CN116266002A - Laminate body - Google Patents

Laminate body Download PDF

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Publication number
CN116266002A
CN116266002A CN202211611726.XA CN202211611726A CN116266002A CN 116266002 A CN116266002 A CN 116266002A CN 202211611726 A CN202211611726 A CN 202211611726A CN 116266002 A CN116266002 A CN 116266002A
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China
Prior art keywords
layer
liquid crystal
film
adhesive
compound
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Pending
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CN202211611726.XA
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Chinese (zh)
Inventor
李银玉
藤田政大
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority claimed from JP2022183141A external-priority patent/JP2023090645A/en
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Publication of CN116266002A publication Critical patent/CN116266002A/en
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02Physical, chemical or physicochemical properties
    • B32B7/023Optical properties
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3083Birefringent or phase retarding elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/041Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3016Polarising elements involving passive liquid crystal elements
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528Polarisers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00Condition, form or state of the layers or laminate
    • B32B2305/55Liquid crystals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/42Polarizing, birefringent, filtering

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)

Abstract

The present invention provides a laminate which can inhibit the generation of pitting corrosion at a metal layer even when the laminate is attached to the metal layer and exposed to a hot and humid environment. The laminate includes, in order, a 1 st liquid crystal cured layer that is a cured product layer of a polymerizable liquid crystal compound, an adhesive layer, and a 2 nd liquid crystal cured layer that is a cured product layer of a polymerizable liquid crystal compound. The adhesive layer is a cured product layer of an adhesive composition containing a curable component and a photo-cationic polymerization initiator. The curable component contains an alicyclic epoxy compound and an oxetane compound having 2 or more oxetanyl groups in the molecule. The content of the photo-cationic polymerization initiator in the adhesive composition is 2.0 parts by mass or less relative to 100 parts by mass of the curable component.

Description

Laminate body
Technical Field
The present invention relates to a laminate.
Background
In display devices such as liquid crystal display devices and organic EL display devices, optical films such as retardation layers and linear polarization layers are used. It is known that a retardation layer and a linearly polarizing layer are formed using a liquid crystal cured layer obtained by polymerizing and curing a polymerizable liquid crystal compound, and that the liquid crystal cured layer is laminated via an adhesive layer, and the obtained laminate is used as an optical film (for example, patent document 1).
In a touch panel type display device used mainly for a mobile information terminal such as a smart phone or a tablet, a metal layer for constituting a touch sensor may be provided on an image display element. In the case of incorporating an optical film into a touch panel display device, the optical film may be bonded to a metal layer via an adhesive layer or the like.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2020-56988
Disclosure of Invention
Problems to be solved by the invention
When the laminate is used as an optical film and a member having the laminate bonded to a metal layer is placed in a hot and humid environment, fine holes (hereinafter, sometimes referred to as "pitting") through which light can pass may be generated in the surface of the metal layer.
The purpose of the present invention is to provide a laminate which, even when bonded to a metal layer and exposed to a hot and humid environment, can suppress the occurrence of pitting at the metal layer.
Means for solving the problems
[ 1 ] A laminate comprising, in order, a 1 st liquid crystal cured layer as a cured product layer of a polymerizable liquid crystal compound, an adhesive layer, and a 2 nd liquid crystal cured layer as a cured product layer of a polymerizable liquid crystal compound,
The adhesive layer is a cured product layer of an adhesive composition containing a curable component and a photo-cationic polymerization initiator,
the curable component contains an alicyclic epoxy compound and an oxetane compound having 2 or more oxetanyl groups in the molecule,
the content of the photo-cationic polymerization initiator in the adhesive composition is 2.0 parts by mass or less relative to 100 parts by mass of the curable component.
The laminate according to [ 2 ], wherein the oxetane compound is an aliphatic compound.
The laminate according to [ 1 ] or [ 2 ], wherein the photo-cation polymerization initiator is an aromatic onium salt.
The laminate according to [ 4 ], wherein the anionic component of the photo-cationic polymerization initiator contains a fluorine atom.
The laminate according to any one of [ 1 ] to [ 4 ], wherein the 1 st liquid crystal cured layer is a lambda/2 retardation layer,
the 2 nd liquid crystal solidified layer is a lambda/4 phase difference layer.
The laminate according to item [ 6 ], which further comprises a linearly polarizing layer laminated on the side of the 1 st liquid crystal cured layer opposite to the adhesive layer side.
The laminate according to any one of [ 1 ] to [ 6 ], further comprising a metal layer laminated on the side of the 2 nd liquid crystal cured layer opposite to the adhesive layer side.
Effects of the invention
According to the laminate of the present invention, even when the laminate is bonded to a metal layer and exposed to a hot and humid environment, the occurrence of pitting of the metal layer can be suppressed.
Drawings
Fig. 1 is a schematic cross-sectional view schematically showing a laminate according to an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view schematically showing a laminate according to another embodiment of the present invention.
Fig. 3 is a schematic cross-sectional view schematically showing a laminate according to another embodiment of the present invention.
Fig. 4 is a schematic cross-sectional view schematically showing a laminate according to another embodiment of the present invention.
Description of the reference numerals
1. 2, 3, 4 laminates, 11 1 st liquid crystal cured layer, 12 nd liquid crystal cured layer, 21 adhesive layer, 22 1 st bonding layer, 23 2 nd bonding layer, 31 polarizing plate, 35 metal layer.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiments.
(laminate)
Fig. 1 to 4 are schematic cross-sectional views schematically showing a laminate according to an embodiment of the present invention. As shown in fig. 1 to 4, the laminated bodies 1 to 4 of the present embodiment sequentially include a 1 st liquid crystal cured layer 11 as a cured product layer of a polymerizable liquid crystal compound, an adhesive layer 21, and a 2 nd liquid crystal cured layer 12 as a cured product layer of a polymerizable liquid crystal compound. The 1 st liquid crystal cured layer 11 is preferably in direct contact with the adhesive layer 21. The adhesive layer 21 is preferably in direct contact with the 2 nd liquid crystal cured layer 12.
The laminated bodies 1 to 4 may have the 1 st alignment film on the adhesive layer 21 side of the 1 st liquid crystal cured layer 11 or on the side opposite to the adhesive layer 21 side, in direct contact with the 1 st liquid crystal cured layer 11. The laminated bodies 1 to 4 may have the 2 nd alignment film on the adhesive layer 21 side of the 2 nd liquid crystal cured layer 12 or on the side opposite to the adhesive layer 21 side in direct contact with the 2 nd liquid crystal cured layer 12.
The laminated bodies 1 to 4 may be circularly polarizing plates. When the laminated bodies 1 to 4 are circularly polarizing plates, they include a linearly polarizing layer and a λ/4 retardation layer, which will be described later. As described later, a linearly polarizing layer may be provided in addition to the 1 st liquid crystal cured layer 11 and the 2 nd liquid crystal cured layer 12, or one of the 1 st liquid crystal cured layer 11 and the 2 nd liquid crystal cured layer 12 may be a linearly polarizing layer, and the other may be a λ/4 retardation layer.
The laminate of the present embodiment may include a linearly polarizing layer laminated on the side opposite to the adhesive layer 21 side of the 1 st liquid crystal cured layer 11. Fig. 2 and 4 show the laminated bodies 2 and 4 in which the polarizing plate 31 having a protective film on one or both surfaces of the linear polarizing layer is laminated on the side opposite to the adhesive layer 21 side of the 1 st liquid crystal cured layer 11. The 1 st liquid crystal cured layer 11 may be in direct contact with the polarizing plate 31 or the linear polarizing layer, or may be laminated via the 1 st adhesive layer 22. The 1 st lamination layer 22 is an adhesive layer or an adhesive layer.
The laminate of the present embodiment may include the metal layer 35 laminated on the side opposite to the adhesive layer 21 side of the 2 nd liquid crystal cured layer 12, like the laminates 3 and 4 shown in fig. 3 and 4. The 2 nd liquid crystal cured layer 12 and the metal layer 35 are generally laminated via the 2 nd bonding layer 23, in which case the 2 nd liquid crystal cured layer 12 and the 2 nd bonding layer 23 may be in direct contact, and the 2 nd bonding layer 23 and the metal layer 35 may be in direct contact. The 2 nd lamination layer 23 is an adhesive layer or an adhesive layer.
The laminate of the present embodiment may include the 2 nd adhesive layer 23 on the side of the 2 nd liquid crystal cured layer 12 opposite to the adhesive layer 21 side, and may further include a release film on the side of the 2 nd adhesive layer 23 opposite to the 2 nd liquid crystal cured layer 12.
The laminate can be applied to a display device. Examples of the display device include a liquid crystal display device and an organic EL display device. The display device may be a mobile terminal such as a smart phone or a tablet, or may be a television, a digital photo frame, an electronic billboard, a measuring instrument, office equipment, medical equipment, or an electronic computer device.
(adhesive layer)
The adhesive layer 21 is a cured product layer of an adhesive composition containing a curable component and a photo-cationic polymerization initiator. The curable component contains an alicyclic epoxy compound, an oxetane compound, and an oxetane compound having 2 or more oxetanyl groups in the molecule.
The laminated bodies 1 to 4 are obtained by laminating the 1 st liquid crystal cured layer 11 and the 2 nd liquid crystal cured layer 12 via the adhesive composition described above, and curing the adhesive composition to form the adhesive layer 21. By forming the adhesive layer 21 using the adhesive composition having the above-described composition, even when the members having the laminates 1 and 2 bonded to the metal layer or the laminates 3 and 4 are exposed to a hot and humid environment (for example, a temperature of 85 ℃ and a relative humidity of 85%), the occurrence of pitting in the metal layer can be suppressed.
The thickness of the adhesive layer 21 may be, for example, 20 μm or less, 15 μm or less, 10 μm or less, or 0.5 μm or more, 1 μm or more, or 3 μm or more.
The curable component contained in the adhesive composition may contain other curable components than the curable component. Examples of the other curable component include aliphatic epoxy compounds, aromatic epoxy compounds, and monofunctional oxetane compounds having 1 oxetanyl group in the molecule.
The adhesive composition may contain a curable component and other components than the photo-cationic polymerization initiator. Examples of the other components include photosensitizers, polymerization promoters, ion capturing agents, antioxidants, light stabilizers, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow regulators, plasticizers, antifoaming agents, antistatic agents, leveling agents, pigments, organic solvents, and the like.
The adhesive composition is preferably an active energy ray-curable adhesive composition in which a curable component is polymerized and cured by irradiation with active energy rays such as ultraviolet rays, visible rays, X-rays, or electron beams. The adhesive composition is more preferably an ultraviolet-curable adhesive composition that cures by irradiation with ultraviolet rays.
In the case where the adhesive composition is ultraviolet-curable, the cumulative amount of the light irradiation intensity may be, for example, 10mJ/cm 2 Above, it may be 100mJ/cm 2 The above may be 1000mJ/cm 2 Hereinafter, the ratio may be 800mJ/cm 2 The following is given. The ultraviolet light to be irradiated to the adhesive composition may be UVA (wavelength 320 to 400 nm), UVB (wavelength 280 to 320 nm), or both.
(alicyclic epoxy Compound)
The curable component contained in the adhesive composition contains an alicyclic epoxy compound. The alicyclic epoxy compound is a compound having an alicyclic epoxy group, and is a compound containing no aromatic ring. In the present specification, the alicyclic epoxy group means an epoxy group bonded to an alicyclic ring, and means an oxygen atom-O-in the structure shown below. In the following formula, m is an integer of 2 to 5. The alicyclic epoxy compound is a compound represented by the following formulaFall (CH) 2 ) m More than 1 hydrogen atom and a group in a form after the hydrogen atom is bonded to other chemical structures. (CH) 2 ) m More than 1 hydrogen atom in (a) may be substituted with a linear alkyl group such as methyl or ethyl. By including the alicyclic epoxy compound in the adhesive composition, when the members having the laminates 1 and 2 bonded to the metal layer or the laminates 3 and 4 are exposed to a hot and humid environment (for example, a temperature of 85 ℃ C. And a relative humidity of 85%) it is possible to suppress occurrence of pitting corrosion in the metal layer.
[ chemical formula 1]
Figure BDA0003999031520000051
The alicyclic epoxy group of the alicyclic epoxy compound may be 1 or 2 or more, but is preferably 2.
Examples of the alicyclic epoxy compound include 3, 4-epoxycyclohexane carboxylic acid 3',4' -epoxycyclohexyl methyl ester, 1, 2-epoxy-4-vinylcyclohexane, 1, 2-epoxy-1-methyl-4- (1-methyl epoxyethyl) cyclohexane, 3, 4-epoxycyclohexyl methyl methacrylate, 4- (1, 2-epoxyethyl) -1, 2-bis (hydroxymethyl) -1-butanol 4- (1, 2-epoxycyclohexane adduct, ethylenebis (3, 4-epoxycyclohexane formate), oxydiethylenebis (3, 4-epoxycyclohexane formate), 1, 4-cyclohexanedimethylbis (3, 4-epoxycyclohexane formate), 3- (3, 4-epoxycyclohexylmethoxycarbonyl) propyl 3, 4-epoxycyclohexane carboxylate, and the like. The alicyclic epoxy compound may be used in an amount of 1 or 2 or more.
The content of the alicyclic epoxy compound in the adhesive composition may be 10.0 parts by mass or more, or may be 20.0 parts by mass or more, or may be 30.0 parts by mass or more, or may be 60.0 parts by mass or less, or may be 50.0 parts by mass or less, or may be 40.0 parts by mass or less, based on 100 parts by mass of the total amount of the curable components. When the adhesive composition contains 2 or more alicyclic epoxy compounds, the content of the alicyclic epoxy compounds is the total amount of the alicyclic epoxy compounds contained in the adhesive composition.
(oxetane compound)
The curable component contained in the adhesive composition contains an oxetane compound. The oxetane compound has 2 or more oxetanyl groups in the molecule. The oxetane compound may be any of aliphatic compounds such as chain aliphatic compounds and alicyclic compounds, and aromatic compounds containing an aromatic ring, as long as it is a polyfunctional oxetane compound having 2 or more oxetanyl groups in the molecule. The oxetane compound preferably has 2 oxetane groups in the molecule. The oxetane compound is preferably an aliphatic compound, and is preferably a chain aliphatic compound. The oxetane compound referred to in the present specification is a compound having no epoxy group in the molecule. By including an oxetane compound in the adhesive composition, the curing speed and viscosity of the adhesive composition can be adjusted, and the reactivity can be improved.
Examples of oxetane compounds include 3, 7-bis (3-oxetanyl) -5-oxo-nonane, 1, 4-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] benzene, 1, 2-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ethane, 1, 3-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1, 4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1, 6-bis (3-ethyl-3-oxetanylmethoxy) hexane, 3-ethyl-3 { [ (3-ethyloxetan-3-yl) methoxy ] methyl } oxetane, and xylylene bis oxetane. The oxetane compound may be used in an amount of 1 or 2 or more.
The content of the oxetane compound in the adhesive composition may be 20 parts by mass or more, or may be 30 parts by mass or more, or may be 40 parts by mass or more, or may be 80 parts by mass or less, or may be 70 parts by mass or less, or may be 60 parts by mass or less, based on 100 parts by mass of the total amount of the curable components. When the adhesive composition contains 2 or more oxetane compounds, the content of the oxetane compounds is the total amount of the oxetane compounds contained in the adhesive composition.
(aliphatic epoxy Compound)
The adhesive composition may contain an aliphatic epoxy compound as a curable component other than the curable component described above. In the present specification, the aliphatic epoxy compound is a compound having no aromatic ring or alicyclic epoxy group. The number of epoxy groups in the aliphatic epoxy compound may be 1 or 2 or more, but is preferably 2 or more.
Examples of the aliphatic epoxy compound having 1 epoxy group include methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, 1, 2-epoxyhexane, 1, 2-epoxyoctane, 1, 2-epoxydecane, 1, 2-epoxydodecane, 1, 2-epoxytetradecane, 1, 2-epoxyhexadecane, 1, 2-epoxyoctadecane, epoxyphenylethane, phenyl glycidyl ether, tolyl glycidyl ether, p-sec-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, 1-vinyl-3, 4-epoxycyclohexane and α -epoxypinane.
Examples of the aliphatic epoxy compound having 2 or more epoxy groups include polyglycidyl ethers of aliphatic polyols or alkylene oxide adducts thereof. More specifically, 1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol; diglycidyl ether of 1, 4-butanediol; diglycidyl ether of 1, 6-hexanediol; diglycidyl ether of neopentyl glycol; triglycidyl ethers of glycerol; triglycidyl ether of trimethylolpropane; diglycidyl ether of polyethylene glycol; diglycidyl ether of propylene glycol; and polyglycidyl ethers of polyether polyols obtained by adding 1 or 2 or more alkylene oxides (ethylene oxide, propylene oxide) to aliphatic polyols such as ethylene glycol, propylene glycol or glycerin.
The content of the aliphatic epoxy compound in the adhesive composition may be 1 part by mass or more, or may be 5 parts by mass or more, or may be 10 parts by mass or more, or may be 50 parts by mass or less, or may be 40 parts by mass or less, or may be 30 parts by mass or less, or may be 20 parts by mass or less, based on 100 parts by mass of the total amount of the curable components.
(aromatic epoxy Compound)
The adhesive composition may contain an aromatic epoxy compound as a curable component other than the curable component described above. An aromatic epoxy compound is a compound containing at least 1 epoxy group and at least 1 aromatic ring in the molecule.
Examples of the aromatic epoxy compound include glycidyl phenyl ether; resorcinol diglycidyl ether; naphthalene-type epoxy compounds as polyglycidyl ethers of naphthalene or naphthalene derivatives; bisphenol-type epoxy compounds as glycidyl ethers of bisphenol derivatives such as bisphenol A, bisphenol F, bisphenol S, bisphenol M, and bisphenol P; fluorene-type epoxy compounds as glycidyl ethers of fluorene or fluorene derivatives; etc.
The content of the aromatic epoxy compound in the adhesive composition may be 1 part by mass or more, or may be 5 parts by mass or more, or may be 10 parts by mass or more, or may be 50 parts by mass or less, or may be 40 parts by mass or less, or may be 30 parts by mass or less, or may be 20 parts by mass or less, based on 100 parts by mass of the total amount of the curable components.
(monofunctional oxetane Compound)
The adhesive composition may contain a monofunctional oxetane compound as a curable component other than the curable component described above. The monofunctional oxetane compound has 1 oxetanyl group in the molecule. The monofunctional oxetane compound may be any of aliphatic compounds such as chain aliphatic compounds and alicyclic compounds, and aromatic compounds containing an aromatic ring, as long as it has 1 oxetanyl group in the molecule. The monofunctional oxetane compound preferably contains an aromatic ring in the molecule. The monofunctional oxetane compound as referred to in the present specification is a compound having no epoxy group in the molecule.
Examples of the monofunctional oxetane compound include 3-ethyl-3- (phenoxy) methyl oxetane, 3- [ (benzyloxy) methyl ] -3-ethyl oxetane, 3-ethyl-3- (cyclohexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-hydroxymethyl oxetane, and 3-ethyl-3- (chloromethyl) oxetane. The monofunctional oxetane compound may be used in an amount of 1 or 2 or more.
The content of the monofunctional oxetane compound in the adhesive composition may be 1 part by mass or more, or may be 10 parts by mass or more, or may be 20 parts by mass or more, or may be 50 parts by mass or less, or may be 40 parts by mass or less, or may be 30 parts by mass or less, based on 100 parts by mass of the total amount of the curable components. When the adhesive composition contains 2 or more monofunctional oxetane compounds, the content of the monofunctional oxetane compounds is the total amount of the monofunctional oxetane compounds contained in the adhesive composition.
(photo cationic polymerization initiator)
The adhesive composition includes a photo-cationic polymerization initiator. This can polymerize and cure the curable component contained in the adhesive composition to form a cured product layer. The photo-cation polymerization initiator is a substance that generates a cation species or a lewis acid by irradiation with active energy rays and initiates polymerization of a curable component. Since the photo-cation polymerization initiator exerts a catalytic action by light, the photo-cation polymerization initiator is excellent in storage stability and workability even when mixed into a curable component. Examples of the photo-cation polymerization initiator include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; iron-arene complexes, and the like. The photo cation polymerization initiator is preferably an aromatic onium salt.
Examples of the aromatic diazonium salt include the following compounds.
Phenyl diazonium hexafluoroantimonate,
Phenyl diazonium hexafluorophosphate,
Phenyl diazonium hexafluoroborate, and the like.
Examples of the aromatic iodonium salts include the following compounds.
Diphenyliodonium tetrakis (pentafluorophenyl) borate,
Diphenyl iodonium hexafluorophosphate,
Diphenyl iodonium hexafluoroantimonate,
Bis (4-nonylphenyl) iodonium hexafluorophosphate, and the like.
Examples of the aromatic sulfonium salt include the following compounds.
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoroantimonate,
Triphenylsulfonium tetrakis (pentafluorophenyl) borate,
4,4' -bis (diphenylsulfonium) diphenyl sulfide bis hexafluorophosphate,
4,4 '-bis [ bis (. Beta. -hydroxyethoxy) phenylsulfonium ] diphenylsulfide bis hexafluoroantimonate, 4' -bis [ bis (. Beta. -hydroxyethoxy) phenylsulfonium ] diphenylsulfide bis hexafluorophosphate, 7- [ bis (p-toluoyl) sulfonium ] -2-isopropylthioxanthone hexafluoroantimonate,
7- [ bis (p-toluyl) sulfonium ] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate,
4-phenylcarbonyl-4' -diphenylsulfonium-diphenyl sulfide hexafluorophosphate,
4- (p-tert-butylphenylcarbonyl) -4' -diphenylsulfonium-diphenyl sulfide hexafluoroantimonate,
4- (p-tert-butylphenylcarbonyl) -4' -bis (p-toluoyl) sulfonium-diphenyl sulfide tetrakis (pentafluorophenyl) borate, and the like.
Examples of the iron-aromatic hydrocarbon complex include the following compounds.
Xylene-cyclopentadienyl iron (II) hexafluoroantimonate,
Cumene-cyclopentadienyl iron (II) hexafluorophosphate,
Xylene-cyclopentadienyl iron (II) tris (trifluoromethanesulfonyl) methanate, and the like.
The content (solid content) of the photo-cationic polymerization initiator in the adhesive composition is 2.0 parts by mass or less, or 1.9 parts by mass or less, or 1.8 parts by mass or less, or 1.6 parts by mass or less, or 1.5 parts by mass or less, or 1.4 parts by mass or less, or generally 0.1 parts by mass or more, or 0.5 parts by mass or more, or 1.0 part by mass or more, based on 100 parts by mass of the total amount of the curable components. In the case where 2 or more photo-cation polymerization initiators are contained in the adhesive composition, the content of the photo-cation polymerization initiator is the total amount of the photo-cation polymerization initiators contained in the adhesive composition. By setting the content of the photo-cation polymerization initiator to be within the above range, even when the members having the laminated bodies 1 and 2 bonded to the metal layers or the laminated bodies 3 and 4 are exposed to a hot and humid environment (for example, a temperature of 85 ℃ C., a relative humidity of 85%) it is possible to suppress occurrence of pitting corrosion in the metal layers.
(photosensitive auxiliary agent)
The adhesive composition may contain a photosensitive auxiliary agent as a curable component and other components than the photo-cationic polymerization initiator. The photo-sensitive auxiliary is a compound that promotes a polymerization initiation reaction based on a photo-cationic polymerization initiator. The photosensitizing aid is preferably a naphthalene based compound.
Examples of the photosensitizing auxiliary include 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1, 4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1, 4-diethoxynaphthalene, 1, 4-dipropoxynaphthalene, and 1, 4-dibutoxynaphthalene.
The content of the photosensitive auxiliary agent in the adhesive composition may be 0.1 part by mass or more, or 0.5 part by mass or more, or 1.0 part by mass or more, or 5.0 parts by mass or less, or 4.0 parts by mass or less, or 3.0 parts by mass or less, based on 100 parts by mass of the total amount of the curable components.
(1 st liquid crystal cured layer, 2 nd liquid crystal cured layer)
The 1 st liquid crystal cured layer 11 and the 2 nd liquid crystal cured layer 12 (hereinafter, both may be collectively referred to as "liquid crystal cured layers") are cured layers of polymerizable liquid crystal compounds. The polymerizable liquid crystal compound has at least 1 polymerizable group and has liquid crystallinity. As the polymerizable liquid crystal compound, a known polymerizable liquid crystal compound can be used.
The liquid crystal cured layer may be a retardation layer or a linearly polarizing layer. For example, the 1 st liquid crystal cured layer 11 may be a linear polarization layer, and the 2 nd liquid crystal cured layer 12 may be a λ/4 retardation layer. In addition to the 1 st liquid crystal cured layer 11 and the 2 nd liquid crystal cured layer 12, a linearly polarizing layer may be provided, and when the 1 st liquid crystal cured layer 11 and the 2 nd liquid crystal cured layer 12 are both retardation layers, the combination of the 1 st liquid crystal cured layer 11 and the 2 nd liquid crystal cured layer 12 may include [ i ] λ/2 retardation layer and λ/4 retardation layer, or [ ii ] λ/4 retardation layer and positive C retardation layer. The lambda/4 phase difference layer may have inverse wavelength dispersibility.
The λ/2 retardation layer is a layer that imparts a retardation of pi (=λ/2) in the electric field vibration direction (polarization plane) of incident light, and has a function of changing the direction (polarization direction) of linearly polarized light. If light of circularly polarized light is incident, the rotation direction of the circularly polarized light can be reversed. The λ/2 retardation layer is a layer in which Re (λ) =λ/2 is satisfied as an in-plane retardation value at a specific wavelength λ [ nm ]. Although Re (λ) =λ/2 may be achieved at any wavelength in the visible light region, it is preferably achieved at a wavelength of 550 nm. Re (550) as an in-plane retardation value at a wavelength of 550nm preferably satisfies 210 nm.ltoreq.Re (550). Ltoreq.300 nm. In addition, it is more preferable that Re (550) to 290nm is not more than 220 nm.
The λ/4 phase difference layer is a layer that imparts a phase difference of pi/2 (=λ/4) in the electric field vibration direction (polarization plane) of incident light, and has a function of converting linearly polarized light of a certain specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light). The λ/4 retardation layer is a layer satisfying Re (λ) =λ/4 as an in-plane retardation value at a specific wavelength λ [ nm ], and may be achieved at any wavelength in the visible light region, but is preferably achieved at a wavelength of 550 nm. Re (550) as an in-plane retardation value at a wavelength of 550nm preferably satisfies 100 nm.ltoreq.Re (550). Ltoreq.160 nm. In addition, 110 nm.ltoreq.Re (550). Ltoreq.150 nm is more preferably satisfied.
In the case where the liquid crystal cured layer is a linearly polarizing layer, the linearly polarizing layer may be formed using a polymerizable liquid crystal compound having absorption anisotropy in addition to liquid crystallinity, or may be formed using a composition containing a polymerizable liquid crystal compound and a dye having absorption anisotropy. Examples of the linearly polarizing layer as the liquid crystal cured layer include polarizing layers described in japanese patent application laid-open No. 2013-33249.
The type of polymerizable liquid crystal compound used for forming the liquid crystal cured layer is not particularly limited, and a rod-like liquid crystal compound, a discotic liquid crystal compound, and a mixture thereof may be used. The cured product layer formed by polymerizing the polymerizable liquid crystal compound is cured in a state where the polymerizable liquid crystal compound is oriented in a proper direction, thereby exhibiting a phase difference. When the rod-shaped polymerizable liquid crystal compound is oriented horizontally or vertically with respect to the planar direction of the laminate, the optical axis of the polymerizable liquid crystal compound coincides with the long axis direction of the polymerizable liquid crystal compound. When the disk-shaped polymerizable liquid crystal compound is aligned, the optical axis of the polymerizable liquid crystal compound is present in a direction perpendicular to the disk surface of the polymerizable liquid crystal compound. As the rod-like polymerizable liquid crystal compound, for example, a polymerizable liquid crystal compound described in JP-A-11-513019 (claim 1 and the like) can be suitably used. As the disk-shaped polymerizable liquid crystal compound, those described in JP-A2007-108732 (paragraphs [0020] to [0067] and the like) and JP-A2010-244038 (paragraphs [0013] to [0108] and the like) can be suitably used.
The polymerizable group of the polymerizable liquid crystal compound is a group participating in polymerization reaction, and is preferably a photopolymerizable group. The photopolymerizable group means a group capable of participating in polymerization reaction by utilizing a reactive radical, an acid, or the like generated from a photopolymerization initiator. Examples of the polymerizable group include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, (meth) acryloyloxy, epoxyethyl, oxetanyl, styryl, and allyl. Among them, (meth) acryloyloxy, ethyleneoxy, ethyleneoxide and oxetanyl groups are preferred, and acryloyloxy is more preferred. The liquid crystallinity of the polymerizable liquid crystal compound may be either thermotropic liquid crystal or lyotropic liquid crystal, or nematic liquid crystal or smectic liquid crystal when the thermotropic liquid crystal is classified into ordered ones. In the case where 2 or more polymerizable liquid crystal compounds are used in combination for forming a cured layer of the polymerizable liquid crystal compound, at least 1 type of polymerizable compound having 2 or more polymerizable groups in the molecule is preferable.
The liquid crystal cured layer may be formed by applying a composition for forming a liquid crystal cured layer containing a polymerizable liquid crystal compound, a solvent, and various additives as needed to an alignment film described later to form a coating film, and curing (hardening) the coating film to form a cured product layer of the polymerizable liquid crystal compound. Alternatively, the composition may be applied to a base film to form a coating film, and the coating film may be stretched together with the base film to be cured. The composition may contain a polymerization initiator, a reactive additive, a leveling agent, a polymerization inhibitor, and the like in addition to the polymerizable liquid crystal compound and the solvent. The polymerizable liquid crystal compound, solvent, polymerization initiator, reactive additive, leveling agent, polymerization inhibitor, etc. may be appropriately used.
As the base film, a film formed of a resin material, for example, a film using a resin material described as a thermoplastic resin used for forming a protective film described later, can be used. The thickness of the base film is not particularly limited, but is usually preferably 1 to 300 μm or less, more preferably 20 to 200 μm, and still more preferably 30 to 120 μm in view of workability such as strength and workability. The base film may be incorporated into the laminate together with the cured product layer of the polymerizable liquid crystal compound, or the base film may be peeled off to incorporate only the cured product layer of the polymerizable liquid crystal compound, or the cured product layer and an alignment film described later into the laminates 1 to 4.
The thickness of the 1 st liquid crystal cured layer 11 and the 2 nd liquid crystal cured layer 12 may be 0.1 μm or more, or 0.5 μm or more, or 1 μm or more, or 10 μm or less, or 8 μm or less, or 5 μm or less, or 3 μm or less, independently of each other.
(1 st orientation film, 2 nd orientation film)
The laminated bodies 1 to 4 may contain a 1 st orientation film and/or a 2 nd orientation film (hereinafter, both may be collectively referred to as "orientation film"). The alignment film has an alignment regulating force for aligning the polymerizable liquid crystal compound in a desired direction. The alignment film may be a vertical alignment film that aligns the molecular axis of the polymerizable liquid crystal compound vertically with respect to the planar direction of the laminate, a horizontal alignment film that aligns the molecular axis of the polymerizable liquid crystal compound horizontally with respect to the planar direction of the laminate, or an oblique alignment film that aligns the molecular axis of the polymerizable liquid crystal compound obliquely with respect to the planar direction of the laminate. In the case where the retardation layer includes 2 or more alignment films, the alignment films may be the same or different from each other.
As the alignment film, an alignment film having solvent resistance that is not dissolved by coating or the like of a composition for forming a liquid crystal layer containing a polymerizable liquid crystal compound and heat resistance for heat treatment for removal of a solvent and alignment of a polymerizable liquid crystal compound is preferable. Examples of the alignment film include an alignment polymer layer made of an alignment polymer, a photo-alignment polymer layer made of a photo-alignment polymer, a groove alignment film having a surface of the layer with a concave-convex pattern formed by rubbing treatment or the like, and a plurality of grooves (grooves).
(Linear polarization layer)
The linear polarization layer transmits linearly polarized light having a vibration plane orthogonal to an absorption axis when unpolarized light is incident. The linear polarization layer may be a polyvinyl alcohol resin film (hereinafter, sometimes referred to as "PVA-based film") to which a dichroic dye is adsorbed and aligned, or may be a film of a liquid crystal cured layer. As the film of the liquid crystal cured layer, the film described above can be given. The linear polarization layer is preferably a PVA-based resin film to which a dichroic dye is adsorbed and aligned. When the laminated bodies 1 to 4 include a linearly polarizing layer in addition to the 1 st liquid crystal cured layer 11 and the 2 nd liquid crystal cured layer 12, the 1 st liquid crystal cured layer 11 and the 2 nd liquid crystal cured layer 12 are preferably retardation layers.
Examples of the linear polarizing layer of the PVA film include a polarizing layer obtained by dyeing and stretching a PVA film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, and an ethylene-vinyl acetate copolymer partially saponified film with a dichroic dye. If necessary, a cleaning step may be performed in which the PVA-based film to which the dichroic dye is adsorbed and aligned by dyeing is treated with an aqueous boric acid solution, and then the aqueous boric acid solution is rinsed off. The steps may be performed by a known method.
Polyvinyl alcohol-based resins (hereinafter sometimes referred to as "PVA-based resins") can be produced by saponifying polyvinyl acetate-based resins. The polyvinyl acetate resin may be polyvinyl acetate which is a homopolymer of vinyl acetate, or may be a copolymer of vinyl acetate and another monomer copolymerizable with vinyl acetate. Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
The saponification degree of the PVA-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The PVA-based resin may be modified, and for example, polyvinyl formal, polyvinyl acetal, or the like modified with an aldehyde may be used. The average polymerization degree of the PVA-based resin is usually about 1000 to 10000, preferably about 1500 to 5000. The saponification degree and the average polymerization degree of the PVA based resin can be determined in accordance with JIS K6726 (1994). If the average polymerization degree is less than 1000, it is difficult to obtain preferable polarization performance, and if it exceeds 10000, film processability may be poor.
Examples of the dichroic dye adsorbed to the PVA film and aligned include iodine and a dichroic dye. The dichroic dye is preferably iodine. Examples of the dichroic dye include Red BR (Red BR), red LR (Red LR), red R (Red R), pink LB (Pink LB), ruby Red BL (rubene BL), purplish Red GS (Bordeaux GS), sky Blue LG (Sky Blue LG), lemon Yellow, blue BR (Blue BR), blue 2R (Blue 2R), navy RY (Navy RY), green LG (Green LG), purple LB (Violet LB), purple B (Violet B), black H (Black H), black B (Black B), black GSP (Black GSP), yellow3G (Yellow 3G), yellow R (Yellow R), orange LR (Orange LR), orange 3R (Orange 3R), scarlet GL (Scarlet GL), scarlet KGL (Scarlet KGL), congo Red (con Red), brilliant Violet BK (Brilliant Violet BK), supra Blue G, supra Blue GL, supra Orange, direct Sky Blue (Direct Blue) Blue S (Direct Fast Orange S), direct Black Blue (Blue) and Direct Orange light (Blue S (Direct Fast Orange S)).
The method for producing the linear polarization layer as the PVA-based film may include a step of preparing a base film, applying a solution of a resin such as a PVA-based resin on the base film, and drying the solution to remove the solvent, thereby forming a resin layer on the base film. The primer layer may be formed in advance on the resin layer-forming surface of the base film. As the base film, a film using a resin material described as a thermoplastic resin for forming a protective film described later can be used. Examples of the material of the primer layer include a resin obtained by crosslinking a hydrophilic resin used for the linearly polarizing layer.
Then, the amount of solvent such as moisture in the resin layer is adjusted as needed, and thereafter, the base film and the resin layer are uniaxially stretched, and then the resin layer is dyed with a dichroic dye to adsorb the dichroic dye to the resin layer and orient the same. Then, if necessary, a cleaning step of treating the resin layer to which the dichroic dye is adsorbed and aligned with an aqueous boric acid solution and then washing out the aqueous boric acid solution is performed. Thus, a resin layer having a dichroic dye adsorbed thereto and aligned, that is, a PVA film serving as a linear polarizing layer can be produced. The steps may be performed by a known method.
When the dichroic dye is iodine, the amount of boric acid in the aqueous solution containing boric acid, which is obtained by treating the PVA-based film or resin layer to which iodine is adsorbed and aligned, is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. The aqueous solution containing boric acid preferably contains potassium iodide. The amount of potassium iodide in the aqueous solution containing boric acid is usually about 0.1 to 15 parts by mass, preferably about 5 to 12 parts by mass, per 100 parts by mass of water. The immersion time in the aqueous solution containing boric acid is usually about 60 to 1200 seconds, preferably about 150 to 600 seconds, and more preferably about 200 to 400 seconds. The temperature of the aqueous solution containing boric acid is usually 50℃or higher, preferably 50 to 85℃and more preferably 60 to 80 ℃.
The uniaxial stretching of the PVA-based film, the base film, and the resin layer may be performed before dyeing, during boric acid treatment after dyeing, or in a plurality of stages thereof. The PVA-based film, the base film, and the resin layer may be uniaxially stretched in the MD direction (film conveyance direction), and in this case, stretching may be performed uniaxially between rolls having different peripheral speeds, or stretching may be performed uniaxially using a hot roll. In addition, the PVA-based film, the base film, and the resin layer may be uniaxially stretched in the TD direction (the direction perpendicular to the film conveying direction), and in this case, a so-called tenter method may be used. The stretching may be a dry stretching performed in the atmosphere or a wet stretching performed in a state where the PVA-based film or the resin layer is swollen with a solvent. In order to exhibit the performance of the linearly polarizing layer, the stretching ratio is 4 times or more, preferably 5 times or more, and particularly preferably 5.5 times or more. The upper limit of the stretching ratio is not particularly limited, but is preferably 8 times or less from the viewpoint of suppressing breakage or the like.
The linear polarization layer manufactured by the manufacturing method using the base film can be obtained by peeling the base film after laminating the protective film. According to this method, further thinning of the linear polarization layer can be achieved.
The thickness of the linear polarization layer as the PVA film is preferably 1 μm or more, may be 2 μm or more, may be 5 μm or more, and is preferably 30 μm or less, more preferably 15 μm or less, may be 10 μm or less, and may be 8 μm or less.
(polarizing plate)
The laminated bodies 1 to 4 may include a polarizing plate 31 having a protective film on one or both surfaces of the linear polarizing layer. The linear polarization layer and the protective film may be in direct contact, or may be laminated via a 3 rd lamination layer (adhesive layer or pressure-sensitive adhesive layer).
(protective film)
As the protective film, for example, a film formed of a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, water resistance, isotropy, stretchability, and the like is used. Specific examples of the thermoplastic resin include cellulose resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyether sulfone resin; polysulfone resin; a polycarbonate resin; polyamide resins such as nylon and aromatic polyamide; polyimide resin; polyolefin resins such as polyethylene, polypropylene and ethylene-propylene copolymers; a cyclic polyolefin resin having a ring system and a norbornene structure (also referred to as a norbornene-based resin); (meth) acrylic resins; a polyarylate resin; a polystyrene resin; polyvinyl alcohol resins and mixtures thereof.
The protective film may be a phase difference film having an optional phase difference value. The retardation film can be obtained by stretching (uniaxial stretching, biaxial stretching, or the like) a film made of the thermoplastic resin, or forming a liquid crystal layer on the film.
The protective film may be a film having an antireflection property, an antiglare property, a hard coat property, or the like. In the case where the protective film does not have the above-described characteristics, a surface functional layer such as an antireflection layer, an antiglare layer, or a hard coat layer may be provided on one surface of the polarizing plate. The surface functional layer is preferably disposed in direct contact with the protective film. The surface functional layer is preferably provided on the opposite side of the protective film from the linearly polarized layer side.
The protective film is usually 5 μm or more, but may be 10 μm or more, and is usually 200 μm or less, but may be 150 μm or less, or may be 100 μm or less, or may be 80 μm or less.
(Metal layer)
The metal layer 35 can be used, for example, as a conductive layer for a touch sensor constituting a touch panel. The metal layer 35 is a layer formed of 1 or more metals. The metal layer 35 may have a passivation film (oxide film) formed on its surface. The metal layer 35 may have a single-layer structure or a multilayer structure. The passivation film was not counted as 1 layer.
Examples of the metal constituting the metal layer 35 include aluminum (Al), copper (Cu), gold (Au), silver (Ag), titanium (Ti), palladium (Pd), chromium (Cr), nickel (Ni), tungsten (W), platinum (Pt), iron (Fe), indium (In), tin (Sn), iridium (Ir), rhodium (Rh), neodymium (Nd), molybdenum (Mo), and an alloy containing 2 or more of these metals. Among them, the metal layer 35 preferably contains aluminum or copper as a main component, and may contain titanium as an additive. Here, the main component is a metal which accounts for 50 mass% or more of the metal constituting the metal layer 35.
The metal layer 35 may be formed on the light-transmitting substrate, for example, a continuous film formed over the entire surface of the light-transmitting substrate, or a metal wiring layer formed on the surface of the light-transmitting substrate. The metal wiring layer may be a metal mesh. The light-transmitting base material may be any material having light-transmitting properties, and examples thereof include films, glass substrates, and the like using a resin material described as a thermoplastic resin for forming the protective layer.
The method for forming the metal layer 35 is not particularly limited as long as it is formed on the surface of the light-transmitting substrate by, for example, vapor deposition methods such as chemical vapor deposition or physical vapor deposition, inkjet printing, gravure printing, electroplating, electroless plating, or the like. The metal layer 35 is preferably formed by sputtering.
The thickness of the metal layer 35 is usually 0.01 μm or more, but may be 0.05 μm or more, and is preferably 3 μm or less, more preferably 1 μm or less, and still more preferably 0.8 μm or less from the viewpoint of thickness reduction.
When the metal layer 35 is a metal wiring layer, the line width thereof is usually 10 μm or less, or may be 5 μm or less, or may be 3 μm or less, or may be 0.5 μm or more.
(1 st bonding layer, 2 nd bonding layer, 3 rd bonding layer)
Examples of the 1 st bonding layer, the 2 nd bonding layer, and the 3 rd bonding layer (hereinafter, these layers may be collectively referred to as "bonding layer") include an adhesive layer and an adhesive layer.
The adhesive layer is a layer formed using an adhesive. The pressure-sensitive adhesive is a substance exhibiting adhesiveness by adhering itself to an adherend, and is called a so-called pressure-sensitive adhesive. The adhesive may be the adhesive composition described above, and a known adhesive having excellent optical transparency may be used. As the known adhesive, for example, an adhesive containing a base polymer such as an acrylic polymer, a urethane polymer, a silicone polymer, or a polyvinyl ether can be used. The adhesive may be an active energy ray-curable adhesive, a thermosetting adhesive, or the like. Among them, an adhesive comprising an acrylic resin excellent in transparency, adhesion, removability (reworkability), weather resistance, heat resistance and the like as a base polymer is suitable. The pressure-sensitive adhesive layer is preferably composed of a pressure-sensitive adhesive containing a (meth) acrylic resin, a crosslinking agent, and a silane coupling agent, and may contain other components.
The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 5 μm or more, and may be 10 μm or more, and may be 15 μm or more, and may be 20 μm or more, and may be 25 μm or more, and is usually 300 μm or less, and may be 250 μm or less, and may be 100 μm or less, and may be 50 μm or less.
The adhesive layer can be formed by curing a curable component in the adhesive composition. The adhesive composition used for forming the adhesive layer is an adhesive other than a pressure-sensitive adhesive (adhesive), and examples thereof include an aqueous adhesive and an active energy ray-curable adhesive.
Examples of the aqueous adhesive include an adhesive obtained by dissolving or dispersing a polyvinyl alcohol resin in water. The drying method when the aqueous adhesive is used is not particularly limited, and for example, a method of drying using a hot air dryer or an infrared dryer may be used.
Examples of the active energy ray-curable adhesive include solvent-free active energy ray-curable adhesives containing curable compounds that cure by irradiation with active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays. The use of the solvent-free active energy ray-curable adhesive can improve interlayer adhesion.
The active energy ray-curable adhesive preferably contains one or both of a cationically polymerizable curable compound and a radically polymerizable curable compound, in order to exhibit good adhesion. The active energy ray-curable adhesive may further include a cationic polymerization initiator such as a photo-cationic polymerization initiator or a radical polymerization initiator for initiating the curing reaction of the curable compound.
The thickness of the adhesive layer is preferably 0.1 μm or more, but may be 0.5 μm or more, and is preferably 10 μm or less, but may be 5 μm or less.
(Release film)
When the laminate includes the 2 nd adhesive layer 23 on the side of the 2 nd liquid crystal cured layer 12 opposite to the side of the adhesive layer 21 and the 2 nd adhesive layer 23 is an adhesive layer, the laminate may include a release film that covers and protects the 2 nd adhesive layer 23 and is releasable from the 2 nd adhesive layer 23. The release film has a base material layer and a release treatment layer. The substrate layer may be a resin film. The resin film may be formed of, for example, a thermoplastic resin used for forming the protective film. The release treatment layer may be a known release treatment layer, and examples thereof include a layer formed by applying a release agent such as a fluorine compound or a silicone compound to a base layer.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
The materials used in the examples and comparative examples are shown below.
[ alicyclic epoxy Compound ]
CEL2021P:
3, 4-epoxycyclohexane carboxylic acid 3',4' -epoxycyclohexyl methyl ester (trade name: CEL2021P, manufactured by Daicel Co., ltd.)
[ aliphatic epoxy Compound ]
EHPE3150:
1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol (trade name: EHPE3150, manufactured by Daicel Co., ltd.)
EX-211:
Neopentyl glycol diglycidyl ether (trade name: DENACOL EX-211, manufactured by Nagase Chemtex Co., ltd.)
2-EHGE:
2-ethylhexyl glycidyl ether (manufactured by Tokyo chemical industry Co., ltd.)
[ oxetane Compound ]
TCM-104:
3- [ (benzyloxy) methyl ] -3-ethyloxetane (comprising an aromatic oxetane compound, trade name: TCM-104, manufactured by TRONLY)
OXT-221:
3-Ethyl-3 { [ (3-Ethyloxybutan-3-yl) methoxy ] methyl } oxetan (trade name: OXT-221, manufactured by Toyama Synthesis Co., ltd.)
[ aromatic epoxy Compound ]
EX-201:
Resorcinol glycidyl ether (trade name: DENACOL EX-201, manufactured by Nagase Chemtex Co., ltd.)
[ photo cationic polymerization initiator ]
CPI-100P:
Sulfonium photopolymerization initiator (trade name: CPI-100P, san-Apro (Co., ltd., 50% by mass solution)
[ photosensitive auxiliary ]
DEN:
1, 4-Diethoxynaphthalene
[ preparation of adhesive compositions (1) to (8) ]
The curable components, photopolymerization initiators, and photosensitizing auxiliaries shown in tables 1 and 2 were mixed and defoamed in the mixing ratios shown in tables 1 and 2, to prepare liquid adhesive compositions (1) to (8), respectively. The numerical values in tables 1 and 2 represent parts by mass. The photopolymerization initiator was blended in the form of a 50 mass% propylene carbonate solution, and the values shown in tables 1 and 2 were amounts as solid components contained therein.
[ preparation of adhesive composition (9) and (10) ]
The curable components, photopolymerization initiator and photo-sensitive auxiliary agent described in Table 3 were mixed and defoamed in the mixing ratios described in Table 3 to prepare liquid adhesive compositions (9) and (10), respectively. The numerical values in table 3 represent parts by mass. The photopolymerization initiator was blended in the form of a 50 mass% propylene carbonate solution, and the values shown in table 3 are amounts as solid components contained therein.
[ production of polarizing plate ]
A polyvinyl alcohol film having a thickness of 20 μm, a polymerization degree of 2400 and a saponification degree of 99.9% or more was uniaxially stretched at a stretching ratio of 4.5 times on a roller heated to a temperature of 125℃and immersed in water at a temperature of 28℃for 30 seconds while maintaining the stretched state, and then immersed in a dyeing bath at a temperature of 28℃for 30 seconds while containing 0.05 parts by mass of iodine and 5 parts by mass of potassium iodide per 100 parts by mass of water. Then, the solution was immersed in an aqueous boric acid solution (1) containing 5.5 parts by mass of boric acid and 15 parts by mass of potassium iodide per 100 parts by mass of water at 64℃for 110 seconds. Then, the solution was immersed in an aqueous boric acid solution (2) containing 5.5 parts by mass of boric acid and 15 parts by mass of potassium iodide per 100 parts by mass of water at 67℃for 30 seconds. Thereafter, the resultant was washed with pure water at a temperature of 10℃and dried at a temperature of 80℃to obtain a linearly polarized layer. The thickness of the resulting linearly polarized layer was 7. Mu.m.
A protective film (cycloolefin (COP) film having a hard coat layer on one surface) having a thickness of 25 μm was bonded to one surface of the obtained linear polarizing layer via an aqueous adhesive (thickness: 0.1 μm), and the laminate was bonded to the surface (COP film side surface) opposite to the hard coat layer at the time of bonding, and dried at a temperature of 90 ℃. The surface of the protective film on the COP film side was subjected to corona treatment before the linearly polarizing layer was bonded to the protective film. The aqueous adhesive was prepared by adding 3 parts by mass of acetoacetyl-modified polyvinyl alcohol (Z-200, manufactured by Japanese Synthesis) and 1.5 parts by mass of a water-soluble polyamide epoxy Resin (Sumirez Resin 650, manufactured by Chemtex, aqueous solution having a solid content of 30%) to 100 parts by mass of water.
[ production of 1 st liquid Crystal cured layer (1) with substrate ]
A1 st orientation film (1) is formed by applying a coating liquid for forming the 1 st orientation film (1) to a base film (1) which is a transparent resin base and drying the coating liquid, thereby subjecting the film to a lambda/2 orientation treatment. Then, a coating liquid containing a polymerizable discotic liquid crystal monomer is applied to the 1 st alignment film (1), and the liquid crystal monomer is polymerized and cured by heating and UV irradiation, and then the alignment is immobilized, whereby the 1 st liquid crystal cured layer (1) with a substrate having a 1 st liquid crystal cured layer (1) with a thickness of 2 μm is formed on the substrate film (1). The 1 st liquid crystal solidified layer (1) is a lambda/2 phase difference layer.
[ production of 1 st liquid Crystal cured layer (2) with substrate ]
(preparation of composition for Forming photo-alignment film)
The following ingredients were mixed, and the resultant mixture was stirred at a temperature of 80 ℃ for 1 hour, thereby obtaining a composition for forming a photo-alignment film.
Light-oriented polymer [ a polymer represented by the following formula (number average molecular weight: about 28200, mw/Mn: 1.82) ] described in JP-A2013-33249: 2 parts by mass
[ chemical formula 2]
Figure BDA0003999031520000211
Solvent [ o-xylene ]: 98 parts by mass
(preparation of composition (1) for Forming a liquid Crystal cured layer)
The following components were mixed and stirred at a temperature of 80℃for 1 hour, thereby obtaining a composition (1) for forming a liquid crystal cured layer.
A polymerizable liquid crystal compound (X1) represented by the following formula: 100 parts by mass
[ chemical formula 3]
Figure BDA0003999031520000221
A polymerizable liquid crystal compound (X2) represented by the following formula: 33 parts by mass
[ chemical formula 4]
Figure BDA0003999031520000222
Polymerization initiator [ 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) -1-butanone (Irgacure (registered trademark) 369; manufactured by BASF Japan Co.) ]: 8 parts by mass
Leveling agents [ polyacrylate compounds (BYK-361N; BYK-Chemie Co.) ]: 0.1 part by mass
Reactive additive [ LALOMER LR9000; BASF Japan Co. ]: 6.7 parts by mass
Solvent [ cyclopentanone ]: 546 parts by mass
Solvent [ N-methylpyrrolidone ]: 364 parts by mass
(production of 1 st liquid Crystal cured layer (2) with substrate)
The surface of the base material film (2) (manufactured by UNITKA Co., ltd. "FF-50", single-sided release-treated polyethylene terephthalate (PET) film, thickness of the base material: 50 μm) on the side opposite to the release-treated surface was subjected to corona treatment. The composition for forming a photo-alignment film prepared above was applied to the corona-treated surface by a bar coater, dried at 120℃for 2 minutes, and cooled to room temperature to form a dried film. The dried film was subjected to a treatment to give a film thickness of 100mJ/cm 2 Polarized ultraviolet light was irradiated so as to have an intensity of 313nm, and a 1 st alignment layer (2) having a thickness of 100nm was formed as a photo-alignment film.
The composition (1) for forming a cured liquid crystal layer prepared above was coated on the 1 st alignment layer (2) using a bar coater to form a coating film. Then, the film was heated and dried at 120℃for 2 minutes, and then cooled to room temperature to obtain a dried film. Thereafter, the dried film was irradiated with an ultraviolet irradiation device at an exposure of 1000mJ/cm 2 Ultraviolet rays (365 nm basis)Thus, a 1 st liquid crystal cured layer (2) having a thickness of 2 μm was formed by curing the polymerizable liquid crystal compound in a state of being oriented in the horizontal direction with respect to the surface of the 1 st liquid crystal cured layer (2), and the 1 st liquid crystal cured layer (2) with a base material layer was obtained. The layer structure of the 1 st liquid crystal cured layer (2) with the substrate layer is the substrate film (2)/the 1 st alignment layer (2)/the 1 st liquid crystal cured layer (2).
[ production of 2 nd liquid Crystal cured layer (1) with substrate ]
An alignment film for lambda/4 alignment, namely a 2 nd alignment film (1) formed by subjecting a substrate film (3) as a transparent resin substrate to a rubbing treatment is formed. Then, a coating liquid containing a rod-like polymerizable nematic liquid crystal monomer is applied to the 2 nd alignment film (1), and the liquid crystal monomer is polymerized and cured to be immobilized while maintaining refractive index anisotropy, thereby obtaining a 2 nd liquid crystal cured layer (1) with a substrate, in which a 2 nd liquid crystal cured layer having a thickness of 1 μm is formed on the substrate film (3). The 2 nd liquid crystal solidified layer (1) is a lambda/4 phase difference layer.
[ production of 2 nd liquid Crystal cured layer (2) with substrate ]
(preparation of composition for Forming orientation film)
A composition for forming an alignment film was prepared by adding 2-butoxyethanol to commercially available SUNEVR SE-610 (manufactured by Nissan chemical Co., ltd.) as an alignment polymer. The content of the solid content relative to the total amount of the composition for forming an alignment film was 1%, and the content of the solvent was 99%. The solid content of the oriented polymer is converted according to the concentration described in the article specifications.
(preparation of composition (2) for Forming a liquid Crystal cured layer)
The following components were mixed and stirred at 80℃for 1 hour, and then cooled to room temperature to obtain a composition (2) for forming a liquid crystal cured layer. The content ratios shown below are the content ratios of the respective components with respect to the total amount of the composition (2) for forming a liquid crystal cured layer.
A polymerizable liquid crystal compound [ LC242 ] represented by the following formula; BASF Co.): 19.2 mass%
[ chemical formula 5]
Figure BDA0003999031520000241
Polymerization initiator [ Irgacure907; BASF Japan Co. ]: 0.5 mass%
Leveling agent [ BYK-Chemie JAPAN; BYK361N ]: 0.1 mass%
Reactive additive [ Laromer LR-9000; BASF Japan Co. ]: 1.1% by mass
Solvent [ propylene glycol 1-monomethyl ether 2-acetate (PGMEA) ]: 79.1% by mass
(production of 2 nd liquid Crystal cured layer (2) with substrate)
The surface of the base film (4) (cycloolefin polymer (COP) film, ZF-14, manufactured by ZEON Co., ltd.) was treated 1 time with a corona treatment apparatus under conditions of an output of 0.3kW and a treatment speed of 3 m/min. The composition for forming an alignment film prepared above was applied to the corona-treated surface by a bar coater, and dried at 90℃for 1 minute to obtain the 2 nd alignment layer (2). The film thickness of the 2 nd alignment layer (2) was measured by a laser microscope, and found to be 1. Mu.m.
The liquid crystal cured layer-forming composition (2) prepared above was coated on the 2 nd alignment layer (2) using a bar coater to form a coating film. Then, after drying at 90℃for 1 minute, ultraviolet rays (cumulative light amount at 365nm wavelength under nitrogen atmosphere: 1000 mJ/cm) were irradiated with a high-pressure mercury lamp 2 ) Thus, a 2 nd liquid crystal cured layer (2) having a thickness of 500nm was formed by curing the polymerizable liquid crystal compound in a state of being oriented in a vertical direction with respect to the surface of the 2 nd liquid crystal cured layer (2), and the 2 nd liquid crystal cured layer (2) with a base material layer was obtained. The layer structure of the 2 nd liquid crystal solidified layer (2) with the substrate layer is the substrate film (4)/the 2 nd orientation layer (2)/the 2 nd liquid crystal solidified layer (2).
[ example 1 ]
(production of liquid Crystal cured layer laminate (1))
Corona treatment was performed on the 1 st liquid crystal cured layer (1) side of the 1 st liquid crystal cured layer (1) with a substrate and the 2 nd liquid crystal cured layer (1) side of the 2 nd liquid crystal cured layer (1) with a substrate obtained in the above. The 1 st liquid crystal cured layer (1) side of the 1 st liquid crystal cured layer (1) with a substrate and the 2 nd liquid crystal cured layer (1) side of the 2 nd liquid crystal cured layer (1) with a substrate were bonded via the adhesive composition (1) prepared as described above using a laminator. At this time, the 1 st liquid crystal cured layer (1) with a substrate and the 2 nd liquid crystal cured layer (1) with a substrate are laminated such that the angle formed by the slow axis of the 1 st liquid crystal cured layer (1) and the slow axis of the 2 nd liquid crystal cured layer (1) is 120 °. The coating amount of the adhesive composition (1) was adjusted so that the thickness of the adhesive layer (1) formed from the adhesive composition (1) was 4.5. Mu.m.
Then, from the 2 nd liquid crystal cured layer (1) side with the substrate, an ultraviolet irradiation device (manufactured by FUSION UV SYSTEMS Co., ltd.) was used to accumulate 400mJ/cm of light 2 (UV-B) ultraviolet irradiation to cure the adhesive composition (1) to obtain a liquid crystal cured layer laminate (1) having a layer structure of a 1 st liquid crystal cured layer (1) with a substrate (substrate film (1)/1 st alignment film (1)/1 st liquid crystal cured layer (1))/adhesive layer (1)/2 nd liquid crystal cured layer (1) with a substrate (2 nd liquid crystal cured layer (1)/2 nd alignment film (1)/substrate film (3)).
(production of laminate)
The substrate film (1) on the 1 st liquid crystal cured layer (1) side with the substrate and the 1 st alignment film (1) were peeled off from the liquid crystal cured layer laminate (1), and the exposed surface was bonded to the linearly polarizing layer side of the polarizing plate obtained as described above using a 1 st bonding layer (acrylic adhesive layer having a thickness of 5 μm). The angle formed by the absorption axis of the linear polarization layer and the slow axis of the 1 st liquid crystal cured layer (1) (lambda/2 phase difference layer) was 12.5 deg., and the angle formed by the absorption axis of the linear polarization layer and the slow axis of the 2 nd liquid crystal cured layer (1) (lambda/4 phase difference layer) was 107.5 deg.. Then, the 2 nd liquid crystal cured layer (1) side substrate film (3) and the 2 nd alignment film (1) with the substrate were peeled off, and a 2 nd lamination layer (acrylic pressure-sensitive adhesive layer having a thickness of 15 μm) was laminated on the exposed surface to obtain a laminate (1). The laminate (1) has a layer structure of a protective film (hard coat layer/COP film)/3 rd lamination layer (aqueous adhesive layer)/linear polarization layer/1 st lamination layer (adhesive layer)/1 st liquid crystal cured layer (1) (lambda/2 retardation layer)/adhesive layer (1)/2 nd liquid crystal cured layer (1) (lambda/4 retardation layer)/2 nd lamination layer (adhesive layer).
[ examples 2 to 7, comparative example 1 ]
Laminates (2) to (8) were obtained in the same manner as in example 1, except that adhesive layers (2) to (8) were formed using adhesive compositions (2) to (8) instead of adhesive composition (1).
The laminates obtained in examples 1 to 7 and comparative example 1 were evaluated as follows. The results are shown in tables 1 and 2.
[ evaluation of Metal corrosiveness ]
After corona treatment of the protective film surfaces of the laminates (1) to (8) produced in examples and comparative examples, an adhesive layer side of an adhesive sheet (a material having an adhesive layer with a thickness of 150 μm formed on a release film) was bonded to the protective film, and a laminate with an adhesive sheet was obtained. The laminate with the adhesive sheet was cut into a size of 60mm (absorption axis direction of the linear polarizing layer) ×50mm (transmission axis direction of the linear polarizing layer), and the 2 nd lamination layer was laminated on the metal layer side of the 340mm×260mm glass substrate with the metal layer. The glass substrate with a metal layer was a substrate having al—ti deposited on the surface of alkali-free glass. Thereafter, 0.4t glass having a size of 80mm×80mm was bonded to the surface of the pressure-sensitive adhesive layer exposed by peeling the release film from the laminate with the pressure-sensitive adhesive sheet. It was placed in an autoclave at a temperature of 50℃and a pressure of 5kgf/cm 2 (490.3 kPa) was pressurized for 20 minutes to give a test sample (1). The layer structure of the test sample (1) was 0.4t glass/adhesive layer/protective film (hard coat layer/COP film)/3 rd lamination layer (aqueous adhesive layer)/linear polarization layer/1 st lamination layer (adhesive layer)/1 st liquid crystal cured layer (1) (λ/2 retardation layer)/any of the adhesive layers (1) to (8)/2 nd liquid crystal cured layer (2) (λ/4 retardation layer)/2 nd lamination layer (adhesive layer)/glass substrate with metal layer (al—ti vapor deposition layer/alkali-free glass).
After the test sample (1) was left to stand in a hot and humid environment at a temperature of 85 ℃ and a relative humidity of 85% for 240 hours and 500 hours, a backlight was irradiated from the back surface of the glass substrate with a metal layer in a dark room, and the state of the metal layer on the portion to which the test sample (1) was bonded was observed from the 0.4t glass side, and evaluation was performed based on the following criteria.
A: the number of pitting (holes through which light can pass) generated on the surface of the metal layer is 5 or less.
B: the number of pitting (holes through which light can pass) generated on the surface of the metal layer is more than 5 and less than 15.
C: the number of pitting (holes through which light can pass) generated on the surface of the metal layer is 15 or more.
[ evaluation of optical durability ]
The laminate (1) to (8) produced in examples and comparative examples were cut to a size of 30mm×30mm, and laminated on a glass substrate via a 2 nd lamination layer to obtain evaluation samples. The glass substrate used was an alkali-free glass substrate [ trade name "Eagle XG" manufactured by Corning Co., ltd.). Using the evaluation sample, a wet heat test was performed for 24 hours in a wet heat environment at a temperature of 85 ℃ and a relative humidity of 85%, and the transmittance of the visibility-corrected monomer and the visibility-corrected polarization degree before and after the wet heat test were determined in accordance with the following procedures. First, an evaluation sample was placed on a spectrophotometer (product name "V7100" manufactured by japan spectroscopy) with an integrating sphere so that incident light was incident from a polarizing film surface (the side opposite to the glass substrate), and the transmittance and the polarization were measured. Then, the transmittance and the polarization degree were subjected to visibility correction using a 2-degree field of view (C light source) of JIS Z8701 to determine a visibility correction single transmittance and a visibility correction polarization degree.
The value obtained by subtracting the value of the visibility-correcting monomer transmittance before the wet heat test from the value of the visibility-correcting monomer transmittance after the wet heat test was calculated as the variation of the monomer transmittance, and evaluated based on the following criteria.
A: the variation in the transmittance of the monomer is 1.70 or less.
B: the amount of change in the transmittance of the monomer is greater than 1.70.
The value obtained by subtracting the value of the visibility correction polarization degree before the damp-heat test from the value of the visibility correction polarization degree after the damp-heat test was calculated as the change amount of the polarization degree, and evaluated based on the following criteria.
A: the amount of change in the degree of polarization is 0.3 or less.
B: the amount of change in the degree of polarization is greater than 0.3.
[ evaluation of adhesion ]
The laminated bodies (1) to (8) produced in examples and comparative examples were cut to a length of 200mm (absorption axis direction of the linearly polarized layer) and a width of 25mm (transmission axis direction of the linearly polarized layer), and then the 2 nd lamination layer was laminated on the sodium glass substrate. Then, a blade of a dicing blade was inserted between the 1 st liquid crystal cured layer and the 2 nd liquid crystal cured layer, and the peeled portion was peeled off from the end portion by 30mm in the longitudinal direction, and the peeled portion was held by a holding portion made by a universal tensile tester (manufactured by Shimadzu corporation) [ AG-1 ]. The test piece in this state was subjected to a temperature of 23℃and a relative humidity of 55% in an atmosphere in accordance with JIS K6854-2:1999 "adhesive-peel adhesion Strength test method-part 2: 180 degree peel "180 degree peel test was performed at a jig moving speed of 300 mm/min, and an average peel force of 170mm length excluding 30mm of the nip portion was obtained. Note that the term "incapable of being cut" as indicated by the term "2" in tables 1 and 2 means that the adhesion between the 1 st liquid crystal cured layer and the 2 nd liquid crystal cured layer is strong, and that the 1 st liquid crystal cured layer and the 2 nd liquid crystal cured layer cannot be separated even if a blade of a dicing blade is interposed therebetween.
[ Table 1 ]
Figure BDA0003999031520000281
1: amount of solid component
2: can not be cut open
TABLE 2
Figure BDA0003999031520000291
1: amount of solid component
2: can not be cut open
Example 8
(production of liquid Crystal cured layer laminate (2))
Corona treatment was performed on the 1 st liquid crystal cured layer (2) side of the 1 st liquid crystal cured layer (2) with a substrate and the 2 nd liquid crystal cured layer (2) side of the 2 nd liquid crystal cured layer (2) with a substrate obtained in the above. The 1 st liquid crystal cured layer (2) side of the 1 st liquid crystal cured layer (2) with a substrate and the 2 nd liquid crystal cured layer (2) side of the 2 nd liquid crystal cured layer (2) with a substrate were bonded via the adhesive composition (9) prepared above using a laminator. The coating amount of the adhesive composition (9) was adjusted so that the thickness of the adhesive layer (9) formed from the adhesive composition (9) was 4.5. Mu.m.
Then, from the 2 nd liquid crystal cured layer (2) side with the substrate, an ultraviolet irradiation device (manufactured by FUSION UV SYSTEMS Co., ltd.) was used to accumulate 400mJ/cm of light 2 (UV-B) ultraviolet irradiation to cure the adhesive composition (9), thereby obtaining a liquid crystal cured layer laminate (2) having a layer structure of a 1 st liquid crystal cured layer (2) with a substrate (substrate film (2)/1 st alignment film (2)/1 st liquid crystal cured layer (2))/adhesive layer (9)/2 nd liquid crystal cured layer (2) with a substrate (2 nd liquid crystal cured layer (2)/2 nd alignment film (2)/substrate film (4)).
(production of laminate)
The surface of the liquid crystal cured layer laminate (2) on the side of the 1 st liquid crystal cured layer (2) with the base material, which is exposed by the release base film (2) and the 1 st alignment film (2), was bonded to the linearly polarizing layer side of the polarizing plate obtained as described above using the 1 st bonding layer (acrylic adhesive layer having a thickness of 5 μm). The absorption axis of the linear polarization layer forms an angle of 45 degrees with the slow axis of the 1 st liquid crystal curing layer (2). Then, the base material film (4) and the 2 nd alignment film (2) on the 2 nd liquid crystal cured layer (2) side with the base material are peeled off, and a 2 nd lamination layer (acrylic pressure-sensitive adhesive layer having a thickness of 15 μm) is laminated on the exposed surface to obtain a laminate (9). The laminate (9) has a layer structure of a protective film (hard coat layer/COP film)/a 3 rd lamination layer (aqueous adhesive layer)/a linear polarization layer/a 1 st lamination layer (adhesive layer)/a 1 st liquid crystal cured layer (2) (horizontal alignment retardation layer)/an adhesive layer (9)/a 2 nd liquid crystal cured layer (2) (vertical alignment retardation layer)/a 2 nd lamination layer (adhesive layer).
Comparative example 2
A laminate (10) was obtained in the same manner as in example 8, except that the adhesive composition (10) was used in place of the adhesive composition (9) to form the adhesive layer (10).
The laminate obtained in example 8 and comparative example 2 was evaluated as follows. The results are shown in Table 3.
[ evaluation of Metal corrosiveness ]
After corona treatment of the protective film surfaces of the laminates (9) and (10) produced in examples and comparative examples, an adhesive layer side of an adhesive sheet (a material having an adhesive layer with a thickness of 150 μm formed on a release film) was bonded to the protective film, and a laminate with an adhesive sheet was obtained. The laminate with the adhesive sheet was cut into a size of 60mm (absorption axis direction of the linear polarizing layer) ×50mm (transmission axis direction of the linear polarizing layer), and the 2 nd lamination layer was laminated on the metal layer side of the 340mm×260mm glass substrate with the metal layer. The glass substrate with a metal layer was a substrate having al—ti deposited on the surface of alkali-free glass. Thereafter, 0.4t glass having a size of 80mm×80mm was bonded to the surface of the pressure-sensitive adhesive layer exposed by peeling the release film from the laminate with the pressure-sensitive adhesive sheet. It was placed in an autoclave at a temperature of 50℃and a pressure of 5kgf/cm 2 (490.3 kPa) was pressurized for 20 minutes to give a test sample (2).
The layer structure of the test sample (2) was 0.4t glass/adhesive layer/protective film (hard coat layer/COP film)/3 rd lamination layer (aqueous adhesive layer)/linear polarization layer/1 st lamination layer (adhesive layer)/1 st liquid crystal cured layer (2) (horizontal alignment retardation layer)/adhesive layer (9) or (10)/2 nd liquid crystal cured layer (2) (vertical alignment retardation layer)/2 nd lamination layer (adhesive layer)/glass substrate with metal layer (Ti (100 nm)/Al (500 nm)/alkali-free glass).
After the test sample (2) was left to stand in a hot and humid environment at a temperature of 85 ℃ and a relative humidity of 85% for 250 hours and 500 hours, a backlight was irradiated from the back surface of the glass substrate with a metal layer in a dark room, and the state of the metal layer in the portion to which the test sample was bonded was observed from the 0.4t glass side, and evaluation was performed based on the following criteria.
A: the number of pitting (holes through which light can pass) generated on the surface of the metal layer is 5 or less.
B: the number of pitting (holes through which light can pass) generated on the surface of the metal layer is more than 5 and less than 15.
C: the number of pitting (holes through which light can pass) generated on the surface of the metal layer is 15 or more.
[ evaluation of optical durability ]
The laminates (9) and (10) produced in examples and comparative examples were cut to a size of 30mm×30mm, and laminated on a glass substrate via a 2 nd lamination layer to obtain evaluation samples. The glass substrate used was an alkali-free glass substrate [ trade name "Eagle XG" manufactured by Corning Co., ltd.). Using the evaluation sample, a wet heat test was performed for 24 hours in a wet heat environment at a temperature of 85 ℃ and a relative humidity of 85%, and the transmittance of the visibility-corrected monomer and the visibility-corrected polarization degree before and after the wet heat test were determined in accordance with the following procedures. First, an evaluation sample was placed on a spectrophotometer (product name "V7100" manufactured by japan spectroscopy) with an integrating sphere so that incident light was incident from a polarizing film surface (the side opposite to the glass substrate), and the transmittance and the polarization were measured. Then, the transmittance and the polarization degree were subjected to visibility correction using a 2-degree field of view (C light source) of JIS Z8701 to determine a visibility correction single transmittance and a visibility correction polarization degree.
The absolute value of the value obtained by subtracting the value of the visibility-correcting monomer transmittance before the wet heat test from the value of the visibility-correcting monomer transmittance after the wet heat test was calculated as the variation of the monomer transmittance, and evaluated based on the following criteria.
A: the variation in the transmittance of the monomer is 1.70 or less.
B: the amount of change in the transmittance of the monomer is greater than 1.70.
The value obtained by subtracting the value of the visibility correction polarization degree before the damp-heat test from the value of the visibility correction polarization degree after the damp-heat test was calculated as the change amount of the polarization degree, and evaluated based on the following criteria.
A: the amount of change in the degree of polarization is 0.3 or less.
B: the amount of change in the degree of polarization is greater than 0.3.
[ Table 3 ]
Figure BDA0003999031520000331
/>

Claims (7)

1. A laminate of a substrate and a carrier,
comprising, in order, a 1 st liquid crystal cured layer as a cured product layer of a polymerizable liquid crystal compound, an adhesive layer, and a 2 nd liquid crystal cured layer as a cured product layer of a polymerizable liquid crystal compound,
the adhesive layer is a cured product layer of an adhesive composition containing a curable component and a photo-cationic polymerization initiator,
the curable component comprises an alicyclic epoxy compound and an oxetane compound having 2 or more oxetanyl groups in the molecule,
The content of the photo-cationic polymerization initiator in the adhesive composition is 2.0 parts by mass or less relative to 100 parts by mass of the curable component.
2. The laminate according to claim 1, wherein,
the oxetane compound is an aliphatic compound.
3. The laminate according to claim 1 or 2, wherein,
the photo-cation polymerization initiator is an aromatic onium salt.
4. The laminate according to claim 3, wherein,
the anionic component of the photo-cationic polymerization initiator contains a fluorine atom.
5. The laminate according to claim 1 or 2, wherein,
the 1 st liquid crystal solidified layer is a lambda/2 phase difference layer,
the 2 nd liquid crystal solidified layer is a lambda/4 phase difference layer.
6. The laminate according to claim 5, further comprising a linearly polarizing layer laminated on a side of the 1 st liquid crystal cured layer opposite to the adhesive layer side.
7. The laminate according to claim 1 or 2, further comprising a metal layer laminated on a side of the 2 nd liquid crystal cured layer opposite to the adhesive layer side.
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