は、セルロース系樹脂、(メタ)アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリイミド系樹脂及びシクロオレフィン系樹脂からなる群から選ばれる少なくとも1種の樹脂であり、
    下記式(1)を満たすことを特徴とする光学フィルム。
       A(405)≧0.5      (1)
    [式(1)中、A(405)は波長405nmにおける吸光度を表す。]
    An optical film formed from a resin composition containing a resin (A) and a photoselective absorption compound (B),
    The resin (A) is at least one resin selected from the group consisting of cellulose resins, (meth) acrylic resins, polyester resins, polyamide resins, polyimide resins and cycloolefin resins,
    An optical film characterized by satisfying the following formula (1).
    A (405) 0.5 0.5 (1)
    [In Formula (1), A (405) represents the absorbance at a wavelength of 405 nm. ]
  2.  下記式(2)を満たす請求項1に記載の光学フィルム。
      A(440)≦0.1       (2)
    [式(2)中、A(440)は波長440nmにおける吸光度を表す。]
    The optical film of Claim 1 which satisfy | fills following formula (2).
    A (440) ≦ 0.1 (2)
    [In Formula (2), A (440) represents the light absorbency in wavelength 440nm. ]
  3.  さらに、下記式(3)を満たす請求項1又は2に記載の光学フィルム。
       A(405)/A(440)≧5      (3)
    [式(3)中、A(405)は波長405nmにおける吸光度を表し、A(440)は波長440nmにおける吸光度を表す。]
    Furthermore, the optical film of Claim 1 or 2 which satisfy | fills following formula (3).
    A (405) / A (440) ≧ 5 (3)
    [In Formula (3), A (405) represents the absorbance at a wavelength of 405 nm, and A (440) represents the absorbance at a wavelength of 440 nm. ]
  4.  23℃における貯蔵弾性率Eが、100MPa以上である請求項1~3のいずれかに記載の光学フィルム。 The optical film according to any one of claims 1 to 3, wherein the storage elastic modulus E at 23 ° C is 100 MPa or more.
  5.  光選択吸収化合物(B)の含有量が、樹脂(A)100質量部に対して、0.01~20質量部である請求項1~4のいずれかに記載の光学フィルム。 The optical film according to any one of claims 1 to 4, wherein the content of the light selective absorption compound (B) is 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin (A).
  6.  光選択吸収化合物(B)が、式(4)を満たす化合物である請求項1~5に記載の光学フィルム。
     ε(405)≧20  (4)
    〔式(5)中、ε(405)は波長405nmにおける化合物のグラム吸光係数を表す。グラム吸光係数の単位はL/(g・cm)である。〕
    The optical film according to any one of claims 1 to 5, wherein the photoselective absorption compound (B) is a compound satisfying the formula (4).
    ε (405) 20 20 (4)
    [In Formula (5), (epsilon) (405) represents the gram absorption coefficient of the compound in wavelength 405 nm. The unit of gram absorption coefficient is L / (g · cm). ]
  7.  光選択吸収化合物(B)は、式(5)を満たす化合物である請求項6に記載の光学フィルム。
    ε(405)/ε(440)≧20      (5)
    [式(6)中、ε(405)は波長405nmにおける化合物のグラム吸光係数を表し、ε(440)は波長440nmにおけるグラム吸光度係数を表す。]
    The optical film according to claim 6, wherein the photoselective absorption compound (B) is a compound satisfying the formula (5).
    ε (405) / ε (440) ≧ 20 (5)
    [In Formula (6), (epsilon) (405) represents the gram absorption coefficient of the compound in wavelength 405 nm, and (epsilon) (440) represents the gram absorption coefficient in wavelength 440 nm. ]
  8.  光選択吸収化合物(B)が、分子内にメロシアニン構造を有する化合物である請求項1~7に記載の光学フィルム。 The optical film according to any one of claims 1 to 7, wherein the photoselective absorption compound (B) is a compound having a merocyanine structure in the molecule.
  9.  請求項1~8のいずれかに記載の光学フィルムの少なくとも一方の面に、粘着剤層を有する粘着剤付き光学フィルム。 An adhesive-coated optical film having an adhesive layer on at least one surface of the optical film according to any one of claims 1 to 8.
  10.  請求項9に記載の粘着剤付き光学フィルムを有する表示装置。 The display apparatus which has an optical film with an adhesive of Claim 9.
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