WO2019004043A1 - 粘着剤シート及び粘着剤層付フィルム - Google Patents

粘着剤シート及び粘着剤層付フィルム Download PDF

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WO2019004043A1
WO2019004043A1 PCT/JP2018/023584 JP2018023584W WO2019004043A1 WO 2019004043 A1 WO2019004043 A1 WO 2019004043A1 JP 2018023584 W JP2018023584 W JP 2018023584W WO 2019004043 A1 WO2019004043 A1 WO 2019004043A1
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meth
group
sensitive adhesive
pressure
film
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PCT/JP2018/023584
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English (en)
French (fr)
Japanese (ja)
Inventor
智恵 阪上
亜依 小橋
悠司 淺津
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住友化学株式会社
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Priority to KR1020197038008A priority Critical patent/KR20200024780A/ko
Priority to KR1020237025309A priority patent/KR20230113849A/ko
Priority to CN201880042798.2A priority patent/CN110799611A/zh
Publication of WO2019004043A1 publication Critical patent/WO2019004043A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

  • the present invention relates to a pressure-sensitive adhesive sheet and a film with a pressure-sensitive adhesive layer using the pressure-sensitive adhesive sheet.
  • Patent Document 1 describes a polarizing plate in which an ultraviolet light absorber excellent in ultraviolet light absorbing performance in a wavelength range of 370 nm or less is added to a protective film of the polarizing plate.
  • the present invention exhibits a high absorption selectivity to ultraviolet light and visible light of a short wavelength near a wavelength of 405 nm, thereby having a good suppression function for deterioration of the retardation film or the organic EL light emitting device due to ultraviolet light or short light of a short wavelength. It is providing a pressure sensitive adhesive sheet.
  • a pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing a (meth) acrylic resin (A) and a light selective absorption compound, and the pressure-sensitive adhesive sheet satisfying the following formulas (1) and (2).
  • a (405) 0.5 0.5 (2) [In Formula (1), A (350) represents the light absorbency in wavelength 350 nm. In Formula (2), A (405) represents the absorbance at a wavelength of 405 nm.
  • a (440) ⁇ 0.1 (3) [In Formula (3), A (440) represents the absorbance at a wavelength of 440 nm.
  • ⁇ (405) 20 20 (5) [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). ] [6] The pressure-sensitive adhesive sheet according to [5], wherein the compound which selectively absorbs light of wavelength 405 nm is a compound satisfying the formula (6). ⁇ (405) / ⁇ (440) ⁇ 20 (6) [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 pressure-sensitive adhesive sheet of the present invention exhibits a high absorption selectivity to ultraviolet light and visible light with 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 ultraviolet light.
  • the pressure-sensitive adhesive sheet of the present invention exhibits high absorption selectivity to visible light having a short wavelength near 405 nm even after the weathering test, and can suppress deterioration due to ultraviolet light or visible light having a short wavelength. It can.
  • good display characteristics and durability can be provided.
  • An example of the laminated constitution of the adhesive sheet of this invention is shown.
  • An example of the laminated constitution of the optical laminated body containing the adhesive sheet of this invention is shown.
  • An example of the laminated constitution of the optical laminated body containing the adhesive sheet of this invention is shown.
  • An example of the laminated constitution of the optical laminated body containing the adhesive sheet of this invention is shown.
  • the pressure-sensitive adhesive sheet of the present invention is molded from a pressure-sensitive adhesive composition containing a (meth) acrylic resin (A) and a light selective absorption compound, and satisfies the following formulas (1) and (2).
  • a (350) 0.5 0.5 (1)
  • a (405) 0.5 0.5 (2)
  • a (350) represents the light absorbency in wavelength 350 nm.
  • a (405) represents the absorbance at a wavelength of 405 nm. ]
  • the value of A (350) is less than 0.5, the absorption at a wavelength of 350 nm is low, and the effect of suppressing deterioration of a display device such as a retardation film or an organic EL element in ultraviolet light is small.
  • the value of A (350) is preferably 0.5 or more, more preferably 0.8 or more, and particularly preferably 1.0 or more.
  • the value of A (405) is less than 0.5, the absorption at a wavelength of 405 nm is low, and the effect of suppressing deterioration of a retardation film or visible light of short wavelength visible light such as an organic EL element is small.
  • the value of A (405) is preferably 0.6 or more, more preferably 0.8 or more, and particularly preferably 1.0 or more.
  • the upper limit is not particularly limited, but is usually 10 or less.
  • the pressure-sensitive adhesive sheet of the present invention preferably further satisfies either of the following formulas (3) and (4), and more preferably both of the following formulas (3) and (4).
  • a (440) ⁇ 0.1 (3) [In Formula (3), A (440) represents the absorbance at a wavelength of 440 nm. ]
  • a (405) / A (440) ⁇ 5 (4) [In Formula (4), A (405) represents the light absorbency in wavelength 405 nm, and A (440) represents the light absorbency in wavelength 440 nm. ]
  • the value of A (440) exceeds 0.1, there is a tendency to impair good color expression in the display device. In addition, the luminance is also reduced because the light emission of the display device is inhibited.
  • 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 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 value of A (405) / A (440) is preferably 10 or more, more preferably 30 or more, and particularly preferably 60 or more.
  • the pressure-sensitive adhesive layer of the present invention is formed from a pressure-sensitive adhesive composition containing at least a (meth) acrylic resin and a light selective absorption compound.
  • the pressure-sensitive adhesive composition preferably further contains a crosslinking agent.
  • the light selective absorption compound is not particularly limited as long as it is a compound that selectively absorbs light of wavelength 350 nm or light of wavelength 405 nm.
  • the light selective absorption compound preferably contains a compound that selectively absorbs light of wavelength 350 nm and a compound that selectively absorbs light of wavelength 405 nm.
  • Examples of the compound that selectively absorbs light having a wavelength of 350 nm include an ultraviolet absorber.
  • the UV absorber is not particularly limited, but, for example, oxybenzophenone based UV absorber, benzotriazole based UV absorber, salicylic acid ester based UV absorber, benzophenone based UV absorber, cyanoacrylate based UV absorber, triazine based UV absorber And organic UV absorbers such as agents.
  • the UV absorber may be a commercially available product.
  • a triazine-based UV absorber “Kemisorb 102” manufactured by Chemi-Pro Chemical Co., Ltd., “ADEKA STAB LA 46” made by ADEKA CORPORATION, “ADEKA STAB LAF 70”, BASF Japan "Tinuvin 109", “Tinubin 171", “Tinubin 234", “Tinubin 327", “Tinubin 328", “Tinubin 928", “Tinubin 400", “Tinubin 460", “Tinubin” 405 “,” tinuvin 477 “and the like.
  • the ultraviolet absorber may be an inorganic ultraviolet absorber.
  • inorganic ultraviolet absorbers include titanium oxide, zinc oxide, indium oxide, tin oxide, talc, kaolin, calcium carbonate, titanium oxide composite oxide, zinc oxide composite oxide, ITO (tin-doped indium oxide), ATO (Antimony-doped tin oxide) and the like.
  • titanium oxide-based composite oxides include silica, zinc oxide doped with alumina, and the like.
  • the compound capable of selectively absorbing light having a wavelength of 405 nm (hereinafter sometimes referred to as a light selective absorption compound (B)) is preferably a compound satisfying the following formula (5), and further, the following formula (6) It is more preferable that the compound satisfies ⁇ (405) 20 20 (5) [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).
  • (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.
  • ⁇ (405) The larger the value of ⁇ (405), the easier it is to absorb light with a wavelength of 405 nm, and the deterioration of the retardation film in ultraviolet light or visible light with a short wavelength is suppressed. If the value of ⁇ (405) is less than 20 L / (g ⁇ cm), the content of the light selective absorption compound (B) in the pressure-sensitive adhesive composition is not increased, the ultraviolet light of the retardation film or the organic EL light emitting element And it tends to be difficult to express the function of suppressing deterioration by visible light of short wavelength. 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.
  • ⁇ (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 compound which selectively absorbs light of wavelength 405 nm 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 Group A above. 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 total content of the light selective absorption compound is usually 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, more preferably 100 parts by mass of the (meth) acrylic resin.
  • the amount is 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass.
  • the mass ratio of the photoselective absorption compound (A) to the photoselective absorption compound (B) (photoselective absorption compound (A) / photoselective absorption compound (B)) is usually 0.05 to 20, preferably 0 .1 to 10.
  • the (meth) acrylic resin (A) is preferably a polymer having a constituent unit derived from (meth) acrylic acid ester as a main component (preferably containing 50% by mass or more).
  • 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) is a structural unit derived from an acrylic acid alkyl ester (a1) having a homopolymer glass transition temperature Tg of less than 0 ° C., and an alkyl acrylate having a homopolymer Tg of 0 ° C. or more. It is preferable to contain the structural unit derived from 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.
  • acrylic acid alkyl ester (a1) examples include ethyl acrylate, n- and i-propyl acrylate, n- and i-butyl acrylate, n-pentyl acrylate, n- and i-hexyl acrylate , N-heptyl acrylate, n- and i-octyl acrylate, 2-ethylhexyl acrylate, n- and i-nonyl acrylate, n- and i-decyl acrylate, and n-dodecyl acrylate alkyl
  • acrylic acid alkyl esters having about 2 to 12 carbon atoms.
  • acrylic acid alkyl ester (a1) only one type may be used, or two or more types may be used in combination. Among them, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate and the like are preferable from the viewpoint of followability and rework when the pressure-sensitive adhesive sheet of the present invention is laminated on an optical film.
  • Acrylic acid alkyl ester (a2) is an (acrylic acid alkyl ester) other than acrylic acid alkyl ester (a1)
  • Specific examples of acrylic acid alkyl ester (a2) include methyl acrylate, cyclohexyl acrylate, isoboronyl acrylate, Examples include stearyl acrylate, t-butyl acrylate and the like.
  • the acrylic acid alkyl ester (a2) only one type may be used, or two or more types may be used in combination. Among them, from the viewpoint of high temperature durability, the 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.
  • the (meth) acrylic resin (A) substantially contains a structural unit derived from a monomer having an amino group from the viewpoint of preventing the peel force enhancement of the separate film that can be laminated on the outer surface of the pressure-sensitive adhesive sheet. Preferably not.
  • “not substantially contained” means that it is 0.1 parts by mass or less in 100 parts by mass 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
  • the structural unit derived from the monomer which has group, the structural unit derived from a (meth) acrylamide type monomer, etc. are also mentioned.
  • 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 sheet in a high-temperature environment is improved, and defects such as floating peeling between an adherend and the pressure-sensitive adhesive sheet and cohesive failure of the pressure-sensitive adhesive sheet It is easy to control. It is advantageous from the viewpoint of coatability that a weight average molecular weight is 2.5 million or less.
  • 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 sheet and the coatability of the pressure-sensitive adhesive composition.
  • 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, and 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 to-be-adhered body base material of an adhesive sheet that Tg is below an upper limit, and it is advantageous for the durable improvement of an adhesive sheet 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 (A).
  • 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 crosslinking agent (B) reacts with a polar functional group (for example, a hydroxy group, an amino group, a carboxyl group, a heterocyclic group, etc.) in the (meth) acrylic resin (A).
  • a polar functional group for example, a hydroxy group, an amino group, a carboxyl group, a heterocyclic group, etc.
  • 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, etc.
  • 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 mass.
  • the pressure-sensitive adhesive composition of the present invention may further contain a silane compound (d).
  • a silane compound (d) for example, 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
  • 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 pressure-sensitive adhesive composition contains a silane compound represented by the following formula (d1), the adhesion to a substrate, glass, transparent electrode or the like can be further improved, so that it is hard to generate floating peeling or foaming under high temperature environment.
  • a durable pressure-sensitive adhesive layer can be formed.
  • 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 -CH 2- 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.
  • R d8 , R d9 , R d10 , R d11 and R d12 each independently represent an alkyl group having 1 to 5 carbon atoms as exemplified for the aforementioned R 21 , 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.
  • 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 mass, preferably 0.03 to 5 parts by mass, per 100 parts by mass of the (meth) acrylic resin (a).
  • the amount is preferably 0.05 to 2 parts by mass, and more preferably 0.1 to 1 parts by mass. It is advantageous for suppression of bleed-out of the silane compound (d) from the pressure-sensitive adhesive layer if it is not more than the above upper limit value, and adhesion between the pressure-sensitive adhesive layer and the metal layer, glass substrate, etc. 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.
  • the pressure-sensitive adhesive composition is dissolved or dispersed in a solvent to form a solvent-containing pressure-sensitive adhesive composition, which is then applied to the surface of a substrate and dried to form Be done.
  • the pressure-sensitive adhesive layer-attached optical film has a method of laminating the optical film on the pressure-sensitive adhesive sheet surface of the formed pressure-sensitive adhesive sheet-attached substrate and then peeling off the substrate, and an adhesive composition on a resin film such as an optical film. The method of apply
  • a plastic film is suitable, and specifically, a release film to which a release treatment has been applied can be mentioned.
  • a release film there may be mentioned one in which a release treatment such as silicone treatment is applied to one surface of a film made of a resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate or polyarylate.
  • a release film may be attached to the pressure-sensitive adhesive layer sheet for temporary protection of the pressure-sensitive adhesive sheet.
  • FIG. 1 shows an example of the layer configuration of the pressure-sensitive adhesive sheet of the present invention.
  • the pressure-sensitive adhesive sheet 1 shown in FIG. 1 is in a state in which a release film 2 is attached for temporary protection.
  • the release film may be laminated on one side of the pressure-sensitive adhesive sheet, or may be laminated on both sides.
  • stacked on the at least one surface of the adhesive layer of this invention is also included in this invention.
  • An optical laminate including the pressure-sensitive adhesive sheet of the present invention is shown in FIGS.
  • the optical laminate 10A described in FIG. 2 is an optical laminate including a protective form 8, an adhesive layer 7, a polarizing film 9, an adhesive layer 7, a protective film 3, an adhesive sheet 1, and a release film 2.
  • the protective film 3 may have a retardation.
  • the layer configuration of the protective form 8, the adhesive layer 7, the polarizing film 9, the adhesive layer 7, and the protective film 3 corresponds to a polarizing plate represented by an optical film 40.
  • the optical laminate 10B described in FIG. 3 and the optical laminate 10C described in FIG. 4 have a protective form 8, an adhesive layer 7, a polarizing film 9, an adhesive layer 7, a protective film 3, an adhesive sheet 1, an optical film.
  • 40 is an optical laminate including the pressure-sensitive adhesive layer 7 a and the light emitting element 30 (liquid crystal cell, OLED cell), and the optical film 40 is an optical film having a multilayer structure.
  • the optical film 40 is a film having an optical function of transmitting, reflecting, absorbing, etc. a light beam, and may be a single layer film or a multilayer film.
  • Examples of the optical film 40 include a polarizing film (polarizing plate), a retardation film, a brightness enhancement film, an antiglare film, an antireflective film, a diffusion film, a light collecting film, a window film, etc.
  • 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 oriented) sold from liquid crystal film
  • WV film sold by Fuji Film Co., Ltd.
  • VAC film (trade name: film in which disk-like liquid crystals are obliquely oriented)
  • VAC film (trade name: film in which disk-like liquid crystals are obliquely oriented)
  • new VAC film (trade name: film of biaxial orientation type), 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 (trade name) sold by Fuji Film Co., Ltd.
  • Zero-tac registered trademark sold by Konica Minolta Co., Ltd.
  • Zeon Neippon Zeon Co., Ltd.
  • ZF-14 trade name
  • 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 thickness of the retardation film is usually 0.1 to 100 ⁇ m.
  • the total thickness may be 0.5 to 200 ⁇ m.
  • 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.
  • stacked optical film 40 is mentioned.
  • a configuration including a hydrophilic film 40 in which the 1 ⁇ 4 wavelength retardation layer 50 a and the positive C layer 80 are laminated via an adhesive layer or a pressure-sensitive adhesive layer can also be mentioned.
  • the first wavelength retardation layer 50 for giving a phase difference of 1 ⁇ 4 wavelength shown in FIG. 3 and the 1 ⁇ 2 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. 3, it is more preferable that at least one of them is the fifth form.
  • the 1 ⁇ 4 wavelength retardation layer 50 a is preferably the optical film of the first embodiment, and it is more preferable to satisfy the formulas (7) and (8).
  • a polarizing film is a film that 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,
  • a film in which a dichroic dye is adsorbed and oriented to a polyvinyl 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 polarizer 2 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 of the pressure-sensitive adhesive layer-carrying optical film 1.
  • 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.
  • thermoplastic resin As the base film, a film made of the same thermoplastic resin as the thermoplastic resin can be used, and preferably, polyester resins such as polyethylene terephthalate, polycarbonate resins, cellulose resins such as triacetyl cellulose, norbornene resins It is a film made of cyclic polyolefin resin such as resin, polystyrene resin and the like.
  • polyester resins such as polyethylene terephthalate, polycarbonate resins, cellulose resins such as triacetyl cellulose, norbornene resins
  • cyclic polyolefin resin such as resin, polystyrene resin and the like.
  • 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 adhesive layer formed from the water-based adhesive is usually 0.001 to 5 ⁇ m.
  • 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 adhesive layer formed from the active energy ray-curable adhesive is usually 0.1 to 20 ⁇ m.
  • 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 the 1 ⁇ 4 wavelength layer having reverse wavelength dispersion described above are laminated.
  • 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.
  • a 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 of Unexamined-Japanese-Patent No. 2017-94488, etc. are mentioned, for example.
  • the optical laminate including the pressure-sensitive adhesive layer sheet of the present invention is laminated on a display element such as an organic EL element or a liquid crystal cell and used in a display device such as an organic EL display or a liquid crystal display (FPD: flat panel display) I can do things.
  • a display element such as an organic EL element or a liquid crystal cell
  • FPD liquid crystal display
  • GPC gel permeation chromatography
  • TSK gel XL made by Tosoh Co., Ltd.
  • Shodex GPC KF-802 made by Showa Denko Co., Ltd.
  • the sample concentration was 5 mg / mL
  • the sample introduction amount was 100 ⁇ L
  • the temperature was 40 ° C.
  • the flow rate was 1 mL / min.
  • Synthesis Example 1 Synthesis of Photoselective Absorbent Compound (1)
  • ⁇ 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 obtained solution (0.006 g / L) is put in a 1 cm quartz cell, and the quartz cell is set in a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation), and a wavelength of 1 nm step 300 to 800 nm by double beam method. Absorbance was measured in the range. 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 [Wherein, ⁇ ( ⁇ ) 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, and L is It represents the optical path length cm of the quartz cell.
  • Synthesis Example 2 Synthesis of Photoselective Absorbent Compound (2) 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, 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 the mixture was stirred with a magnetic stirrer.
  • acetic anhydride (Wako Pure Chemical Industries, Ltd. 3.6 g
  • 2-butyloctyl cyanoacetate manufactured by Tokyo Chemical Industry Co., Ltd.
  • 60 g of acetonitrile manufactured by Wako Pure Chemical Industries, Ltd.
  • the value of ⁇ (405) of the compound represented by formula (aa2) is 45 L / (g ⁇ cm), and the value of ⁇ (420) is 2.1 L / (G ⁇ cm).
  • the measurement of a weight average molecular weight and a number average molecular weight can use four "TSK gel XL (made by Tosoh Corp.)” and "Shodex GPC KF-802 (made by Showa Denko KK)" as columns in a GPC apparatus.
  • This series is arranged by connecting a total of 5 in series, using tetrahydrofuran as an eluent, using a sample concentration of 5 mg / mL, a sample introduction amount of 100 ⁇ L, a temperature of 40 ° C., and a flow rate of 1 mL / min. did.
  • Synthesis Example 4 Synthesis of Pressure-Sensitive Adhesive Composition (1) Relative to 100 parts of solid content of an ethyl acetate solution (1) (resin concentration: 20%) of the (meth) acrylic resin obtained in Synthesis Example 3. 0.4 parts of a crosslinking agent, 0.4 parts of a silane compound, 2 parts of the photoselective absorptive compound (1) synthesized in Synthesis Example 1 and 2.0 parts of Smithsorb 350 (manufactured by Sumika Chemtex Co., Ltd.) Ethyl acetate was added to a solid content concentration of 14% to obtain a pressure-sensitive adhesive composition (1).
  • the compounding quantity of the said crosslinking agent is a weight part number as an active ingredient.
  • 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.
  • Synthesis Example 5 Synthesis of Pressure-Sensitive Adhesive Composition (2) 2.0 parts of the photoselective absorption compound (2) obtained in Synthesis Example 2 and 2-hydroxy-4-methoxybenzophenone (Tokyo) A pressure-sensitive adhesive composition (2) was obtained in the same manner as in Synthesis Example 4 except that 1.0 part of Chemical Industries, Ltd. was used).
  • Synthesis Example 6 Synthesis of Pressure-Sensitive Adhesive Composition (3)
  • the photoselective absorptivity compound was selected from the photoselective absorption compound (2) obtained in Synthesis Example 2 and EST-5 (Sumitomo Seika Co., Ltd.) 1.0.
  • a pressure-sensitive adhesive composition (3) was obtained in the same manner as in Synthesis Example 4 except that parts were replaced.
  • Synthesis Example 7 Synthesis of Pressure-Sensitive Adhesive Composition (4) Synthesis Example 4 except that the photoselective absorption compound is only 2 parts of the photoselective absorption compound (1) obtained in Synthesis Example 1 and the Sumithorp 350 is not mixed.
  • a (meth) acrylic resin pressure-sensitive adhesive composition (7) was obtained in the same manner as in the above.
  • Synthesis Example 8 Synthesis of Pressure-Sensitive Adhesive Composition (5) Synthesis Example 4 except that the photoselective absorption compound is only 2 parts of the photoselective absorption compound (2) obtained in Synthesis Example 2 and the Sumithorp 350 is not overturned.
  • a (meth) acrylic resin pressure-sensitive adhesive composition (5) was obtained in the same manner as in the above.
  • Example 1 Preparation of Pressure-Sensitive Adhesive Sheet (1) A separate film consisting of a polyethylene terephthalate film to which a release treatment was applied, of the obtained pressure-sensitive adhesive composition (1) [trade name “PLR obtained from Lintec Co., Ltd. It applied so that the thickness after drying might be set to 15 micrometers using an applicator, and it dried at 100 degreeC for 1 minute, and the adhesive layer (1) was produced on the mold release treatment surface of -382190 ''.
  • the obtained pressure-sensitive adhesive layer (1) was bonded to a 23 ⁇ m cycloolefin film by a laminator, and then aged for 7 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a pressure-sensitive adhesive sheet (1).
  • Example 2 Preparation of Pressure-Sensitive Adhesive Sheet (2) A pressure-sensitive adhesive sheet (2) was prepared in the same manner as Example 1, except that the pressure-sensitive adhesive composition was replaced with the pressure-sensitive adhesive composition (2) obtained in Synthesis Example 5. Got).
  • Example 3 Preparation of Pressure-Sensitive Adhesive Sheet (3) A pressure-sensitive adhesive sheet (3) was prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive composition was replaced with the pressure-sensitive adhesive composition (3) obtained in Synthesis Example 6. Got).
  • a transparent protective film consisting of a 25 ⁇ m-thick triacetyl cellulose film (sometimes called “KC2UA” manufactured by Konica Minolta Opto Co., Ltd., hereinafter referred to as “TAC film”) formed on a single surface of the obtained polarizer is polyvinyl alcohol It bonded together through the adhesive agent which consists of aqueous solution of type
  • TAC film triacetyl cellulose film
  • a zero retardation film (trade name "ZEONOR” manufactured by Nippon Zeon Co., Ltd., hereinafter "COP film”) made of a cyclic polyolefin resin having a thickness of 23 ⁇ m on the surface opposite to the triacetyl cellulose film in the above polarizer
  • COP film a zero retardation film made of a cyclic polyolefin resin having a thickness of 23 ⁇ m on the surface opposite to the triacetyl cellulose film in the above polarizer
  • Example 4 Preparation of pressure-sensitive adhesive polarizing plate (1)
  • the pressure-sensitive adhesive layer-attached polarizing plate (1) has a configuration of TAC film / adhesive layer / polarizing film / adhesive layer / COP film / pressure-sensitive adhesive layer.
  • Example 5 Preparation of pressure-sensitive adhesive polarizing plate (2) In the same manner as in Example 3, except that the 23 ⁇ m cycloolefin film was replaced with the polarizing plate obtained in Production Example 1, a pressure-sensitive adhesive polarizing plate (2 Got).
  • the pressure-sensitive adhesive layer-attached polarizing plate (2) has a configuration of TAC film / adhesive layer / polarizing film / adhesive layer / COP film / pressure-sensitive adhesive layer.
  • Comparative Example 3 Preparation of pressure sensitive adhesive polarizing plate (3) In the same manner as in Comparative Example 2 except that the 23 ⁇ m cycloolefin film was replaced with the polarizing plate obtained in Production Example 1, a pressure sensitive adhesive polarizing plate (3 Got).
  • the pressure-sensitive adhesive layer-attached polarizing plate (3) has a configuration of TAC film / adhesive layer / polarizing film / adhesive layer / COP film / pressure-sensitive adhesive layer.
  • the obtained polarizing plate with adhesive was cut into a size of 30 mm ⁇ 30 mm, and then the adhesive layer was bonded to a glass substrate to obtain a measurement sample.
  • the layer configuration of the measurement sample is glass substrate / adhesive layer / COP film / adhesive layer / polarizer / adhesive layer / TAC film.
  • a non-alkali glass substrate (trade name "Eagle XG" manufactured by Corning Inc.) was used.
  • the absorbance of the polarizing plate with the pressure-sensitive adhesive layer was calculated from the transmission spectrum of the transmission axis aroma of the polarizing plate.
  • the polarizing plate with an adhesive confirmed deterioration suppression in visible light with a short wavelength of 405 nm.
  • the pressure-sensitive adhesive sheet of the present invention is excellent in light absorbing function near a wavelength of 350 nm and light absorbing function near a wavelength of 405 nm. Therefore, when the pressure-sensitive adhesive sheet of the present invention is laminated on a retardation film or an organic EL element, the pressure-sensitive adhesive sheet of the present invention can block ultraviolet light for the retardation film or the organic EL element and light near a wavelength of 405 nm. It is possible to suppress the deterioration of the retardation film or the organic EL element from both of the above and visible light of short wavelength.
  • the pressure-sensitive adhesive sheet 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).
  • the pressure-sensitive adhesive sheet of the present invention has a low light absorption performance at a wavelength of about 440 nm, and can exhibit good color expression without inhibiting the light emission of the liquid crystal display device.
  • the pressure-sensitive adhesive sheet-attached optical film of the present invention has a good light absorbing function near a wavelength of 405 nm. Furthermore, even after the weathering test, the light absorbing function near a wavelength of 405 nm is good, and has good weatherability (durability).
  • the pressure-sensitive adhesive sheet and the pressure-sensitive adhesive sheet-containing optical film of the present invention are suitably used for a liquid crystal panel and a liquid crystal display device.

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WO2020196284A1 (ja) * 2019-03-28 2020-10-01 住友化学株式会社 粘着剤組成物
WO2020196282A1 (ja) * 2019-03-28 2020-10-01 住友化学株式会社 粘着剤組成物
WO2021070800A1 (ja) * 2019-10-11 2021-04-15 住友化学株式会社 粘着剤組成物
WO2021172179A1 (ja) * 2020-02-28 2021-09-02 コニカミノルタ株式会社 光学フィルム、偏光板及び有機エレクトロルミネッセンス画像表示装置
CN114502680A (zh) * 2019-10-11 2022-05-13 住友化学株式会社 粘合剂组合物

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7257810B2 (ja) * 2019-02-20 2023-04-14 日東電工株式会社 切削加工された粘着剤層付光学積層体の製造方法
KR102594786B1 (ko) * 2019-07-09 2023-10-26 후지필름 가부시키가이샤 점착제 시트, 적층체, 표시 장치, 유기 일렉트로 루미네선스 표시 장치
JP2021099480A (ja) * 2019-12-23 2021-07-01 住友化学株式会社 光学積層体および画像表示装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002053824A (ja) * 2000-06-02 2002-02-19 Fuji Photo Film Co Ltd 紫外線吸収粘着フイルム
JP2007284516A (ja) * 2006-04-14 2007-11-01 Toyo Ink Mfg Co Ltd 紫外線遮断性樹脂組成物及びその利用
JP2013075978A (ja) * 2011-09-30 2013-04-25 Nitto Denko Corp 粘着シート
JP2017120430A (ja) * 2015-12-28 2017-07-06 住友化学株式会社 光学積層体
JP2017165941A (ja) * 2015-12-25 2017-09-21 日東電工株式会社 有機ｅｌ表示装置用粘着剤組成物、有機ｅｌ表示装置用粘着剤層、有機ｅｌ表示装置用粘着剤層付き偏光フィルム、及び有機ｅｌ表示装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006308936A (ja) 2005-04-28 2006-11-09 Fuji Photo Film Co Ltd 偏光板および液晶表示装置
KR101162558B1 (ko) * 2010-09-06 2012-07-05 미쓰비시 쥬시 가부시끼가이샤 화상 표시 장치 구성용 적층체의 제조 방법, 및 이 적층체를 사용하여 이루어지는 화상 표시 장치

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002053824A (ja) * 2000-06-02 2002-02-19 Fuji Photo Film Co Ltd 紫外線吸収粘着フイルム
JP2007284516A (ja) * 2006-04-14 2007-11-01 Toyo Ink Mfg Co Ltd 紫外線遮断性樹脂組成物及びその利用
JP2013075978A (ja) * 2011-09-30 2013-04-25 Nitto Denko Corp 粘着シート
JP2017165941A (ja) * 2015-12-25 2017-09-21 日東電工株式会社 有機ｅｌ表示装置用粘着剤組成物、有機ｅｌ表示装置用粘着剤層、有機ｅｌ表示装置用粘着剤層付き偏光フィルム、及び有機ｅｌ表示装置
JP2017120430A (ja) * 2015-12-28 2017-07-06 住友化学株式会社 光学積層体

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113825811A (zh) * 2019-03-28 2021-12-21 住友化学株式会社 粘合剂组合物
CN113825811B (zh) * 2019-03-28 2024-01-05 住友化学株式会社 粘合剂组合物
JP2020164836A (ja) * 2019-03-28 2020-10-08 住友化学株式会社 粘着剤組成物
JP2020164835A (ja) * 2019-03-28 2020-10-08 住友化学株式会社 粘着剤組成物
CN113874455A (zh) * 2019-03-28 2021-12-31 住友化学株式会社 粘合剂组合物
JP7456224B2 (ja) 2019-03-28 2024-03-27 住友化学株式会社 粘着剤組成物
WO2020196282A1 (ja) * 2019-03-28 2020-10-01 住友化学株式会社 粘着剤組成物
WO2020196284A1 (ja) * 2019-03-28 2020-10-01 住友化学株式会社 粘着剤組成物
TWI820319B (zh) * 2019-03-28 2023-11-01 日商住友化學股份有限公司 黏著劑組成物
WO2021070800A1 (ja) * 2019-10-11 2021-04-15 住友化学株式会社 粘着剤組成物
CN114502687A (zh) * 2019-10-11 2022-05-13 住友化学株式会社 粘合剂组合物
CN114502680B (zh) * 2019-10-11 2023-12-01 住友化学株式会社 粘合剂组合物
CN114502680A (zh) * 2019-10-11 2022-05-13 住友化学株式会社 粘合剂组合物
WO2021172179A1 (ja) * 2020-02-28 2021-09-02 コニカミノルタ株式会社 光学フィルム、偏光板及び有機エレクトロルミネッセンス画像表示装置

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