CN109564318A - Stacked film - Google Patents

Stacked film Download PDF

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Publication number
CN109564318A
CN109564318A CN201780048413.9A CN201780048413A CN109564318A CN 109564318 A CN109564318 A CN 109564318A CN 201780048413 A CN201780048413 A CN 201780048413A CN 109564318 A CN109564318 A CN 109564318A
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CN
China
Prior art keywords
layer
resin
film
stacked film
resin layer
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CN201780048413.9A
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Chinese (zh)
Inventor
藤长将司
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Publication of CN109564318A publication Critical patent/CN109564318A/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • 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
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering

Abstract

The present invention provides a kind of stacked film that high-polarization is also able to maintain under hygrothermal environment.A kind of stacked film includes polarizer layer, and wherein dichroism pigment is orientated in polyvinyl alcohol resin；Resin layer, using the resin film on the direction of the absorption axiss oblique with polarizer layer with slow axis as forming material；And adhesive layer, polarizer layer is carried out with resin layer be bonded, resin layer includes plasticizer, and adhesive layer contains the solidfied material of the adhesive composite of oxetane compound as forming material, and oxetane compound is in main chain with ehter bond.

Description

Stacked film
Technical field
The present invention relates to stacked films.
Background technique
In the past, the feed element as the polarised light in the display devices such as liquid crystal display device, additionally as polarised light Detecting element is widely used for polarization plates.About polarization plates, it is known that utilized in the single or double of polarizing coating (polarizer layer) viscous Connect the composition that agent etc. is fitted with protective film.
As polarizing coating, it is known that obtained by the dichroism pigments such as iodine are orientated in the film comprising polyvinyl alcohol resin Polarizing coating.Iodine in polarizing coating exists in the form of iodo-complexes, and dependent on the orientation of polyvinyl alcohol resin, iodo-complexes is certainly Body is also orientated.It is known: the light of visibility region to be absorbed by the iodo-complexes, polarizing coating shows polarization characteristic (polarization Degree).
In addition, as needed, having to the polarizing coating fitting for being equipped with protective film when polarization plates are applied to display device The various optical layers such as the phase plate or optical compensation films of optical characteristics (resin layer) (such as patent document 1).Have in optical layer When include the additives such as plasticizer for improving film properties.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2011-186481 bulletin
Summary of the invention
Subject to be solved by the invention
But the polarization plates recorded in patent document 1 (such as 60 DEG C of room temperature, humidity 95% in the case where being placed in hygrothermal environment In the environment of) in the case where, degree of polarization can reduce sometimes.
The present invention is to carry out in light of this situation, and its purpose is to provide high polarization is also able to maintain under hygrothermal environment The stacked film of degree.
Means for solving the problems
The inventors of the present invention have carried out in-depth study repeatedly in order to solve the above problems, results presumption: in hygrothermal environment The plasticizer for including in lower optical layer is mobile to polarizing coating, reacts with the iodo-complexes for facilitating polarised light, thus iodo-complexes It disappears, as a result the degree of polarization of obtained polarization plates reduces.In contrast, as bonding between polarizing coating and optical layer The forming material of oxidant layer, by the solidfied material of adhesive composite of the application comprising oxetane compound, prediction can press down Movement of the plasticizer processed to polarizing coating, has thus completed the present invention.
A scheme of the invention provides a kind of stacked film, includes polarizer layer, wherein dichroism pigment is in polyethylene It is orientated in alcohol system resin；Resin layer will have the tree of slow axis on the direction of the absorption axiss oblique with polarizer layer Adipose membrane is as forming material；And adhesive layer, polarizer layer is carried out with resin layer be bonded, resin layer includes plasticizer, Adhesive layer contains the solidfied material of the adhesive composite of oxetane compound as forming material, oxetanes Compound has ehter bond in main chain.
In a scheme of the invention, oxetane compound preferably comprises more than two oxetanes rings.
In a scheme of the invention, polarizer layer and resin layer all can be strips.
The effect of invention
A scheme according to the present invention, provides the stacked film that high-polarization is also able to maintain under hygrothermal environment.
Detailed description of the invention
Fig. 1 is the schematic cross-section for showing an example of layer structure of the stacked film of present embodiment.
Fig. 2 is the schematic cross-section for showing the variation of layer structure of the stacked film of present embodiment.
Specific embodiment
<stacked film>
Fig. 1 is the schematic cross-section for showing an example of layer structure of the stacked film of present embodiment.As shown in Figure 1, this reality The stacked film 1 for applying mode has polarizer layer 11, resin layer 21 and polarizer layer 11 is carried out be bonded glue with resin layer 21 Connect oxidant layer 31.In other embodiments, it can also be further laminated in the side opposite with resin layer 21 of polarizer layer 11 There is protective film.
The stacked film of present embodiment can be strip, or by the way that the stacked film of strip is cut into regulation Monolithic body obtained from length.The stacked film of strip includes the polarizer layer of strip and the resin layer of strip.About length The polarizer layer of strip and the resin layer of strip, as described later.
[polarizer layer]
Polarizer layer refers to the optical film having the following properties: it absorbs the straight line with the vibration plane parallel with optic axis Polarised light, and through the rectilinearly polarized light with the vibration plane orthogonal with optic axis.Specifically, the polarizing film of present embodiment The film that layer 11 is orientated in polyvinyl alcohol resin (hereinafter sometimes called " PVA system resin ") for dichroism pigment.
The thickness of polarizer layer 11 is preferably 30 μm or less, more preferably 25 μm or less, be more preferably 15 μm or less, Especially preferably 10 μm or less, particularly preferably 7 μm or less.
It, can be by including PVA when polarizer layer 11 is the film that dichroism pigment is orientated in PVA system resin It is that the film former material of resin is stretched and obtains polarizer layer 11.Polarizer layer 11 with a thickness of 7 μm or less when, will be formed in base The film comprising PVA system resin on material is stretched together with substrate, is later removed substrate, also available polarizer layer 11。
As the substrate that can be used in present embodiment, polypropylene screen, polyethylene terephthalate can be enumerated Film, polycarbonate membrane, tri acetyl cellulose membrane, norbornene film, polyester film, polystyrene film etc..
As PVA system resin used in present embodiment, it can enumerate and be saponified to obtain by polyvinyl acetate system resin PVA system resin.As polyvinyl acetate system resin, in addition to the homopolymer as vinyl acetate polyvinyl acetate with Outside, the copolymer of vinyl acetate with the other monomers that can be copolymerized with it can also be enumerated.As can be with vinyl acetate The other monomers of copolymerization can enumerate unsaturated carboxylic acid, alkene, vinyl ethers, unsaturated sulfonic acid, the acrylamide with ammonium Deng.
The saponification degree of PVA system resin is preferably 80 moles of % or more, more preferably 90 moles of % or more and 99.5 mole of % It below, is more preferably 94 moles of % or more and 99 mole of % or less.If saponification degree is 80 moles of % or more, obtained The humidity resistance of stacked film 1 improves.In addition, if saponification degree be 99.5 moles of % hereinafter, if can obtain that there is sufficient polarizability The stacked film 1 of energy.
PVA system resin may be partially modified modified polyvinylalcohol.It is, for example, possible to use based on ethylene and propylene etc. Olefin-modified object；Unsaturated carboxylic acid-modified object based on acrylic acid, methacrylic acid and butenoic acid etc.；Utilize unsaturated carboxylic acid Arrcostab, acrylamide etc. be modified obtained from substance.
The modification ratio of PVA system resin is preferably smaller than 30 moles of %, more preferably less than 10%.If being less than using modified ratio The PVA system resin of 30 moles of %, then can sufficiently adsorb dichroism pigment, can obtain the polarization with sufficient polarization property Piece.
The average degree of polymerization of PVA system resin is preferably 100 or more and 10000 or less, more preferably 1500 or more and 8000 It below, is more preferably 2000 or more and 5000 or less.If average degree of polymerization is 100 or more, can obtain having sufficient The polarizing film of polarization property.In addition, if average degree of polymerization be 10000 hereinafter, if favorable solubility in a solvent, it is easy to form Film comprising PVA system resin.
PVA system resin can be readily available commercially available product, as the preferred example of commercially available product, be indicated with trade name, can With enumerate Co., Ltd. KURARAY manufacture " PVA124 " and " PVA117 " (saponification degree is equal are as follows: 98~99 moles of %), " PVA624 " (saponification degree: 95~96 moles of %), " PVA617 " (saponification degree: 94.5~95.5 moles of %)；Japan's synthesis chemistry Industrial Co., Ltd manufacture " N-300 " and " NH-18 " (saponification degree is equal are as follows: 98~99 moles of %), " AH-22 " (saponification degree: 97.5~98.5 moles of %), " AH-26 " (saponification degree: 97~98.8 moles of %)；Japan Vam&Poval Co., Ltd., (saponification degree is equal are as follows: 98~99 rub by " JC-33 " (saponification degree: 99 moles of % or more), " JF-17 ", " JF-17L " and " JF-20 " Your %), " JM-26 " (saponification degree: 95.5~97.5 moles of %), " JM-33 " (saponification degree: 93.5~95.5 moles of %), " JP- 45 " (saponification degrees: 86.5~89.5 moles of %) etc..
As dichroism pigment used in present embodiment, iodine or dichroic organic dye etc. can be enumerated.As two Color organic dyestuff can enumerate red BR, red LR, red R, pink LB, magenta BL, purplish red GS, sky blue LG, lemon yellow, indigo plant BR, indigo plant 2R, navy blue RY, green LG, purple LB, purple B, black H, black B, black GSP, Huang 3G, Huang R, orange LR, orange 3R, scarlet GL, scarlet KGL, just It is arnotto, brilliant violet BK, super indigo plant (supra blue) G, super indigo plant GL, super orange GL, direct sky blue, chlorazol fast orange d S, strong It is black.
One kind can be only used alone in dichroism pigment, can also share two or more.
[resin layer]
The tree that the resin layer 21 of present embodiment will have slow axis on the direction of the absorption axiss oblique with polarizer layer 11 Adipose membrane is as forming material.Such resin film can be manufactured with drawn processing, above-mentioned resin film with polarizer layer 11 Remain tensile stress on the direction of absorption axiss oblique.The residual stress for remaining on the resin film can become the degree of polarization of polarization plates One of the reason of reduction.
Resin layer 21 with there is slow axis on the direction of the absorption axiss oblique of polarizer layer 11, such as the angle of slow axis is opposite In the absorption axiss of polarizer layer 11 be preferably 45 ± 10 ° or 135 ± 10 °.By making the angle above range of slow axis, fast axle side To light phase and slow-axis direction light phase difference become pi/2.By making the phase difference pi/2 of fast axle and slow axis, When the stacked film 1 of present embodiment is applied to display device, the light circularly polarized light for having passed through stacked film 1 can be made.As a result, Even if the also excellent structure of visibility when across polarisation sem observation can be made.
The resin layer 21 of present embodiment, which preferably has, meets following formula (1)~(4) phase difference characteristics and wavelength color Dissipate the phase separation layer of characteristic.It is aobvious the stacked film 1 of present embodiment to be assembled by making resin layer 21 meet formula (1)~(4) When in showing device, the tone across polariscope from various directions (azimuth and polar angle) when picture can effectively be inhibited to become Change.Thereby, it is possible to improve the visibility of image display device.
(1)100nm≤Re(590)≤180nm、
(2) 0.5 < Rth(590)/Re(590)≤0.8、
(3)0.85≤Re(450)/Re(550) < 1.00 and
(4) 1.00 < Re(630)/Re(550)≤1.1。
In formula, Re(590)、Re(450)、Re(550)、Re(630) respectively indicate measurement wavelength be 590nm, 450nm, Phase difference value in face under 550nm, 630nm, Rth(590) indicate that measurement wavelength is the thickness direction phase difference value under 590nm.This Phase difference value and thickness direction phase difference value refer to the value measured in the environment of 23 DEG C of temperature, relative humidity 55% in a little faces.
About phase difference value R in facee, thickness direction phase difference value Rth, the refractive index of slow-axis direction is set as n in by facex、 The refractive index of fast axis direction in face (direction orthogonal with slow-axis direction in face) is set as ny, the refractive index of thickness direction is set as nz, when the thickness of optical film is set as d, by following formula (S1), formula (S2) Lai Dingyi.
(S1)Re=(nx-ny)×d
(S2)Rth=[{ (nx+ny)/2}-nz]×d
R from the viewpoint of more effectively inhibiting the tone variations in stacked film 1, in formula (1)e(590) preferably 105nm~170nm.R in formula (2)th(590)/ReIt (590) is preferably 0.6~0.75.R in formula (3)e(450)/Re(550) Preferably 0.86~0.98.R in formula (4)e(630)/ReIt (550) is preferably 1.01~1.06.
Such as by stretching to the film comprising aftermentioned resin, resin layer 21 can be made.It, can be with as stretch processing It enumerates and is uniaxially stretched, is biaxial stretch-formed etc..
As draw direction, mechanical flow direction (MD), the direction orthogonal with above-mentioned direction of unstretching film can be enumerated (TD), with the direction etc. of mechanical flow direction (MD) oblique.Herein, unstretching film refers to the film of unstretched state.In list During axis stretches, by unstretching film along either in these directions to stretching.On the other hand, it is biaxial stretch-formed can for It is biaxial stretch-formed while stretched simultaneously on two draw directions, or after being stretched along prescribed direction further along Other directions are stretched gradually biaxial stretch-formed.
Stretch processing can be carried out by following manner: for example using by 2 pairs or more of the peripheral speed increase of outlet side Roll, alongst (mechanical flow direction: MD) is stretched, or two side ends and the edge of unstretching film are caught with fixture The direction (TD) orthogonal with mechanical flow direction be extended.At this point, by adjusting the thickness or adjustment stretching ratio of film, energy It is enough to control phase difference value and wavelength dispersion in the range of above-mentioned formula (1)~(4).
In addition, by resin add wavelength dispersion regulator, wavelength dispersion value can be controlled for above-mentioned formula (3)~ (4) in the range of.
In general, the polarizing coating (polarizer layer) of strip has absorption axiss in the long side direction.From can be with roll-to-roll The resin layer of strip is bonded with the polarizer layer of strip and can be according to the slow of the absorption axiss and resin layer by mode The aspect that the mode that axis angulation reaches above range configures the two is set out, and resin layer 21 is preferably drawn by twin shaft It stretches and stretches and manufacture with being inclined by.
As the resin for forming resin film, it can be cited for example that acetate fiber prime system resin, cyclic olefine resin, polyolefin It is resin, acrylic resin, polyimides system resins, polycarbonate-based resin, polyester based resin etc..
The cellulose-containing partially or completely acetic acid esters compound of acetate fiber prime system resin packet.As acetate fiber prime system tree Rouge, it can be cited for example that triacetyl cellulose, diacetyl cellulose etc..
Resin film comprising acetate fiber prime system resin can be readily available commercially available product, the preference as commercially available product Son indicates with trade name, can enumerate Fuji Photo Film Co., Ltd.'s sale " FUJITAC (registered trademark) TD80 ", " FUJITAC (registered trademark) TD80UF " and " FUJITAC (registered trademark) TD80UZ "；OPTO plants of formulas of KONICA MINOLTA " KC8UX2M " and " KC8UY " etc. of commercial firm's sale.
The cyclic olefine resin for forming resin film is, for example, to have norbornene or polycyclic orbornene-based monomer etc The thermoplasticity amorphous resin (also referred to as amorphous polyolefins system resin) of the unit of monomer comprising cyclic olefin (cycloolefin). Cyclic olefine resin can be the hydride of the ring-opening polymerization polymer of above-mentioned cycloolefin, use the open loop of two or more cycloolefin total The hydride of polymers, or the addition of cycloolefin and chain olefin and/or aromatic compound with vinyl etc. is total Polymers.Alternatively, it is also possible to be imported with polar group.
Resin film is constituted using the copolymer of cycloolefin and chain olefin and/or the aromatic compound with vinyl In the case where, as chain olefin, ethylene, propylene etc. can be enumerated.In addition, as the aromatic compound with vinyl, Styrene, α-methylstyrene, core alkyl-substituted styrene etc. can be enumerated.In such copolymer, include cycloolefin The unit of monomer can be 50 moles of % hereinafter, preferably 15~50 moles of %.
In particular, using cycloolefin and chain olefin and the terpolymer of the aromatic compound with vinyl In the case of, can make the unit of the monomer comprising cycloolefin is fewer amount as described above.In the terpolymer, include The unit of the monomer of chain olefin is preferably 5~80 moles of %.In addition, the monomer comprising the aromatic compound with vinyl Unit be preferably 5~80 moles of %.
Cyclic olefine resin can be readily available commercially available product, as the preferred example of commercially available product, be indicated with trade name, TOPAS ADVANCED POLYMERS GmbH manufacture can be enumerated, sold in Japan by Polyplastics Co., Ltd. " ARTON (registered trademark) " of the sale of " TOPAS (registered trademark) ", JSR Corp., ZEON Co., Ltd., Japan sell The sale of " ZEONOR (ZEONOR) (registered trademark) " and " ZEONEX (ZEONEX) (registered trademark) ", Mitsui Chemicals, Inc " APEL (registered trademark) " etc..
The resin layer 21 of present embodiment be phase separation layer in the case where, the thickness of phase separation layer be preferably 10 μm or more and 50 μm or less.
For the resin layer 21 of present embodiment, on the basis of forming the resin of resin film, in order to resin film It assigns flexibility and is easy to stretch, also include plasticizer.As plasticizer, ethylene glycol, glycerol, propylene glycol, diethyl can be enumerated The polyalcohols such as glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane.
One kind can be used only in plasticizer, can also share two or more.It is particularly suitable for using ethylene glycol, glycerol.
[adhesive layer]
The adhesive layer 31 of present embodiment includes that the adhesive composite containing oxetane compound (hereinafter has When be known as " this composition ") solidfied material as forming material.Oxetane compound be cationically polymerizable compound it One, it can be solidified by the irradiation of active energy beam (for example, ultraviolet light, visible light, electron ray, X-ray etc.).
The thickness of adhesive layer 31 is preferably 0.01 μm or more and 5 μm or less, more preferably 0.01 μm or more and 2 μm with Under, further preferably 0.01 μm or more and 1 μm or less.If adhesive layer 31 with a thickness of 0.01 μm or more, can obtain Sufficient cementability.In addition, if adhesive layer 31 with a thickness of 5 μm hereinafter, if stacked film 1 be not easy bad order.
Adhesive layer 31 is preferably selected as follows: adhesive composite is applied in the way of with a thickness of 2~3 μm On tri acetyl cellulose membrane, so that its solidification is obtained evaluation sample, select the moisture permeability of the evaluation sample for 300g/m2·24hr Sample below.The lower limit value of moisture permeability is not particularly limited, for example, 50g/m2·24hr.By using for this moisture permeability Adhesive layer, the reduction of degree of polarization can be further reduced.
Evaluation sample can make as follows.Firstly, adhesive composite is applied in the way of with a thickness of 2~3 μm On tri acetyl cellulose membrane, adhesive composite layer is formed.Triacetyl cellulose as the moisture permeability for measuring and evaluating sample Plain film (is calculated using with a thickness of 57.5 μm, moisture permeability by agar diffusion method (JIS Z 0208,40 DEG C of temperature, humidity 90%RH) Value) it is 553g/m2The tri acetyl cellulose membrane of r for 24 hours.It then, is 400mJ/cm according to accumulated light2Mode from bonding agent Ultraviolet light is irradiated in composition layer side, and adhesive composite layer is made to solidify and evaluation sample is made.By agar diffusion method (JIS Z 0208, 40 DEG C of temperature, humidity 90%RH) the obtained moisture permeability for evaluating sample of measurement.
(oxetane compound)
Oxetane compound used in present embodiment has ehter bond in main chain.In turn, oxetanes chemical combination Object is preferably in the molecule containing 2 or more oxetanes rings.In this specification, main chain, which refers to, is indicating oxa- with structural formula Longest carbochain when cyclobutane compound.
Specifically, bis- [(3- ethyl -3- oxetanylmethoxy) first of Isosorbide-5-Nitrae-can be enumerated as oxetane compound Oxygroup methyl] benzene, 3- ethyl -3- (phenoxymethyl) oxetanes, two [(3- ethyl -3- oxetanylmethoxy) methyl] ethers, 3- ethyl -3- (2- Ethylhexoxymethyl) oxetanes etc..Among these, contain 2 or more oxa- ring fourths in the molecule The substance of alkane ring can enumerate Isosorbide-5-Nitrae-bis- [(3- ethyl -3- oxetanylmethoxy) methoxy] benzene, two [(3- ethyl -3- oxa-s Cyclobutyl) methyl] ether.
These oxetane compounds can be readily available commercially available product, as commercially available product, synthesize strain formula with East Asia The trade name of commercial firm's sale indicates, can enumerate " ARON OXETANE (registered trademark) OXT-121 ", " ARON OXETANE (note Volume trade mark) OXT-211 ", " ARON OXETANE (registered trademark) OXT-221 ", " ARON OXETANE (registered trademark) OXT- 212 " etc..
Above-mentioned oxetane compound is low with the compatibility of above-mentioned plasticizer and cross-linked structure is formed when polymerizeing, because And it is believed that plasticizer and is difficult to invade the solidfied material of the composition containing oxetane compound.Thus can speculate: damp and hot Under environment (such as in the environment of 60 DEG C of room temperature, humidity 95%), even if assuming in plasticizer from resin layer 21 to polarizer layer 11 In the case that (arrow direction of Fig. 1) is mobile, it can also inhibit the intrusion of plasticizer.
Relative to the total amount of this composition, the content of oxetane compound is preferably 10 mass % or more and 99 matter Measure % or less, more preferably 40 mass % or more and 99 mass % or less.By making the content of oxetane compound should In range, it is capable of forming the excellent solidfied material of crosslink density, is able to suppress the movement of plasticizer.
In this composition, one kind can be only used alone in oxetane compound, can also be shared two or more.
(other compositions)
(epoxide)
In addition, on the basis of above-mentioned oxetane compound, also can according to need in this composition and contain ring Oxygen compound.Epoxide and oxetane compound are similarly one of cationically polymerizable compound, can pass through work The irradiation of property energy-ray and solidify.By making this composition contain epoxide, resin layer 21 and polarizing film can be improved The cementability of layer 11.
As epoxide, it is sweet that aromatic epoxy compound, the shrink of polyalcohol with ester ring can be enumerated Oily ether, aliphatic epoxy compound, cycloaliphatic epoxy etc..
As aromatic epoxy compound, the diglycidyl ether of bisphenol-A, the diglycidyl ether of Bisphenol F can be enumerated With the bisphenol-type epoxy resin of the diglycidyl ether of bisphenol S etc；Phenol novolac epoxy resins, cresol novolak ring The phenolic resin varnish type epoxy resin of oxygen resin and hydroxy benzaldehyde phenol novolac epoxy resins etc；Tetrahydroxy benzene methylmethane Glycidol ether, the glycidol ether of tetrahydroxybenzophenone and the multifunctional type ring oxygen of epoxidation polyvinylphenol etc Resin etc..
As the glycidol ether of the polyalcohol with ester ring, can enumerate: by aromatic polyol in catalyst In the presence of, hydrogenation selectively carried out to aromatic rings under elevated pressure, and thus obtained core is hydrogenated into polyhydroxy chemical combination Object carries out substance obtained from glycidyl ether.As aromatic polyol, bisphenol-A, Bisphenol F, bisphenol S etc can be enumerated Bisphenol type compounds；Phenol resol resins, cresol novolac resin, hydroxy benzaldehyde phenol resol resins it The phenolic varnish type resin of class；The multifunctional type of tetrahydroxy diphenyl methane, tetrahydroxybenzophenone, polyvinylphenol etc Compound etc..
The alicyclic ring as obtained from epoxychloropropane is made to carry out hydrogenation with the aromatic rings to these aromatic polyols Formula polyalcohol reacts, it is possible thereby to which glycidol ether is made.
Among the glycidol ether of such polyalcohol with ester ring, as preferred substance, it can enumerate The diglycidyl ether of hydrogenated bisphenol-A.
As aliphatic epoxy compound, aliphatic polyol or the poly epihydric alcohol of its alkylene oxide addition product can be enumerated Ether etc..Specifically, the diglycidyl ether of 1,4-butanediol can be enumerated；The diglycidyl ether of 1,6- hexylene glycol；Glycerol Triglycidyl ether；The triglycidyl ether of trimethylolpropane；The diglycidyl ether of polyethylene glycol；Two contractings of propylene glycol Water glycerin ether；The diglycidyl ether of neopentyl glycol；Added by the aliphatic polyol to ethylene glycol, propylene glycol or glycerol etc At the polyglycidyl ether etc. of polyether polyol obtained from one kind or two or more alkylene oxide (ethylene oxide or propylene oxide).
In addition, monofunctional epoxy compound shown in following formula (I)s can also be enumerated as aliphatic epoxy compound. R1It is the alkyl that the carbon atom number with or without branch is 1~15.The carbon atom number of alkyl is preferably 6 or more, more preferably It is 6~10.Wherein preferred branched alkyl.As monofunctional epoxy compound shown in formula (I), the contracting of 2- ethylhexyl can be enumerated Water glycerin ether.
[changing 1]
Cycloaliphatic epoxy refers to that there is intramolecular the carbon atom of at least one and ester ring to be formed together epoxy second The compound of the structure of alkane ring.Herein, " it is formed together the structure of oxirane ring with the carbon atom of ester ring " and refers to and is following Structure shown in formula (II).The integer that n in formula is 2~5.
[changing 2]
Remove (the CH in the formula (II)2)nIn 1 or 2 or more hydrogen atom after form group and other chemistry tie The compound that structure is combined into becomes cycloaliphatic epoxy.In addition, forming the (CH of ester ring2)nIn 1 or 2 with On hydrogen atom can be replaced by the straight-chain alkyl of methyl or ethyl etc.
It is more excellent with the adaptation of polarizing film from being easy to get as epoxide, preferably cycloaliphatic epoxy Protective layer in terms of set out, more preferably have 7-oxa-bicyclo[4.1.0 (substance of the n=4 in above-mentioned formula (II)) or epoxy cycloheptane The epoxide of (substance of the n=5 in above-mentioned formula (II)).
In this composition, one kind can be only used alone in epoxide, can also be shared two or more.
(free-radical polymerised compound)
In addition, other than the cationically polymerizables compounds such as above-mentioned oxetane compound, above-mentioned epoxide, Also it may include free-radical polymerised compound.
As free-radical polymerised compound, the change that intramolecular has at least one (methyl) acryloxy can be enumerated Close object (hereinafter sometimes called " (methyl) acrylic compounds "), intramolecular has at least one (methyl) acrylamido Compound (hereinafter sometimes called " (methyl) acrylamide based compound ") etc..It should be noted that " (methyl) acryloyl Oxygroup " refers to methacryloxy or acryloxy, (methyl) acrylamido refer to methacryl amide base or Acryloyl group amide groups.
As (methyl) acrylic compounds, intramolecular can be enumerated at least one (methyl) acryloxy (methyl) acrylate monomer, intramolecular have (methyl) acrylate oligomer of at least two (methyl) acryloxy etc.. They can be used alone respectively, can also share two or more.In the case where sharing two or more, (methyl) acrylate Monomer can be two or more, and (methyl) acrylate oligomer may be two or more, naturally it is also possible to by (methyl) propylene 1 kind or more of a kind or more of acid ester monomer and (methyl) acrylate oligomer is shared.
As (methyl) acrylamide based compound, N- can be enumerated and replace (methyl) acrylamide compound.N- replaces (methyl) acrylamide compound is that have substituent group (methyl) acrylamide compound at N-.The typical case of its substituent group For alkyl.N- substituent groups can be mutually bonded and form ring, constitute-the CH of the ring2Oxygen atom can be substituted by.In addition, The substituent group of alkyl, oxygroup (=O) etc can be bonded on the carbon atom for constituting the ring.N- replaces (methyl) acrylamide It usually utilizes (methyl) acrylic acid or its chloride and primary amine or reacting for secondary amine and manufactures.
In this composition, one kind can be only used alone in free-radical polymerised compound, can also be shared two or more.
(cationic polymerization initiators)
This composition includes the cationically polymerizables compound such as above-mentioned oxetane compound or above-mentioned epoxide In the case where, it preferably further include cationic polymerization initiators.Cationic polymerization initiators pass through luminous ray, ultraviolet light, X Ray, electron ray isoreactivity energy-ray irradiation and generate cation kind or lewis acid, cause cationically polymerizable Close the polymerization reaction of object.As cationic polymerization initiators, aromatic diazonium salt, aromatic iodonium salts or aromatic series can be enumerated The salt such as sulfonium salt, iron-arene complex etc..
As aromatic diazonium salt, it can be cited for example that benzene diazonium hexafluoro antimonate, benzene diazonium hexafluoro phosphate, benzene diazonium Hexafluoro borate etc..
As aromatic iodonium salts, it can be cited for example that diphenyl iodine four (pentafluorophenyl group) borate, diphenyl iodine Hexafluorophosphate, diphenyl iodine hexafluoro antimonate, two (4- nonyl phenyl) iodine hexafluorophosphates etc..
As aromatic series sulfonium salt, it can be cited for example that triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoro antimonate, triphen Base sulfonium four (pentafluorophenyl group) borate, 4, the 4 '-bis- hexafluorophosphates of bis- [diphenyl sulfonium] diphenylsulfides-, 4,4 '-bis- [two (β- Hydroxyl-oxethyl) phenyl sulfonium] the bis- hexafluoro antimonates of diphenyl sulfide-, 4,4 '-bis- [two (beta-hydroxy ethyoxyl) phenyl sulfoniums] diphenyl The bis- hexafluorophosphates of thioether -, 7- [two (to toluyl groups) sulfoniums] -2-isopropylthioxanthone hexafluoro antimonate, [two (to first by 7- Benzoyl) sulfonium] -2-isopropylthioxanthone four (pentafluorophenyl group) borate, 4- phenylcarbonyl group -4 '-diphenyl sulfonium-diphenyl sulphur Ether hexafluorophosphate, 4- (to tert-butyl-phenyl carbonyl) -4 '-diphenyl sulfonium-diphenylsulfide hexafluoro antimonate, 4- are (to tertiary fourth Base phenylcarbonyl group) -4 '-two (to toluyl groups) sulfonium-diphenylsulfide four (pentafluorophenyl group) borates etc..
As iron-arene complex, it can be cited for example that dimethylbenzene-cyclopentadiene iron (II) hexafluoro antimonate, cumene-ring Pentadiene iron (II) hexafluorophosphate, dimethylbenzene-cyclopentadiene iron (II) three (trifluoromethyl sulfonyl) methanides etc..
These cationic polymerization initiators can be readily available commercially available product, such as be indicated respectively with trade name, Ke Yiju " KAYARAD (registered trademark) PCI-220 " and " KAYARAD (registered trademark) PCI- of Nippon Kayaku K. K's sale out 620 ", " UVACURE (registrar that " UVI-6990 " of Dow Chemical's sale, DAICEL-CYTEC Co., Ltd. sell Mark) 1590 ", Asahi Denka Co., Ltd. sale " Adeka Optomer (registered trademark) SP-150 " and " Adeka Optomer " CI-5102 ", " CIT-1370 ", " CIT-1682 ", " CIP- that (registered trademark) SP-170 ", Tso Tat Co., Ltd., Japan sell " DPI-101 ", " DPI- of 1866S ", " CIP-2048S " and " CIP-2064S ", the sale of Midori Kagaku Co., Ltd. 102”、“DPI-103”、“DPI-105”、“MPI-103”、“MPI-105”、“BBI-101”、“BBI-102”、“BBI-103”、 “BBI-105”、“TPS-101”、“TPS-102”、“TPS-103”、“TPS-105”、“MDS-103”、“MDS-105”、“DTS- 102 " " PI-2074 " etc. sold with " DTS-103 ", Rhodia company.
In these cationic polymerization initiators, from be capable of the light of absorbing wavelength 300nm or more, obtain curability it is excellent and It sets out in terms of solidfied material with good mechanical strength and adaptation, optimization aromatic sulfonium salt.
In this composition, cationic polymerization initiators be can be used alone, and can also be use mixing two or more.
(radical polymerization initiator)
In the case that this composition includes above-mentioned free-radical polymerised compound, preferably further draw comprising free radical polymerization Send out agent.As long as radical polymerization initiator can cause (methyl) acrylic acid series chemical combination by the irradiation of active energy beam Well known radical polymerization initiator can be used in the substance of the polymerization of the free-radical polymerised compounds such as object.
As radical polymerization initiator, acetophenone, 3- methyl acetophenone, benzyl dimethyl ketal, 1- (4- can be enumerated Isopropyl phenyl)-2- hydroxy-2-methyl propane-1- ketone, 2- methyl-1-[4- (methyl mercapto) phenyl-2- morpholino propane-1- ketone With the acetophenone series initiators of 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone etc；Benzophenone, 4- chlorobenzophenone and 4, The benzophenone series initiators of 4 '-diaminobenzophenones etc；The benzoin ether of benzoin propyl ether and benzoin ethyl ether etc Series initiators；The thioxanthones series initiators of 4-isopropylthioxanthone etc；And xanthone, Fluorenone, camphorquinone, benzaldehyde, Anthraquinone etc..
Radical polymerization initiator can be readily available commercially available product, such as be indicated respectively with trade name, can enumerate " Irgacure (registered trademark) 184 " of BASF AG's manufacture, " Irgacure (registered trademark) 907 ", " Darocure (registration Trade mark) 1173 ", " Lucirin (registered trademark) TPO " etc..
In this composition, one kind can be only used alone in radical polymerization initiator, can also be shared two or more.
(other additives)
In this composition, other than above compound, can include in the range of lossless effect of the present invention photosensitizer, Solvent, levelling agent, antioxidant, light stabilizer, ultraviolet absorbing agent etc..
As the photosensitizer that can be used in present embodiment, it can be cited for example that carbonyls, organic sulfur-containing chemical combination Object, persulfide, redox based compound, azo-compound, diazonium compound, halide, photo-reduction pigment etc..
As the solvent that can be used in present embodiment, there is the aliphatic hydrocarbon of such as n-hexane, hexamethylene etc；First Benzene, dimethylbenzene etc it is aromatic hydrocarbon；The alcohols of methanol, ethyl alcohol, propyl alcohol, isopropanol and n-butanol etc；Acetone, first and second The ketone of ketone, methyl iso-butyl ketone (MIBK) and cyclohexanone etc；The esters of methyl acetate, ethyl acetate and butyl acetate etc；Methyl The dioxane of cellosolve, ethyl cellosolve and butyl cellosolve etc；The halogenated hydrocarbon etc. of methylene chloride, chloroform etc.
As the levelling agent that can be used in present embodiment, it is total that silicone-based, fluorine system, polyether system, acrylic acid can be used The various compounds such as polymers system, titanate esters system.
As the antioxidant that can be used in present embodiment, it can be cited for example that the primary of phenol system or amine system etc is anti- Oxidant, secondary antioxidants of sulphur system etc..
As the light stabilizer that can be used in present embodiment, the amine system light stabilizer (HALS) etc. that is obstructed can be enumerated.
As the ultraviolet absorbing agent that can be used in present embodiment, can enumerate benzophenone series, enumerate BTA system, Benzoic ether system etc..
[protective film]
Fig. 2 is the schematic cross-section for showing the variation of layer structure of the stacked film of present embodiment.As shown in Fig. 2, In stacked film 2, in the side opposite with 21 side of resin layer is laminated with of polarizer layer 11, protective film can further be laminated 23.As the material for forming protective film 23, resin same as the material for forming above-mentioned resin layer 21 can be used.Form resin The material of layer 21 may be the same or different respectively with the material for forming protective film 23.
Protective film 23 can be laminated to polarizer layer 11 by adhesive layer 33.
As adhesive layer 33, water system bonding agent, active energy ray curable bonding agent can be enumerated, as active energy Ray curing bonding agent is measured, active energy ray curable bonding agent, the free radical polymerization of cationic polymerization system can be enumerated The active energy ray curable bonding agent of system.Alternatively, it is also possible to replace adhesive layer 33, adhesive phase is set.As bonding Oxidant layer can enumerate the adhesive containing acrylic resin.
The side or protective film opposite with the face for being laminated with resin layer 21 of polarizer layer 11 be laminated with polarization Adhesive phase (not shown) can be set in the opposite side in the face of lamella 11.It, can be by stacked film 2 by the way that adhesive phase is arranged Conform to the liquid crystal cell of display device.As adhesive phase, the adhesive containing acrylic resin can be enumerated.The present invention Stacked film preferred disposition in the observation side of liquid crystal cell.
[manufacturing method of stacked film]
The stacked film 1 of present embodiment includes:
(i) adhesive composite containing oxetane compound is formed in the one side of the resin layer 21 with slow axis The process of layer (hereinafter sometimes called " adhesive composite layer ")；
(ii) the adhesive composite layer of resin layer 21 will be formed in polarizer layer 11 and above-mentioned (i) according to resin layer 21 Slow axis relative to the absorption axiss of polarizer layer 11 be that 45 ± 10 ° or 135 ± 10 ° of mode is bonded, stacked gradually Have polarizer layer 11, adhesive composite layer, resin layer 21 laminated body process；And
(iii) to laminated body obtained in above-mentioned (ii) irradiation active energy beam (such as ultraviolet light, visible light, electronics Ray, X-ray etc.), so that adhesive composite layer is solidified the process for obtaining adhesive layer 31.Hereinafter, enumerating concrete example to each Process is illustrated.
In the process shown in above-mentioned (i), firstly, preparing the resin layer 21 with slow axis.In continuously manufacture polarizer layer In the case where 11, the polarizer layer of strip has absorption axiss in the flowing direction sometimes.From can be with roll-to-roll mode system Make laminated body (stacked film) and can be in such a way that the slow axis angulation of the absorption axiss and resin layer 21 is in above range The aspect configured to the two is set out, and resin layer 21 is preferably inclined by stretching and manufactures.
As the stretching-machine for tilting stretching, it can be cited for example that stenter formula stretching-machine.Stenter formula stretching-machine can To laterally or longitudinally or the two directions apply the centripetal force or drawing force or tractive force of left and right friction speed.As in this way Stenter formula stretching-machine, can enumerate laterally be uniaxially stretched machine, simultaneously biaxial drawing machine etc., as long as drawing can be tilted continuously Stretch resin film, so that it may use arbitrary appropriate stretching-machine.
As the method that the one side in resin layer 21 forms adhesive composite layer, it can enumerate and directly be coated with this composition And the method being dried as needed.In addition, this composition is applied to transparent substrate as other methods, can enumerate Film, after being dried as needed, method that its coating layer is transferred to polarizer layer 11.In the latter case, above-mentioned (ii) base material film is removed before process shown in.Resin similar to the above can be used in transparent base film.In addition, in transparent base In material film, the coated face of this composition can implement lift-off processing in advance.
As the coating method of this composition, well known coating method can be used, it can be cited for example that scraper, bar, Die coating machine, comma coating machine, gravure coater etc..
In the process shown in above-mentioned (ii), the bonding agent of resin layer 21 will be formed in polarizer layer 11 and above-mentioned (i) Composition layer is bonded, and the laminated body for being sequentially laminated with polarizer layer 11, adhesive composite layer, resin layer 21 is obtained.
In the process shown in above-mentioned (iii), luminous ray, ultraviolet light, X are irradiated to laminated body obtained in above-mentioned (ii) The active energy beam of ray or electron ray etc, thus makes adhesive composite layer be solidified to form adhesive layer 31, obtains To stacked film 1.
Light source used in the irradiation of active energy beam is not particularly limited, and is sent out using having below wavelength 400nm The light source of light distribution.As such light source, it can be cited for example that low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultra high pressure mercury Lamp, chemical lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp etc..
The exposure intensity of active energy beam is different according to the cured adhesive composite of institute, and cationic polymerization is drawn Exposure intensity in the effective wavelength region of activation of hair agent is preferably set to 10~2500mW/cm2Range.
The irradiation time of active energy beam is different according to the cured adhesive composite of institute, with exposure intensity and irradiation The accumulated light of the product representation of time is preferably set to 10~2500mJ/cm2Range.
It should be noted that adhesive composite layer is formed in the one side of resin layer 21 in above-mentioned Production Example, it can also Both to be formed in the one side of polarizer layer 11, can also be formed in.As shown in Fig. 2, can polarizer layer 11 be bonded The side for having 21 side of resin layer opposite is laminated with protective film 23, can also further be arranged for conforming to the viscous of liquid crystal cell Mixture layer (not shown).
According to the stacked film of above such structure, high-polarization is also able to maintain under hygrothermal environment.
<stacked film former material>
In present embodiment, polarizer layer and resin layer can be strip.The stacked film former material of present embodiment is (long The stacked film of strip) have band-like polarizing coating former material (polarizer layer of strip), band-like resin film former material (strip Resin layer) and polarizing coating former material is subjected to be bonded adhesive layer with resin film former material.
Polarizing coating former material is dichroism pigment using the length in belt type film of the PVA system resin as forming material along film Made of direction is orientated.PVA system resin and dichroism pigment are same as described above.
Resin film former material is using thermoplastic resin and plasticizer as the belt type film of forming material in the length side with the film Made of being stretched on the direction of oblique.It can be carried out as a result, when being laminated with polarizing coating former material in roll-to-roll mode, Manufacturing process can be simplified.Thermoplastic resin and plasticizer are same as described above.
Resin film former material is preferably phase difference film former material.Resin film former material relative to above-mentioned polarizing coating former material absorption axiss with Arbitrary angle is endowed slow axis.Arbitrary angle is preferably for example 45 ± 10 ° relative to the absorption axiss of above-mentioned polarizing coating former material Or 135 ± 10 °.By making the angle above range of slow axis, the stacked film former material of present embodiment is being applied to display dress When setting, excellent structure the visibility across polarisation sem observation can be made.
Adhesive layer contains the solidfied material of the adhesive composite of oxetane compound as forming material.Oxygen Oxetane compounds are same as described above.Above-mentioned oxetane compound it is low with the compatibility of plasticizer and when polymerizeing shape At cross-linked structure, thus it is believed that plasticizer is difficult to invade the solidfied material of the composition containing oxetane compound.Thus It can speculate: under hygrothermal environment (such as in the environment of 60 DEG C of room temperature, humidity 95%), even if assuming former from resin film in plasticizer In the case that material is moved to polarizing coating former material, it can also inhibit the intrusion of plasticizer.
According to the stacked film former material of structure as described above, high-polarization is also able to maintain under hygrothermal environment.
Embodiment
Hereinafter, illustrate the present invention by embodiment, but the present invention and it is not limited to these examples.In the present embodiment The unstretching film used refers to the film of unstretched state.
[evaluation of the humidity resistance of stacked film]
The stacked film of embodiment and comparative example is placed 250 hours in the environment of 65 DEG C of temperature, relative humidity 90%, it is right The visibility correction degree of polarization for placing front and back is compared.At this point, before subtracting placement by the visibility correction degree of polarization after placing The absolute value (Δ Py) of value of visibility when correcting degree of polarization be denoted as zero when being 0.3 or less, Δ Py is denoted as when being greater than 0.3 ×. It should be noted that visibility correction degree of polarization is measured using following methods.As a result it is shown in table 2~5.
(measurement of visibility correction degree of polarization)
For the stacked film of embodiment and comparative example, the spectrophotometer (Japan Spectroscopy Corporation with integrating sphere is utilized Manufacture, " V7100 "), measure the MD transmissivity and TD transmissivity within the scope of wavelength 380nm~780nm.Then, it is transmitted using MD Rate and TD transmissivity calculate the degree of polarization under each wavelength based on formula (T1).
Herein, " MD transmissivity " indicates the direction for making the polarised light projected from glan thompson prism and membrane sample is laminated The transmissivity when axis of homology is parallel.In addition, " TD transmissivity " indicates the direction for making the polarised light projected from glan thompson prism Transmissivity when orthogonal with the stacking axis of homology of membrane sample.
[mathematical expression 1]
(measurement of the moisture permeability of evaluation sample)
Evaluation sample makes as follows.Firstly, using bar coater by adhesive composite in the way of with a thickness of 2~3 μm It is applied on tri acetyl cellulose membrane, forms adhesive composite layer.Three second as the moisture permeability for measuring and evaluating sample Acyl cellulose membrane (is calculated using with a thickness of 57.5 μm, moisture permeability by agar diffusion method (JIS Z 0208,40 DEG C of temperature, humidity 90%RH) Value out) it is 553g/m2The KC6UA of Konica Minolta Opto Inc.'s manufacture of r for 24 hours.Then, using Fusion UV The D VALVE of Systems company manufacture is 400mJ/cm according to accumulated light2Mode from adhesive composite layer side irradiate Ultraviolet light makes adhesive composite layer solidify and evaluation sample is made.Pass through agar diffusion method (JIS Z 0208,40 DEG C of temperature, humidity 90%RH) the moisture permeability of measurement gained evaluation sample.
[Production Example (manufacture of adhesive composite)]
According to blend amount shown in table 2~5, the adhesive composite of embodiment and comparative example is prepared respectively.Wherein, it prepares Used in compound title sometimes referred to as to indicate.
In addition, cationic polymerization initiators " Adeka Optomer (registered trademark) SP-150 " are molten using propylene carbonate The substance of liquid is indicated in table 2~5 with its active ingredient amount.In addition, epoxy crosslinking agent " Sumirez Resin (registrar Mark) 650 " use aqueous solution substance, indicated in table 5 with its active ingredient amount.
It should be noted that each ingredient about adhesive composite, uses compound below.
[adhesive composite of active energy ray-curable]
(cationically polymerizable compound)
" Celloxide (registered trademark) 2021P ": 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexane carboxylates, by Daicel Chemical Co., Ltd. obtains.
" YX8000 ": the diglycidyl ether of bis-phenol is obtained by Mitsubishi chemical Co., Ltd.
[[1,1- is bis- by 4- by -2- by " TECHMORE (registered trademark) VG3101L ": 2- [4- (2,3- glycidoxy) phenyl] [4- ([2,3- glycidoxy] phenyl] ethyl] phenyl] it propane, is obtained by P Co., Ltd. rintec.
" ARON OXETANE (registered trademark) OXT-101 ": 3- ethyl -3- hydroxymethyl oxetane is closed by East Asia It is obtained at Co., Ltd..
" ARON OXETANE (registered trademark) OXT-212 ": 3- ethyl -3- (2- Ethylhexoxymethyl) oxa- ring fourth Alkane is obtained by Toagosei Co., Ltd.
" ARON OXETANE (registered trademark) OXT-221 ": two [(3- ethyl -3- oxetanylmethoxy) methyl] ethers, by east Asia synthesis Co., Ltd. obtains.
The structure of above-mentioned oxetane compound is shown in table 1.
[table 1]
(free-radical polymerised compound)
" A-DCP ": Tricyclodecane Dimethanol diacrylate, chemical industry Co., Ltd., the village You Xinzhong obtain.
(cationic polymerization initiators)
" Adeka Optomer (registered trademark) SP-150 ": 4, the 4 '-bis- hexafluoro phosphorus of bis- [diphenyl sulfonium] diphenylsulfides- The light cationic polymerization initiator of phosphate-gallate series is obtained in the form of polypropylene carbonate ester solution by Asahi Denka Co., Ltd..
(radical polymerization initiator)
" Darocure (registered trademark) 1173 ": 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, by BASF Japan Co., Ltd. obtains.
[water-based adhesive composite]
(polyvinyl alcohol)
" Kuraray Poval (registered trademark) KL-318 ": carboxy-modified polyvinyl alcohol is obtained by Co., Ltd. KURARAY ?.
(epoxy crosslinking agent)
" Sumirez Resin (registered trademark) 650 ": water soluble polyamide epoxy resin (solid component concentration 30% Aqueous solution), by Sumika Chemtex Co., Ltd. obtain.
[other compositions]
" SH710 ": silicone-based levelling agent is obtained by Dow Corning Toray Co., Ltd..
[embodiment 1~13, comparative example 1~6]
(a) production of polarizer layer
Be about 2400 by average degree of polymerization, saponification degree be 99.9 moles of % or more, with a thickness of 30 μm of polyvinyl alcohol films with Dry type is uniaxially stretched to about 5 times, and then under conditions of keeping tensioning state, after being impregnated 1 minute in 60 DEG C of pure water, It is impregnated 60 seconds in the aqueous solution that iodine/potassium iodide/water weight ratio is 0.05/5/100 with 28 DEG C.Later, potassium iodide/boric acid/ The weight ratio of water is to be impregnated 300 seconds in the aqueous solution of 8.5/8.5/100 with 72 DEG C.Then, after cleaning 20 seconds with 26 DEG C of pure water, It is dried with 65 DEG C, produces the polarizer layer that iodine is orientated in the polyvinyl alcohol film through being uniaxially stretched.The thickness of polarizing film It is 12 μm.
(b) preparation of resin layer
As resin layer, it is ready to pass through the tri acetyl cellulose membrane comprising plasticizer that inclination stretches manufacture.
Hard conating is formed in the single side of the tri acetyl cellulose membrane.In addition, resin layer relative to film length direction About 45 ° of slow axis angle average out to.
As the tri acetyl cellulose membrane for stretching manufacture through inclination, material below has been used.
The tri acetyl cellulose membrane of manufacture: Konica Minolta Opto Inc.'s manufacture, KC4UGR- is stretched through inclination HC, thickness=44 μm, Re(590)=106nm, Rth(590)=75nm, Rth(590)/Re(590)=0.71, Re(450)/Re (550)=0.96, Re(630)/Re(550)=1.02)
It should be noted that Re(590)、Re(450)、Re(550)、Re(630) respectively indicate measurement wavelength 590nm, Phase difference value in face under 450nm, 550nm, 630nm, Rth(590) the thickness direction phase difference under measurement wavelength 590nm is indicated Value.
(c) production of stacked film
Then, on the face of the not formed hard conating of above-mentioned (b) resin layer, it is coated with the combination of bonding agent obtained in Production Example Object forms adhesive composite layer.Specifically, using bar coater (first physical and chemical Co., Ltd. manufactures), after solidification The mode coating adhesive composition that film thickness is about 2 μm.Separately for using 23 μm of thickness of norbornene resin as being formed The single side of the unstretching film [trade name " ZEONOR (registered trademark) " of Japanese Zeon Co., Ltd. manufacture] of material implements corona Discharge treatment.Above-mentioned adhesive composite is coated in the same manner as resin layer on its Corona discharge Treatment face, forms bonding agent group Close nitride layer.It should be noted that unstretching film is the raw material of the protective film in stacked film.
One face of the polarizer layer made in above-mentioned (a) is formed in the bonding of resin layer with what is prepared in above-mentioned (b) The fitting of agent composition layer, and another face of polarizer layer is bonded with the adhesive composite layer for being formed in unstretching film, Produce sandwich.Fitting has used adhering device (manufacture of FUJIPLA Co., Ltd., " LPA3301 ").In fitting, make partially The absorption axiss of lamella of shaking and the slow axis angulation of resin layer are 45 °.
Then, using the ultraviolet lamp of subsidiary conveyer belt, [lamp is manufactured using Fusion UV Systems company " D VALVE "], from the unstretching film side of gained sandwich according to accumulated light be 250mJ/cm2Mode irradiate ultraviolet light, make The solidification of adhesive composite layer.So produce comprising protective film/polarizer layer/adhesive layer/resin layer/hard conating stacking Film.
The moisture permeability for the evaluation sample that the adhesive composite as used in each embodiment and comparative example obtains is as described below.
Embodiment 13:293g/m2R, comparative example 1:447g/m for 24 hours2R, comparative example 3:307g/m for 24 hours2R, ratio for 24 hours Compared with example 4:428g/m2R, comparative example 5:529g/m for 24 hours2·24hr
[comparative example 7]
Operation below is carried out in the production of (c) stacked film, in addition to this, comparison example 7 similarly to Example 1 Stacked film.
On one face of the polarizer layer made in above-mentioned (a), combined by water system bonding agent obtained in Production Example Object is bonded the resin layer prepared in above-mentioned (b).Later, it after the drying for carrying out 5 minutes at 80 DEG C, is conserved at 40 DEG C, 23%RH 72 hours, produce stacked film.
[table 2]
[table 3]
[table 4]
[table 5]
[reference example]
(a-1) production of polarizer layer
30 μm of thickness of the polarizer layer that production iodine is orientated in the polyvinyl alcohol film through being uniaxially stretched.
(b-1) preparation of resin layer
Prepare tri acetyl cellulose membrane (KC4FR-1, KONICA MINOLTA OPTO Co. Ltd. system to 43 μm of thickness Make) implement film obtained by saponification process.The film is stretched film, contains plasticizer.
(b-2) preparation of protective film
Prepare to implement film obtained by saponification process to the tri acetyl cellulose membrane of subsidiary hard conating.The film with a thickness of 83 μ m。
(c-1) production of stacked film
It is made in above-mentioned (a-1) using roll by water-based adhesive composite obtained in above-mentioned Production Example It is bonded the resin layer prepared in (b-1) on one face of polarizer layer, is bonded by identical adhesive composite in another side (b-2) protective film prepared in, produces sandwich.At this point, putting down the slow axis of resin layer and the absorption axiss of polarizer layer substantially Row.When the protective film prepared in fitting (b-2), make to become the binding face with polarizer layer there is no the side of hard conating.It connects , by drying oven in the state of keeping the tension of sandwich, keeps bonding agent dry and obtain stacked film.
In the opposite side of the one side Nian Jie with polarizer layer of resin layer, the adhesive phase of storage modulus about 0.7MPa is set (15 μm of thickness).Stacked film is conformed on glass by the adhesive phase, as evaluation sample.With commenting for above-mentioned humidity resistance Valence similarly places the sample 250 hours in the environment of 65 DEG C of temperature, relative humidity 90%, to the visibility for placing front and back Correction degree of polarization is compared.As a result, the variation delta Py of visibility correction degree of polarization is 0.3% or less.
By table 2~5 the result shows that, using containing main chain have ehter bond oxetane compound (" ARON The feelings of OXETANE (registered trademark) OXT-212 " and the adhesive composite of " ARON OXETANE (registered trademark) OXT-221 ") Under condition, Δ Py is 0.3 hereinafter, also keeping high-polarization under hygrothermal environment.
Thereby confirm that the present invention is useful.
Industrial availability
The present invention can be used as the inspection of the feed element or polarised light of the polarised light in the display devices such as liquid crystal display device Survey element.
Description of symbols
1,2 ... stacked films；11 ... polarizer layers；21 ... resin layers；23 ... protective films；31,33 ... adhesive layers

Claims (3)

1. a kind of stacked film, includes
Polarizer layer, wherein dichroism pigment is orientated in polyvinyl alcohol resin；
Resin layer, by the resin film on the direction of the absorption axiss oblique with the polarizer layer with slow axis as forming material Material；And
Adhesive layer, the polarizer layer is carried out with the resin layer it is be bonded,
The resin layer includes plasticizer,
The adhesive layer contains the solidfied material of the adhesive composite of oxetane compound as forming material,
The oxetane compound has ehter bond in main chain.
2. stacked film according to claim 1, wherein the oxetane compound includes more than two oxa- rings Butane ring.
3. stacked film according to claim 1 or 2, wherein the polarizer layer and the resin layer are strip.
CN201780048413.9A 2016-08-03 2017-07-26 Stacked film Pending CN109564318A (en)

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020024368A (en) * 2018-07-26 2020-02-13 三菱ケミカル株式会社 Active energy-curable resin composition, polarizing film protection layer, and polarizing plate using the same
WO2023053798A1 (en) * 2021-09-28 2023-04-06 日東電工株式会社 Polarization film, image display device, and method for producing polarization film

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007133350A (en) * 2005-10-11 2007-05-31 Fujifilm Corp Image display device
CN101923183A (en) * 2009-06-15 2010-12-22 住友化学株式会社 Optical laminate and manufacture method thereof
JP2013061561A (en) * 2011-09-14 2013-04-04 Konica Minolta Advanced Layers Inc Polarizing plate and display device using the same
JP2016029508A (en) * 2015-11-19 2016-03-03 住友化学株式会社 Polarizing laminate film
KR20160049943A (en) * 2014-10-28 2016-05-10 주식회사 엘지화학 Method for manufacturing polarizer, polarizer manufactured by the same and polarizing plate comprising the same
CN105745560A (en) * 2013-09-30 2016-07-06 Lg化学株式会社 Polarizing plate, method for manufacturing same, and image display device comprising same

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008083307A (en) * 2006-09-27 2008-04-10 Konica Minolta Opto Inc Polarizing plate, manufacturing method of polarizing plate, and liquid crystal display device
JP4758327B2 (en) * 2006-11-28 2011-08-24 協立化学産業株式会社 Polarizer
JP4744496B2 (en) 2007-04-16 2011-08-10 日東電工株式会社 Polarizing plate, optical film and image display device
JP2010091602A (en) * 2008-10-03 2010-04-22 Sumitomo Chemical Co Ltd Polarizing plate and liquid crystal display device
JP5446902B2 (en) * 2009-03-05 2014-03-19 Ｄｉｃ株式会社 Cationic polymerizable adhesive and polarizing plate obtained using the same
JP2013152457A (en) * 2011-12-27 2013-08-08 Konica Minolta Inc Polarizing plate and display device using the same
JP5855947B2 (en) * 2012-01-12 2016-02-09 住友化学株式会社 Photocurable adhesive, polarizing plate and laminated optical member using the same
JP6227923B2 (en) * 2012-08-03 2017-11-08 協立化学産業株式会社 Method for producing laminated film, adhesive composition kit and reaction initiator composition
JP2014071202A (en) * 2012-09-28 2014-04-21 Fujifilm Corp Polarizing plate, and liquid crystal display device
WO2014058042A1 (en) * 2012-10-11 2014-04-17 東亞合成株式会社 Photocurable adhesive composition, polarizer and process for producing same, optical member, and liquid-crystal display device
JP6011407B2 (en) * 2013-03-22 2016-10-19 東亞合成株式会社 Active energy ray-curable adhesive composition for plastic film or sheet
JP2016090964A (en) * 2014-11-11 2016-05-23 コニカミノルタ株式会社 Liquid crystal display device and method for manufacturing the same
JP2016136171A (en) * 2015-01-23 2016-07-28 コニカミノルタ株式会社 Optical film, circularly polarizing plate, and organic electroluminescence display device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007133350A (en) * 2005-10-11 2007-05-31 Fujifilm Corp Image display device
CN101923183A (en) * 2009-06-15 2010-12-22 住友化学株式会社 Optical laminate and manufacture method thereof
JP2013061561A (en) * 2011-09-14 2013-04-04 Konica Minolta Advanced Layers Inc Polarizing plate and display device using the same
CN105745560A (en) * 2013-09-30 2016-07-06 Lg化学株式会社 Polarizing plate, method for manufacturing same, and image display device comprising same
KR20160049943A (en) * 2014-10-28 2016-05-10 주식회사 엘지화학 Method for manufacturing polarizer, polarizer manufactured by the same and polarizing plate comprising the same
JP2016029508A (en) * 2015-11-19 2016-03-03 住友化学株式会社 Polarizing laminate film

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