CN109870756A - Optical laminate and its manufacturing method - Google Patents

Optical laminate and its manufacturing method Download PDF

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Publication number
CN109870756A
CN109870756A CN201811465427.3A CN201811465427A CN109870756A CN 109870756 A CN109870756 A CN 109870756A CN 201811465427 A CN201811465427 A CN 201811465427A CN 109870756 A CN109870756 A CN 109870756A
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China
Prior art keywords
polarization plates
layer
film
protective film
optical laminate
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CN201811465427.3A
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CN109870756B (en
Inventor
神野彩乃
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered 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
    • B32B27/08Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B38/00Ancillary operations in connection with laminating processes
    • B32B38/0004Cutting, tearing or severing, e.g. bursting; Cutter details
    • 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
    • B32B7/03Layered 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 with respect to the orientation of features
    • 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
    • B32B7/06Interconnection of layers permitting easy separation
    • 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
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising 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
    • 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
    • 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
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51Elastic
    • 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
    • B32B2457/00Electrical equipment
    • B32B2457/20Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202LCD, i.e. liquid crystal displays
    • 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
    • B32B2457/00Electrical equipment
    • B32B2457/20Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/206Organic displays, e.g. OLED

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)
  • Eyeglasses (AREA)
  • Optical Integrated Circuits (AREA)

Abstract

The present invention provides a kind of optical laminate, successively includes protective film, polarization plates, one layer or more of phase separation layer and adhesive phase, and protective film meets following formula: first the-the second elasticity modulus of elasticity modulus >=300MPa.In formula, so-called first elasticity modulus, it is the tensile modulus of elasticity on the direction orthogonal with the absorption axiss of polarization plates under 23 DEG C of temperature, relative humidity 55%RH, so-called second elasticity modulus is the tensile modulus of elasticity on the direction parallel with the absorption axiss of polarization plates under 23 DEG C of temperature, relative humidity 55%RH.

Description

Optical laminate and its manufacturing method
Technical field
The present invention relates to the optical laminate comprising protective film, polarization plates, phase separation layer and adhesive phase and its manufacturers Method.
Background technique
As polarization plates used in the image display devices such as liquid crystal display device, organic EL display device, in the past, generally It uses to fit in the protective film formed by triacetyl cellulose (TAC) using bonding agent and be formed by polyvinyl alcohol resin Polarizing film obtained by polarization plates.In recent years, consider from viewpoints such as filming, durability, cost, productivities, other than TAC The protective film that resin is formed also gradually is obtained using (such as Japanese Unexamined Patent Publication 2004-245925 bulletin (patent document 1)).
Summary of the invention
Problem to be solved by the invention
Sometimes in the face laminated phase-difference layer and adhesive phase of polarization plates.For such multilayered structure comprising polarization plates Body requires slimming, however can be by from the thin multilayer structure making without stiffness, particularly from the more of long size shape The monolithic body of multilayer structure making obtained from cutting out in laminar structure, which is easy to generate, bends to bowed deformation.In this specification, Also the deformation referred to as " is crimped ".
Multilayer structure making generally by as its polarize plate surface (with the side phase for being laminated with phase separation layer and adhesive phase The surface of anti-side) it is fitted with protective film (the also referred to as surface protection film that can be removed for protecting the surface.) band There is the multilayer structure making of protective film to circulate on the market.Even if in the multilayer structure making with protective film, if thinning, also together Have the tendency that being easy to generate curling when monolithic body is made to sample.
Hereinafter, also will successively include the above-mentioned more with protective film of protective film, polarization plates, phase separation layer and adhesive phase Laminar structure is referred to as " optical laminate ".
In the curling of optical laminate, have two kinds of " just crimp " and " inverse curling ".In optical laminate, it is so-called " just Curling " is the curling for keeping the face of protective film side concave, and so-called " inverse curling " is the curling for making the face protrusion of protective film side.
Once generate inverse curling, by the monolithic body folder of optical laminate across its adhesive phase fit in liquid crystal cells, When the image-displaying members such as organic EL element, makes it easy to cause to generate fitting mistake or bubble is mixed into adhesive phase and image is aobvious Show the not good situation at the interface of element.
The object of the present invention is to provide the optical laminates and its manufacturing method that inhibit inverse curling.
The present invention provides optical laminate and its manufacturing method as shown below.
[1] a kind of optical laminate successively includes protective film, polarization plates, one layer or more of phase separation layer and bonding Oxidant layer,
The protective film meets lower formula (I).
First the-the second elasticity modulus of elasticity modulus >=300MPa (I)
[in formula, so-called first elasticity modulus, be at 23 DEG C of temperature, relative humidity 55%RH with the polarization plates Tensile modulus of elasticity on the orthogonal direction of absorption axiss, so-called second elasticity modulus are in 23 DEG C of temperature, relative humidity 55%RH Under the direction parallel with the absorption axiss of the polarization plates on tensile modulus of elasticity.]
[2] according to the optical laminate recorded in [1], wherein the polarization plates with a thickness of 110 μm or less.
[3] according to the optical laminate recorded in [1] or [2], wherein described one layer or more of phase separation layer includes by liquid The phase separation layer that the solidfied material of brilliant compound is constituted.
[4] a kind of manufacturing method of optical laminate is the optical laminate for manufacturing any one of [1]~[3] and recording Method,
This method comprises:
The protective film layer in the region comprising meeting lower formula (I) is laminated on the one side of polarization plates by first step;
The second step, the surface layer of the polarization plates and the one side opposite side fold one layer or more phase separation layer, And adhesive phase;
The third step cuts out the optical laminate from the region.
First the-the second elasticity modulus of elasticity modulus >=300MPa (I)
[in formula, so-called first elasticity modulus, be at 23 DEG C of temperature, relative humidity 55%RH with the polarization plates Tensile modulus of elasticity on the orthogonal direction of absorption axiss, so-called second elasticity modulus are in 23 DEG C of temperature, relative humidity 55%RH Under the direction parallel with the absorption axiss of the polarization plates on tensile modulus of elasticity.]
[5] according to the manufacturing method recorded in [4], the second step include will include base material film and phase separation layer Laminate layers are laminated on the process that the base material film is removed after the opposite side.
According to the present invention it is possible to provide the optical laminate and its manufacturing method for inhibiting inverse curling.
Detailed description of the invention
Fig. 1 is the schematic sectional view for indicating an example of optical laminate.
Fig. 2 is the schematic sectional view of an example for indicating that the layer of polarization plates is constituted.
Fig. 3 is another schematic sectional view for indicating the layer of polarization plates and constituting.
Fig. 4 is the flow chart for indicating the manufacturing method of optical laminate.
Fig. 5 is the side view for indicating an example of the polarization plates manufacturing process S101 with protective film.
Fig. 6 is the schematic diagram for illustrating the measuring point of production method and MD amount of curl of monolithic body.
Specific embodiment
< optical laminate >
Optical laminate of the invention successively includes protective film, polarization plates, one layer or more of phase separation layer and adhesive Layer (first adhesive phase).
Hereinafter, optical laminate is described in detail.
(1) composition of optical laminate
Fig. 1 is the schematic sectional view for indicating an example of optical laminate of the invention.Optical laminate shown in FIG. 1 is successively Has protective film 1;Polarization plates 2;First adhesive layer 3a;First phase difference layer 3;Second adhesive layer 4a;Second phase difference layer 4;The One adhesive phase 5;Diaphragm 6.
First adhesive phase 5 by as polarization plates 2 and stacking protective film 1 side opposite side, be configured at it is outermost The adhesive phase of side defines.
Protective film 1 is made of the second adhesive phase 50 of base material film 40 and stacking thereon.
In the case where protective film 1 is made of the second adhesive phase 50 of base material film 40 and stacking thereon, so that protection Second adhesive phase 50 possessed by film 1 is be overlapped with the mode of an above-mentioned face contact of polarization plates 2.
According to the present invention, such as in optical laminate as shown in Figure 1, the face protrusion for making 1 side of protective film can be inhibited Inverse curling generation.
According to the optical laminate for inhibiting inverse curling, image is fitted in across its first adhesive phase in folder When display element, generation fitting mistake or bubble can be inhibited to be mixed into the interface of first adhesive phase and image-displaying member Not good situation.
Optical laminate can be long size objects, be also possible to monolithic body, however be typically due to be easy in monolithic body Curling is led to the problem of, therefore optical laminate is preferably monolithic body.
" monolithic body " so-called in this specification refers to from the film (such as film of long size shape (band-like)) of larger size The film of the smaller size cut out.
Herein, the curling of optical laminate may be used also other than above-mentioned " just crimp " and " inverse curling " such classification To be classified as " MD curling " and " TD curling " two kinds.So-called " MD curling " is due to stress (convergent force, expansive force etc.) The reason of and the curling that generates, the long size shape optical layer in the direction of the stress and the monolithic body for being cut out optical laminate The direction MD of stack is parallel.
MD is crimped, specifically, being laminated in the record according to aftermentioned embodiment one from long size shape optics Cut out in body test sample (monolithic body) and by the test sample with the face of concave side be above be placed on horizontal platform when, It can be used as small with the angle of the absorption axis direction of the polarization plates of test sample in two diagonal lines of test sample Curling that two angles on one diagonal line are lifted (absorbing the curling of axis direction) measures its size.In the band of long size shape Have the absorption axis direction of polarization plates in the polarization plates of protective film it is parallel with the direction MD of protective film when, MD curling can be used as measurement With on a diagonal line small with the angle in the direction MD of long size shape optical laminate in two diagonal lines of sample Curling that two angles are lifted measures.
So-called " TD curling ", be due to stress (convergent force, expansive force etc.) caused by crimp, the stress Direction is parallel with the direction TD of long size shape optical laminate of monolithic body for being cut out optical laminate.
In the present invention, it is conceived to MD curling.It can use the so-called inverse curling that the present invention inhibits, refer to as MD curling Inverse curling.
The so-called direction MD refers to that the mechanical flow direction of film, the i.e. length direction of film, the so-called direction TD refer to and the side MD To orthogonal direction.
As long as the layer of optical laminate of the invention is constituted successively comprising protective film, polarization plates, one layer or more of phase difference Layer and adhesive phase, are just not limited to composition shown in FIG. 1, such as can have layer as follows and constitute.
(a) can not have the first adhesive layer 3a and first phase difference layer 3 or the second adhesive layer 4a and second phase difference layer 4。
(b) first phase difference layer 3 can be formed directly into the surface of polarization plates 2.
(c) can be also with the phase separation layer other than first phase difference layer 3 and second phase difference layer 4.
(d) can not have diaphragm 6.
(e) protective film 1 can be single layer structure.
The length of optical laminate as long size shape is, for example, 100~20000m, preferably 1000~10000m. In addition, the width of the optical laminate as long size shape is, for example, 0.5~3m, preferably 1~2.5m.
It the size of optical laminate as monolithic body, shape and cuts out angle and is not particularly limited.
The monolithic body of optical laminate is preferably square configuration, more preferably with the square configuration of long side and short side.It should Square configuration is preferably rectangle.
Monolithic body shape be rectangular situation under, the length of long side is, for example, 50mm~300mm, preferably 70mm ~150mm.The length of short side is, for example, 30mm~200mm, preferably 40mm~100mm.
It, can be from 1 side of protective film in the case where the shape of monolithic body is rectangular situation although being not particularly limited When observing monolithic body, the absorption axis direction of polarization plates 2 forms 45 degree of angle relative to its longer side and a shorter side.
Alternatively, monolithic body shape be rectangular situation under, in the monolithic body from 1 side of protective film, polarization plates Absorption axis direction can be parallel with its long side, or form 90 degree of angle relative to its long side.
Optical laminate (the preferably monolithic body of optical laminate) does not preferably have according to aftermentioned embodiment one Record the inverse curling of measurement, more preferable just crimp amount be 20mm hereinafter, or be flat state without curling, it is further excellent To select just crimp amount be 10mm hereinafter, or be flat state without curling, particularly preferably do not have curling and be flat State.
Optical laminate (the preferably monolithic body of optical laminate) preferably has diaphragm in the outside of first adhesive phase 5 The state crimped in 6 composition or composition without diaphragm 6 is as described above, more preferably in the composition at least with diaphragm 6 The state of curling is as described above.
(2) protective film
The composition of (2-1) protective film
Protective film 1 is the film for protecting the surface of polarization plates 2, is usually shown optical laminate is fitted in such as image After showing element etc., removing is peeled off together with the adhesive phase with second adhesive phase 50.Thus, protective film 1 The above-mentioned surface of polarization plates 2 can be fitted in removing.
Protective film 1 second adhesive phase 50 of base material film 40 and stacking thereon as set forth above, it is possible to be made of.
Base material film 40 can be by thermoplastic resin, such as polyethylene-based resin, polypropylene-based resin, cyclic polyolefin hydrocarbon system tree The polyolefin-based resins such as rouge;The polyester based resins such as polyethylene terephthalate, polyethylene naphthalate;Polycarbonate It is resin;(methyl) acrylic resin etc. is constituted.Base material film 40 can be single layer structure, be also possible to multilayered structure.
Second adhesive phase 50 can be viscous by (methyl) acrylic adhesive, epoxy adhesive, carbamate system Mixture, silicone-based adhesive etc. are constituted.
In addition, protective film 1 is also possible to the resin film that polypropylene-based resin and polyethylene-based resin etc. have self adhesion. In this case, protective film 1 does not have second adhesive phase 50.
The thickness of protective film 1 for example can be 5~150 μm, preferably 10~100 μm, more preferably 20~75 μm, into one Preferably 25~70 μm of step (for example, 60 μm or less, further preferably 55 μm or less).Protective film 1 thickness less than 5 μm In the case where, the case where protections of polarization plates 2 is not enough is had, it is in addition also unfavorable in terms of disposition property.If protective film 1 Thickness be greater than 150 μm, then the filming of optical laminate, protective film re-workability in terms of it is unfavorable.
The elasticity modulus of (2-2) protective film
The protective film 1 that optical laminate has meets lower formula (I):
First the-the second elasticity modulus of elasticity modulus >=300MPa (I)
In formula (I), so-called first elasticity modulus is the absorption with polarization plates 2 under 23 DEG C of temperature, relative humidity 55%RH Tensile modulus of elasticity (MPa) on the orthogonal direction of axis, so-called second elasticity modulus are 23 DEG C of temperature, relative humidity 55%RH Under the direction parallel with the absorption axiss of polarization plates 2 on tensile modulus of elasticity (MPa).
According to the optical laminate for having the protective film 1 for meeting formula (I), the face protrusion for making 1 side of protective film can be inhibited The generation of inverse curling.
The direction orthogonal with the absorption axiss of polarization plates 2 is for example in the feelings using aftermentioned manufacturing method manufacture optical laminate It is synonymous with the direction TD of protective film 1 and polarization plates 2 under condition.
So-called " meeting formula (I) " refers to when the record according to aftermentioned embodiment one measures the protective film, the first bullet Property modulus and the second elasticity modulus meet formula (I).
From the viewpoint of the inverse curling for inhibiting optical laminate, the left side of formula (I) is preferably 400MPa or more, more preferably For 500MPa or more.
In monolithic body, it is however generally that, size is smaller, is more easy to generate inverse curling.Thus, it is small in the size of monolithic body In the case of, in order to be adequately suppressed inverse curling, it is sometimes preferred to further increase the left side of formula (I).
(3) polarization plates
The composition of (3-1) polarization plates
Polarization plates 2 are the polarizers including at least polarizing film, usually also include the thermoplastic for fitting in its one or both sides Property resin film.
Thermoplastic resin film can be the protective film etc. of protection polarizing film.Protective film is bonded in 1 side of protective film of polarization plates 2 In the case where (thermoplastic resin film), which is also possible to phase difference film.Alternatively, it is also possible at this 1 side of protective film of protective film (thermoplastic resin film) is equipped with following resin layers such as antireflection process layer.
Thermoplastic resin film can have the resin layer (such as optical layer) for being laminated in its surface.The example of resin layer is hard Coating, antiglare layer, anti-reflection layer, anti-static electricity interference layer, stain-proofing layer etc..Thermoplastic of the resin layer particularly suitable for 1 side of protective film Property resin film.
Thermoplastic resin film can be pressed from both sides and fit in polarizing film across adhesive layer or adhesive phase.
The thickness of polarization plates 2 is usually 150 μm hereinafter, from the viewpoint of the filming of polarization plates 2, and preferably 110 μm Hereinafter, more preferably 80 μm hereinafter, further preferably 70 μm or less.The thickness of polarization plates 2 is smaller, and optical laminate is more easy to Curling is generated, according to the present invention, even if optical laminate can also be effectively inhibited in the case where the thickness of polarization plates 2 is small Inverse curling.
The thickness of polarization plates 2 is usually 20 μm or more or 30 μm or more.
It is illustrated referring to the example that layer of the Fig. 2 and Fig. 3 to polarization plates is constituted, however layer composition is not limited to these examples Son.
Polarization plates 2a shown in Fig. 2 has polarizing film 10;Fit in the first thermoplastic resin film of the one side of polarizing film 10 20;Fit in the second thermoplastic resin film 30 of the another side of polarizing film 10.First and second thermoplastic resin film 20,30 is for example For protective film.
A side of first and second thermoplastic resin film 20,30 can be omitted as polarization plates 2b shown in Fig. 3.? The second thermoplastic resin film 30 is omitted in polarization plates 2b.It is such that only there is the inclined of thermoplastic resin film in the one side of polarizing film 10 Vibration plate is conducive to the filming of polarization plates.
Although in Fig. 2 and Fig. 3, the illustration is omitted, can it is preferable to use bonding agent carry out polarizing film 10 and first and The fitting of second thermoplastic resin film 20,30.
(3-2) polarizing film
The polarizing film 10 for constituting polarization plates 2 is the linear polarization for having the vibration plane for being parallel to its absorption axis with absorption Light, transmission have the inclined of the absorption-type of the property of the rectilinearly polarized light of (with the axis of homology parallel) vibration plane orthogonal with absorption axiss Shake piece.An example of polarizing film 10 is to make the polyvinyl alcohol resin film absorption dichroism pigment by being uniaxially stretched and be orientated Polarizing film.Such polarizing film 10 for example can use the process including being uniaxially stretched to polyvinyl alcohol resin film;Pass through The process that polyvinyl alcohol resin film dichroism pigment is dyed and adsorbs dichroism pigment;Dichroism pigment will be adsorbed with The process of the crosslinked fluids such as polyvinyl alcohol resin film boric acid aqueous solution processing;And water is carried out after the processing using crosslinked fluid The method of the process washed manufactures.
As polyvinyl alcohol resin, resin obtained by being saponified polyvinyl acetate system resin can be used.As poly- Vinyl acetate resin can be with other than it can enumerate the polyvinyl acetate as the homopolymer of vinyl acetate Enumerate the copolymer etc. of vinyl acetate with the other monomers that can be copolymerized.It can be with the other monomers of vinyl acetate copolymerization Example includes unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class and (methyl) propylene with ammonium Amides etc..
" (methyl) acrylic compounds " so-called in this specification, refer in acrylic compounds and methacrylic at least One side.Also identical in " (methyl) acryloyl group ", " (methyl) acrylate " etc..
The saponification degree of polyvinyl alcohol resin is usually 85~100mol%, preferably 98mol% or more.Polyethenol series Resin can also be modified, such as the polyvinyl formal or polyvinyl acetal being modified by aldehydes also can be used Deng.The average degree of polymerization of polyvinyl alcohol resin is usually 1000~10000, and preferably 1500~5000.
The saponification degree and average degree of polymerization of polyvinyl alcohol resin can be found out according to JIS K 6726.
Film obtained by such polyvinyl alcohol resin film is used by the former material film as polarizing film 10.By polyvinyl alcohol It is that the method that resin is film-made is not particularly limited, well known method can be used.The thickness of polyvinyl alcohol resin film is without spy It does not limit, for example, 10~150 μm or so, preferably 50 μm are hereinafter, more preferably 35 μm or less.
Being uniaxially stretched for polyvinyl alcohol resin film simultaneously or can contaminated before the dyeing of dichroism pigment, with dyeing It is carried out after color.In the case where being uniaxially stretched after dyeing, this is uniaxially stretched can be before crosslinking Treatment or in crosslinking Treatment It carries out.Alternatively, it is also possible to be uniaxially stretched in these multiple stages.
When being uniaxially stretched, it can be stretched between the different roller of peripheral speed with uniaxial manner, heat also can be used Roller is stretched with uniaxial manner.It can be the dry type stretching stretched in an atmosphere in addition, being uniaxially stretched, be also possible to Make the wet tensile stretched in the state of polyvinyl alcohol resin membrane swelling using solvent, water.Stretching ratio is usually 3~ 8 times or so.
As the method for dyeing polyvinyl alcohol resin film with dichroism pigment, for example, can using by the film immersion in Method in aqueous solution containing dichroism pigment.As dichroism pigment, iodine, dichroic organic dye are used.It needs to illustrate , the first impregnation of implementation Xiang Shuizhong preferably before dyeing processing of polyvinyl alcohol resin film.
Generalling use as the crosslinking Treatment after the dyeing using dichroism pigment will be through hyperchromatic polyethenol series tree Adipose membrane is impregnated in the method in the aqueous solution containing boric acid.In the case where using iodine as dichroism pigment, this contains boric acid Aqueous solution preferably comprise potassium iodide.
The thickness of polarizing film 10 is usually 2~40 μm or so.From the viewpoint of the filming of polarization plates 2, polarizing film 10 Thickness be preferably 20 μm hereinafter, more preferably 15 μm hereinafter, further preferably 10 μm or less.Polarizing film 10 is thicker, optics Laminated body is more easy to generate curling, according to the present invention, even if the thickness of polarizing film 10 is, for example, 10 μm or more, is further 15 μm Above, specifically for 20 μm or more, the optical laminate for inhibiting inverse curling can also be provided.
(3-3) first and second thermoplastic resin film
First and second thermoplastic resin film 20,30 is each independently by the thermoplastic resin, preferably with translucency The film being made of optically transparent thermoplastic resin.Constitute the thermoplastic resin of first and second thermoplastic resin film 20,30 It such as can be chain polyolefin-based resins (polypropylene-based resin etc.), cyclic polyolefin hydrocarbon system resin (norbornene resin etc.) Etc polyolefin-based resins;The cellulose-based resin of triacetyl cellulose, diacetyl cellulose etc;Poly terephthalic acid second The polyester based resin of diol ester, polybutylene terephthalate (PBT) etc;Polycarbonate-based resin;Methyl methacrylate system tree (methyl) acrylic resin of rouge etc;Polystyrene resin;Polyvinyl chloride resin;Acrylonitrile/butadiene/styrene It is resin;Acrylonitrile/phenylethylene resin series;Polyvinyl acetate system resin;Polyvinylidene chloride resin;Polyamide-based tree Rouge;Polyacetals system resin;Noryl system resin;Polysulfones system resin;Polyether sulfone system resin;Polyarylate system resin;Polyamide Imide series resin;Polyimides system resins etc..
Chain olefin as chain polyolefin-based resins, in addition to polyvinyl resin, acrylic resin etc can be enumerated Homopolymer other than, the copolymer formed by two or more chain olefins can also be enumerated.More specific example includes poly- third Alkene system resin (acrylic resin of the homopolymer as propylene, the copolymer based on propylene), polyethylene-based resin (as The polyvinyl resin of the homopolymer of ethylene, the copolymer based on ethylene).
Cyclic polyolefin hydrocarbon system resin is the general name for the resin being polymerize using cyclic olefin as polymerized unit.If enumerating ring-type The concrete example of polyolefin-based resins is then the open loop (co) polymer of cyclic olefin, the addition polymer of cyclic olefin, cyclic annular alkene Hydrocarbon is with the copolymer (representative situation is random copolymer) of the chain olefin of ethylene, propylene etc and by them with not Graft polymers and their hydride that saturated carboxylic acid or derivatives thereof has been modified etc..Wherein, it is preferable to use as ring-type Alkene has used the norbornene resin of the orbornene-baseds monomers such as norbornene, polycyclic orbornene-based monomer.
So-called cellulose-based resin refers to and is obtained by raw celluloses such as cotton linters, wood pulps (broad leaf tree slurry, softwood pulp) Cellulose hydroxyl hydrogen atom part or all by acetyl group, propiono and/or bytyry instead of cellulose Organic acid esters or cellulose mixed organic acid ester.For example, by the acetic acid esters of cellulose, propionic ester, butyrate and The resin of the formation such as their mixed ester.Wherein, preferably triacetyl cellulose, diacetyl cellulose, cellulose ethanoate propionic acid Ester, cellulose acetate butyrate.
Polyester based resin is the resin having other than the above-mentioned cellulose-based resin of ester bond, generally by polyacid or its spread out The resin that the condensation polymer of biology and polyalcohol is formed.2 yuan binary acid or derivatives thereof conduct polyacid can be used or it spreads out Biology, for example, terephthalic acid (TPA), M-phthalic acid, dimethyl terephthalate (DMT), naphthalene diformic acid dimethyl ester etc..It can be with Use 2 yuan of glycol as polyalcohol, for example, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexamethylene diformazan Alcohol etc..The example of suitable polyester based resin includes polyethylene terephthalate.
Polycarbonate-based resin is the engineering plastic that the polymer as obtained by being bonded monomeric unit by carbonate group is formed Material, is the resin with high impact properties, heat resistance, anti-flammability, the transparency.Polycarbonate-based resin is also possible to reduce Photoelastic coefficient and modified the resin referred to as modified polycarbonate of polymer backbone, improved the copolymerization of wavelength dependency Polycarbonate etc..
(methyl) acrylic resin is the polymer comprising the Component units from (methyl) acrylic monomer.It should Polymer is the polymer comprising methacrylate in the typical case.Preferably from the structure of methacrylate Polymer of the ratio of unit relative to entire infrastructure unit comprising 50 weight % or more.(methyl) acrylic resin can be The homopolymer of methacrylate is also possible to the copolymer comprising the Component units from other polymerizable monomers.The feelings Under condition, from other polymerizable monomers Component units ratio preferably with respect to entire infrastructure unit be 50 weight % with Under.
As the methacrylate that can constitute (methyl) acrylic resin, preferably alkyl methacrylate.Make For alkyl methacrylate, methyl methacrylate, ethyl methacrylate, n propyl methacrylate, first can be enumerated Base isopropyl acrylate, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid The carbon atom number of the alkyl of 2- ethylhexyl, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate etc is 1~8 Alkyl methacrylate.The carbon atom number of alkyl contained in alkyl methacrylate is preferably 1~4.At (methyl) In acrylic resin, one kind can be only used alone in methacrylate, also can be used together two or more.
As other the above-mentioned polymerizable monomers that can constitute (methyl) acrylic resin, can enumerate acrylate, And it is other in the molecule with the compound of polymerism carbon-to-carbon double bond.Other polymerizable monomers can only be used alone One kind also can be used together two or more.As acrylate, preferably alkyl acrylate.As alkyl acrylate, Ke Yiju Out methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, The carbon of the alkyl of tert-butyl acrylate, 2-EHA, cyclohexyl acrylate, acrylic acid 2- hydroxy methacrylate etc is former The alkyl acrylate etc. that subnumber is 1~8.The carbon atom number of alkyl contained in alkyl acrylate is preferably 1~4.In (first Base) in acrylic resin, one kind can be only used alone in acrylate, also can be used together two or more.
As other in the molecule with the compound of polymerism carbon-to-carbon double bond, ethylene, propylene, benzene second can be enumerated The vinyl cyanide compound of the vinyl compounds such as alkene, acrylonitrile etc.It is other that there is polymerism carbon-to-carbon in the molecule One kind can be only used alone in the compound of double bond, also can be used together two or more.
First and second thermoplastic resin film 20,30, which can be, is laminated the inclined for protecting of the one side for fitting in polarizing film 10 The protective film of vibration piece 10.What first or second thermoplastic resin film 20,30 was also possible to phase difference film, brightness enhancement film etc has both light Learn the protective film of function.
For example, (being stretched uniaxially or biaxially by being stretched to the thermoplastic resin film formed by above-mentioned material Deng), the phase difference film for having been assigned arbitrary phase difference value can be made.First and/or second thermoplastic resin film 20,30 At the surface that can have the hard conating for being laminated in its surface, antiglare layer, anti-reflection layer, anti-static electricity interference layer, stain-proofing layer etc It manages layer (coat).
The thickness of first and second thermoplastic resin film 20,30 is usually 1~100 μm, however is seen from intensity, disposition property etc. Point consideration, preferably 5~60 μm, more preferably 5~50 μm.
First thermoplastic resin film 20, the thickness of the second thermoplastic resin film 30 are smaller, the polarization plates list with protective film Sheet body is more easy to generate curling, however according to the present invention, even if the first thermoplastic resin film 20, the second thermoplastic resin film 30 It is for example thin to 40 μm or less of thickness, further thin to 30 μm hereinafter, the optical laminate for inhibiting inverse curling can also be provided.
In the case where having thermoplastic resin film on the two sides of polarizing film 10 as polarization plates 2a shown in Fig. 2, this A little thermoplastic resin films can be made of thermoplastic resin of the same race, can also be made of thermoplastic resin not of the same race.In addition, Thickness may be the same or different.In the case where fitting in the composition of thermoplastic resin film on two sides difference, it is easy in light It learns and generates curling in laminated body, therefore is of the invention especially advantageous in this case.
(3-4) bonding agent
Polarization is fitted in across adhesive layer as set forth above, it is possible to for example press from both sides the first, second thermoplastic resin film 20,30 Piece 10.As the bonding agent for forming adhesive layer, water system bonding agent, active energy ray-curable bonding agent or heat can be used Solidity bonding agent, preferably water system bonding agent, active energy ray-curable bonding agent.
As water system bonding agent, the bonding agent formed by polyvinyl alcohol resin aqueous solution, water system bi-component can be enumerated Type carbamate system emulsion adhesive etc..Wherein it is possible to suitably use the water formed by polyvinyl alcohol resin aqueous solution It is bonding agent.As polyvinyl alcohol resin, in addition to the polyvinyl acetate to the homopolymer as vinyl acetate can be used Ester carries out obtained by saponification process other than alcotex, can also use to vinyl acetate with can be copolymerized therewith its The copolymer of his monomer carries out polyvinyl alcohol based copolymer obtained by saponification process or is modified their hydroxylic moiety and obtains Modified polyvinylalcohol based polymer etc..Water system bonding agent may include aldehyde compound (glyoxal etc.), epoxide, trimerization The crosslinking agents such as cyanamide based compound, methylol compound, isocyanate compound, amine compounds, multivalent metal salt.
Using water system bonding agent, preferably by polarizing film 10 and the first, second thermoplastic resin film 20,30 After fitting, implement the drying process for removing water contained in water system bonding agent.After drying process, such as it can be set The curing step of 20~45 DEG C of temperature curing.
So-called active energy ray-curable bonding agent is containing because of ultraviolet light, visible light, electron beam, X-ray etc The irradiation of active energy beam and the bonding agent of cured curability compound, preferably ultra-violet solidified bonding agent.
Curability compound can be the curability compound of cationically polymerizable, free-radical polymerised curability chemical combination Object.As the curability compound of cationically polymerizable, for example, epoxy compound (has 1 or 2 in the molecule The compound of a above epoxy group), oxetanes based compound is (in the molecule with 1 or 2 or more oxa- ring fourth The compound of alkane ring) or their combination.As free-radical polymerised curability compound, for example, (methyl) Acrylic compounds (in the molecule with the compound of 1 or 2 or more (methyl) acryloxy) have free radical The other vinyl compounds or their combination of the double bond of polymerism.Also the solidification of cationically polymerizable can be used together Property compound and free-radical polymerised curability compound.Active energy ray-curable bonding agent is usually also comprising for drawing Send out the cationic polymerization initiators and/or radical polymerization initiator of the curing reaction of curability compound.
It, to improve cementability, can be right when polarizing film 10 to be bonded with the first, second thermoplastic resin film 20,30 The binding face of their at least any one party implements surface activation process.As surface activation process, can enumerate sided corona treatment, Corona treatment, discharge treatment (glow discharge process etc.), flame treatment, ozone treatment, UV ozone treatment, ionization activity are penetrated Line handles the dry process of (UV treatment, electron beam treatment etc.) etc;At the ultrasonic wave for having used water, acetone equal solvent The wet processed of reason, saponification process, anchor painting processing etc.These surface activation process can be carried out individually, can also combine two Kind or more.
In the case where the two sides of polarizing film 10 is bonded thermoplastic resin film, for what these thermoplastic resin films were bonded Bonding agent can be bonding agent of the same race, be also possible to bonding agent not of the same race.
(4) phase separation layer
Optical laminate includes one layer or more of the side opposite side with stacking protective film 1 for being laminated in polarization plates 2 Phase separation layer (layer with phase difference characteristics).Fig. 1 shows the examples for providing 2 layers of phase separation layer.
In the case where optical laminate includes 2 layers or more of phase separation layer, these phase separation layers can have phase Tongfang To slow axis, it is possible to have the slow axis in direction different from each other.
One layer or more of phase separation layer contained in optical laminate can be each independently the phase separation layer as film (phase difference film), or the layer formed by coating (coating) phase separation layer formation with composition, preferably by painting The layer for covering (coating) and being formed.
An example of phase separation layer is phase separation layer (the liquid crystal curing type phase difference being made of the solidfied material of liquid-crystal compounds Layer).Liquid-crystal compounds has the liquid crystal aligning of assigned direction in the phase separation layer, and the orientation is due to the solidification of liquid-crystal compounds It is fixed.The orientation restraint that the liquid crystal aligning of assigned direction can use aftermentioned oriented layer is adjusted.
As the liquid-crystal compounds for forming phase separation layer, it is preferable to use the polymerizable liquid crystal chemical combination with polymerizable group Object.Using the polymerization reaction of the polymerizable liquid crystal compound, the state of orientation of liquid-crystal compounds can be fixed.As polymerism liquid The polymerization reaction of brilliant compound can be the heat polymerization using thermal polymerization, be also possible to cause using photopolymerization The photopolymerization reaction of agent, however preferably photopolymerization reaction.
The differently- oriented directivity of liquid-crystal compounds contained in phase separation layer can be limited using oriented layer as described above, However in the case where using polymerizable liquid crystal compound as liquid-crystal compounds, it can also be made by carrying out polarizing light irradiation Light orientation occurs for polymerizable liquid crystal compound, embodies or improves the orientation of polymerizable liquid crystal compound, be thus adjusted.
Liquid crystal curing type phase separation layer can be used well known liquid-crystal compounds and be formed.The type of liquid-crystal compounds is without spy It does not limit, Rod-like liquid crystal compound, disc-like liquid crystal compound and their mixture can be used.
One layer or more of phase separation layer contained in optical laminate can be each independently for example as 1/2 wavelength The phase separation layer that plate, 1/4 wavelength plate, positive c plate, 1/4 wavelength plate of inverse wave length dispersibility etc. play a role.
In the case where optical laminate includes 2 layers of phase separation layer, as their combination, 1/2 wavelength can be enumerated The combination of plate and 1/4 wavelength plate, the combination of 1/4 wavelength plate of positive c plate and inverse wave length dispersibility.
For the thickness of phase separation layer, for phase difference film, usually 1~100 μm, however from intensity, from The consideration of the viewpoints such as setting property, preferably 5~60 μm, more preferably 5~50 μm.
It is being to be formed by coating (coating) as liquid crystal curing type phase separation layer for the thickness of phase separation layer In the case where layer, usually 0.1~10 μm, preferably 0.2~8 μm, more preferably 0.5~5 μm.
Phase separation layer can be laminated in a manner of directly contacting with adjacent layer, can also be pressed from both sides across adhesive layer (such as Fig. 1 Shown in optical laminate the first adhesive layer 3a, the second adhesive layer 4a) stacking.
Adhesive layer can be the layer formed by bonding agent, be also possible to the layer formed by adhesive.
About bonding agent, the record of above-mentioned (3-4) is quoted.About adhesive (adhesive composition), quote following (5) Record.
(5) first adhesive phase
First adhesive phase 5 is following adhesive phase, in polarization plates 2 and the stacking side of protective film 1 opposite one Side is configured at outside (side far from polarization plates 2) compared with above-mentioned one layer or more of phase separation layer, and is laminated in optics In the case that body includes multiple adhesive phases, it is configured at outermost.
First adhesive phase 5 can be used for fitting in optical laminate image-displaying member, other optical components.
First adhesive phase 5 can by with (methyl) acrylic acid series, rubber series, carbamate system, ester system, silicone-based, The resin of polyvingl ether system etc is constituted as the adhesive composition of principal component.Wherein, it is suitably for transparent, weather-proof Property, adhesive composition of excellent (methyl) acrylic resin such as heat resistance as basic polymer.Adhesive composition It is also possible to active energy ray curable, thermohardening type.
As (methyl) acrylic resin (base polymer) used in adhesive composition, such as can be suitably Use is with (methyl) butyl acrylate, (methyl) ethyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid 2- second Polymer or copolymer of the one or more of (methyl) acrylate of the own ester of base etc as monomer.It is preferred that making polarity Monomer and base polymer are copolymerized.As polar monomer, for example, (methyl) acrylic acid, (methyl) acrylic acid 2- hydroxyl Base propyl ester, (methyl) Hydroxyethyl Acrylate, (methyl) acrylamide, N, N- dimethyl aminoethyl (methyl) acrylate, The monomer with carboxyl, hydroxyl, amide groups, amino, epoxy group etc. of (methyl) glycidyl acrylate etc.
Adhesive composition can only include above-mentioned base polymer, however usually also contain crosslinking agent.As crosslinking agent, It may be exemplified out the metal ion more than as divalent and form the crosslinking agent of carboxylic metallic salt between carboxyl at it;As more Amine compounds and the crosslinking agent for forming amido bond between carboxyl at it;As polyepoxy compound or polyalcohol and its with The crosslinking agent of ester bond is formed between carboxyl;The friendship of amido bond is formed between carboxyl as polyisocyanate compound and at it Join agent.Wherein, preferred polyisocyanate compound.
So-called active energy ray curable adhesive composition is the adhesive composition with following property, that is, by To the active energy beam of ultraviolet light, electron beam etc irradiation and solidify, and also have before active energy beam irradiation viscous Conjunction property and can be closely sealed with the adherend such as film, can solidify because of the irradiation of active energy beam, realize the adjustment of closing force. Active energy ray curable adhesive composition is preferably ultraviolet hardening.The combination of active energy ray curable adhesive Object also contains active energy beam polymerizable compound on the basis of base polymer, crosslinking agent.Furthermore according to needs, Photoepolymerizationinitiater initiater, photosensitizer etc. can be contained.
Adhesive composition can be containing for assigning light scattering particle, pearl (resin bead, bead etc.), glass Resin, anti-static electricity interference agent, tackifier, filler (metal powder, other inorganic powders etc.) other than fiber, base polymer, The additives such as antioxidant, ultraviolet absorbing agent, dyestuff, pigment, colorant, defoaming agent, preservative, Photoepolymerizationinitiater initiater.
First adhesive phase 5 can be by the way that the organic solvent diluting liquid of above-mentioned adhesive composition to be coated on substrate simultaneously It is allowed to dry and is formed.Substrate can be phase separation layer, the diaphragm (such as diaphragm 6) etc. of composition optical laminate.It is using In the case where active energy ray curable adhesive composition, by be formed by adhesive phase irradiate active-energy penetrate The solidfied material with desired curing degree can be made in line.
The thickness of first adhesive phase 5 is usually 1~40 μm, however is considered from viewpoints such as the filmings of optical laminate, Preferably 2~30 μm.
(6) diaphragm
Diaphragm (stripping film) 6 is in order to which first adhesive phase 5 is being fitted in image-displaying member or other optical components The preceding film protecting its surface and temporarily attaching.Diaphragm 6 is usually by utilizing the release agents such as silicone-based, fluorine system etc. to implementing on one side The thermoplastic resin film of demoulding processing is constituted, and demoulding process face fits in first adhesive phase 5.
The thermoplastic resin for constituting diaphragm 6 for example can be the polyethylene-based resin, polypropylene of polyethylene etc The polyester based resin etc. of polypropylene-based resin, polyethylene terephthalate or polyethylene naphthalate etc.Diaphragm 6 Thickness be, for example, 10~50 μm.
The manufacturing method > of < optical laminate
Referring to Fig. 4, the manufacturing method of optical laminate of the invention includes following processes:
The protective film layer in the region comprising meeting aftermentioned formula (I) is laminated on the one side of polarization plates and is obtained with protective film Polarization plates first step (the polarization plates manufacturing process with protective film) S101 and
Optical laminate manufacturing process S102.
Optical laminate manufacturing process S102 is preferably included:
The second step, in the surface layer with above-mentioned one side opposite side of the polarization plates of the resulting polarization plates with protective film Folded one layer or more of phase separation layer and adhesive phase;And
The third step cuts out the optical laminate from above-mentioned zone.
Hereinafter, each process is described in detail.
(1) first step
Referring to Fig. 5, the first step that polarization plates 2 are bonded with protective film 1 (the polarization plates manufacturing process with protective film) A pair of rolls (doubling roller) 8,8 can be used for example to carry out in S101.From the viewpoint of manufacture efficiency, this method is in polarization plates 2 And protective film 1 be long size shape in the case where it is particularly advantageous.
Thus, the polarization plates 2 and protective film 1 for being supplied to the polarization plates manufacturing process S101 with protective film are preferably all length Size shape.
The polarization plates 2 of long size shape and the length of protective film 1 are, for example, 100~20000m, preferably 1000~ 10000m.In addition, the polarization plates 2 of long size shape and the width of protective film 1 are, for example, 0.5~3m, preferably 1~2.5m.
The protective film 1 for being supplied to the polarization plates manufacturing process S101 with protective film includes the region for meeting lower formula (I):
First the-the second elasticity modulus of elasticity modulus >=300MPa (I)
The region can be entire protective film 1, be also possible to a part.It should be noted that in the protective film of long size Usually there are the first elasticity modulus and the second elasticity modulus respectively different situation in the direction of the width, however it is long aobvious in length direction Roughly the same value is shown.
In formula (I), so-called first elasticity modulus is the suction with polarization plates 2 at 23 DEG C of temperature, relative humidity 55%RH The tensile modulus of elasticity (MPa) on the orthogonal direction of axis is received, so-called second elasticity modulus is in 23 DEG C of temperature, relative humidity Tensile modulus of elasticity (MPa) on the direction parallel with the absorption axiss of polarization plates 2 under 55%RH.
So-called " meeting formula (I) " refers to that first is elastic when measuring the protective film according to aftermentioned embodiment one record Modulus and the second elasticity modulus meet formula (I).
From the viewpoint of the inverse curling for inhibiting optical laminate, the left side of formula (I) is preferably 400MPa or more, more preferably For 500MPa or more.The left side of formula (I) is usually 2000MPa hereinafter, being 1500MPa or less in typical situation.
As the protective film 1 for being supplied to the polarization plates manufacturing process S101 with protective film, for acquired protective film The left side of measurement formula (I), uses the protective film for meeting formula (I).
For being bonded for polarization plates 2 and protective film 1, such as the polarization plates 2 of long size shape are continuously transported, while continuous Ground transports the protective film 1 of long size shape, presss from both sides between 1 ground of a face overlapping protection film of polarization plates 2 passes through a pair of of doubling roller 8,8 Enter, it is possible thereby to manufacture the polarization plates 7 with protective film for being bonded two films.
The direction MD (carriage direction) of polarization plates 2 is usually parallel with the direction MD (carriage direction) of protective film 1.It is so-called flat Row, the direction the MD angulation in the direction MD and protective film 1 that refer to polarization plates 2 are 0 degree ± 5 degree, preferably 0 degree ± 2 degree.
From the viewpoint of the inverse curling for inhibiting resulting optical laminate, preferably so that the absorption axiss of polarization plates 2 and guarantor Two films are bonded by the mode that the direction MD of cuticula 1 is parallel.It is so-called parallel, refer to the absorption axiss of polarization plates 2 and the side MD of protective film 1 It is 0 degree ± 5 degree, preferably 0 degree ± 2 degree to angulation.
In the case where two films are bonded in the mode for keeping the absorption axiss of polarization plates 2 parallel with the direction MD of protective film 1, with The orthogonal direction of the absorption axiss of polarization plates 2 is synonymous with the direction TD of protective film 1 and polarization plates 2.
Between so that the laminated body of polarization plates 2 and protective film 1 is passed through a pair of of doubling roller 8,8, thus laminated body is pushed from upper and lower, To which two films are closely sealed.
In polarization plates 2 in its outmost surface with transparent hard-coating layer (hard conating of smooth surface) and in the transparent hard painting In the case where being bonded protective film 1 on layer, it is easy to improve the closing force between polarization plates 2 and protective film 1, is thus easily obtained inverse Crimp the trend for the optical laminate being inhibited.Thus, polarization plates 2 preferably have transparent hard-coating layer (table in its outmost surface The smooth hard conating in face).
In the case where protective film 1 is made of the second adhesive phase 50 of base material film 40 and stacking thereon, in polarization plates 2 A face overlapping protection film 1 after when passing through a pair of of doubling roller 8,8, the second adhesive phase 50 of protective film 1 by with polarization plates 2 The mode of an above-mentioned face contact be overlapped.It can be before the stacking of protective film 1 and polarization plates 2, to protective film 1 and polarization plates 2 The binding face of at least any one party carry out corona treatment, sided corona treatment, ultraviolet treatment with irradiation, flame (flame) processing, The surface activation process of saponification process etc.
In the process being bonded using a pair of of doubling roller 8,8, the laminated body of protective film 1 and polarization plates 2 is assigned Pressure (clamping pressure) is, for example, 0.01~0.5MPa, or 0.05~0.3MPa.As doubling roller 8,8, table can be used Face is the metal (alloys such as including SUS.), the known doubling roller such as the roller of rubber system.
In the polarization plates manufacturing process S101 with protective film, tension preferably is being applied to polarization plates 2 and protective film 1 The fitting of two films is carried out simultaneously, and the fitting forward pull of more preferable polarization plates 2 is less than the fitting forward pull of protective film 1.Such tension It controls advantageous from the aspect of the inverse curling for inhibiting resulting optical laminate.Fitting forward pull, which refers to, is bonded (two for two films The laminated body of film pass through a pair of of doubling roller 8,8) before the direction MD for being applied to film tension, can be according to aftermentioned embodiment one The record measurement of item.
Fitting toe-out from the viewpoint of the inverse curling for inhibiting resulting optical laminate, on the direction MD of polarization plates 2 Power is preferably 250N/m hereinafter, more preferably 200N/m or less.
From the same viewpoint, the fitting forward pull on the direction MD of protective film 1 is preferably 260N/m or more, more preferably For 300N/m or more.
(2) the second step
This process be the polarization plates 7 with protective film polarization plates 2 with the side opposite side that is laminated with protective film 1 The phase separation layer of one layer of stacking or more and the process of first adhesive phase 5.Can also the outside of first adhesive phase 5 face also It is laminated with diaphragm 6.
Optical laminate obtained in the process is preferably long size shape.
The length of long size shape optical laminate is, for example, 100~20000m, preferably 1000~10000m.In addition, The width of optical laminate as long size shape is, for example, 0.5~3m, preferably 1~2.5m.
Stacking of the phase separation layer in the polarization plates 7 with protective film can will include the layer of base material film and phase separation layer After stack is laminated in above-mentioned opposite side, the process including peeling base film.This method is liquid crystal curing type phase in phase separation layer It is advantageous in the case where the layer of potential difference layer etc formed and being coated (coating).
In the case where the process of laminated phase-difference layer includes removing the process of above-mentioned base material film, it is easy in resulting optics Inverse curling is generated in laminated body, however according to the present invention, even if can also be made in the case where including the process of peeling base film Make the optical laminate that inverse curling is inhibited.
For example, as first phase difference of the stacking as the layer formed using coating in the polarization plates 7 with protective film The method of layer 3, can enumerate the method including following process.Second phase difference layer 4 can also be carried out similarly stacking.
(a) on base material film formed oriented layer process,
(b) in oriented layer formed first phase difference layer 3 and obtain laminated body process,
(c) with protective film polarization plates 7 on folder across the first adhesive layer 3a be laminated above-mentioned laminated body process and
The process of (d) peeling base film.
As oriented layer, as long as horizontal alignment can be assigned to liquid-crystal compounds contained in phase separation layer, vertically taken To the material of, orientations such as hybrid orientation, tilted alignment, just it is not particularly limited.As oriented layer, for example, by taking The alignment films of tropism polymer formation, the optical alignment film for having used light orientation polymer or groove (groove) alignment films etc., The optical alignment film of light orientation polymer is preferably used.
In the case where oriented layer is the alignment films formed by orientation polymer, surface state, fricting strip can use Part arbitrarily adjusts the orientation restraint for liquid-crystal compounds.In this case, that will include orientation polymer and solvent Composition be coated on base material film and remove solvent, or after being coated on base material film by above-mentioned composition and remove solvent, carry out Well known friction treatment, it is possible thereby to form oriented layer.
It will include with photoreactivity in the case where oriented layer is to have used the optical alignment film of light orientation polymer After the polymer or monomer of group and the composition of solvent are coated on base material film and remove solvent, polarised light is irradiated, it is possible thereby to Obtain oriented layer.As the polarised light irradiated, it is preferable to use polarized UV rays.
It will include that the phase separation layer formation of liquid-crystal compounds and solvent is coated in oriented layer with composition and removes molten After agent, ultraviolet light is irradiated, it is possible thereby to be orientated liquid-crystal compounds with state of orientation corresponding with the orientation restraint of oriented layer And form phase separation layer.
As liquid-crystal compounds, it is preferable to use the polymerizable liquid crystal compound with polymerizable group.Utilize polymerism liquid The polymerization reaction of brilliant compound can fix the state of orientation of liquid-crystal compounds.
The differently- oriented directivity of liquid-crystal compounds contained in phase separation layer can be limited using oriented layer as described above, so And in the case where using polymerizable liquid crystal compound as liquid-crystal compounds, it can also make to gather by carrying out polarizing light irradiation Light orientation occurs for conjunction property liquid-crystal compounds, embodies or improves the orientation of polymerizable liquid crystal compound, be thus adjusted.
Thereafter, by implementing process (c) and (d), the phase separation layer as the layer formed using coating can be laminated in In polarization plates 7 with protective film.
On the other hand, in the case where phase separation layer is phase difference film, preferably prepare the phase difference film of long size shape, only The phase difference film is pressed from both sides using doubling roller and fits in above-mentioned opposite side across adhesive layer.
With protective film polarization plates 7 polarization plates 2 be laminated with protective film 1 side opposite side be laminated one layer After above phase separation layer, then the laminated body of first adhesive phase 5 or first adhesive phase 5 and diaphragm 6 is laminated, available light Learn laminated body.
(3) the third step
In the case that the optical laminate obtained in the second step is long size shape, preferably by this process from long ruler Monolithic body is cut out in very little shaped optical laminated body.
It cuts out and (cuts) to can be used to cut with the known cutting means such as cutting machine and carry out.
For the size of monolithic body, shape and angle is cut out, quotes the record of above-mentioned < optical laminate > (1).
[embodiment]
Hereinafter, provide experimental example and the present invention is further elaborated with, however the present invention is not limited by these examples.
In following examples, according to following methods determine the thickness of polarization plates and film, the elastic modulus difference of protective film, with And the fitting forward pull on the direction MD of polarization plates and protective film.
(1) thickness of polarization plates and film
The digital micrometer " MH-15M " of (strain) Nikon is used to measure.
(2) elastic modulus difference of protective film
For elastic modulus detection sample, with cupping machine ((strain) Shimadzu Seisakusho Ltd. Autograph AG- Xplus testing machine) fixture up and down, the longitudinal direction of said determination sample is clamped in a manner of being divided into 5cm between making fixture Both ends, in the environment of 23 DEG C, relative humidity 55%, with tensile speed 1mm/ minutes by test sample along test sample Length direction stretches, according to the slope of the straight line between 3~6MPa in resulting load-deformation curve, calculate 23 DEG C, it is opposite Tensile modulus of elasticity (MPa) under humidity 55%.At this point, only used and drawn by twin shaft as the thickness for calculating stress The thickness value for the polyethylene terephthalate (base material film) stretched.
It is the first elasticity modulus by the tensile modulus of elasticity that the measurement of the test sample of the first elasticity modulus is calculated, by The tensile modulus of elasticity that the measurement of the test sample of second elasticity modulus is calculated is the second elasticity modulus.
According to resulting first elasticity modulus and the second elasticity modulus, first the-the second elasticity modulus of elasticity modulus is calculated.
Hereinafter, first the-the second elasticity modulus of elasticity modulus is referred to as " elastic modulus difference ".
(3) the fitting forward pull on the direction MD of polarization plates and protective film
Using doubling roller and the tension-sensing roller between a pair of of niproll of doubling roller is set to, determine with In a pair of of doubling roller for being bonded polarization plates with protective film and trip side disposed thereon and near a pair of of niproll of doubling roller it Between the layer tension (N/m) of polarization plates and protective film advanced, as the fitting forward pull on the direction MD.
< Examples 1 to 3,1~2 > of comparative example
(A) production of polarizing film
Continuously transport long size polyvinyl alcohol film (average degree of polymerization: about 2400, saponification degree: 99.9 moles of % with Upper, thickness: 30 μm) while, being uniaxially stretched in the way of dry type is about 4 times, then keeps tense situation constant, at 40 DEG C After being impregnated 1 minute in pure water, impregnated 60 seconds in the aqueous solution that iodine/potassium iodide/water weight ratio is 0.1/5/100 at 28 DEG C. Thereafter, it is impregnated 300 seconds in the aqueous solution that potassium iodide/boric acid/water weight ratio is 10.5/7.5/100 at 68 DEG C.Next, It is 180 seconds dry at 70 DEG C after cleaning 5 seconds with 5 DEG C of pure water, it obtains being adsorbed with iodine on the polyvinyl alcohol film by being uniaxially stretched And the polarizing film for the long size shape being orientated.Polarizing film with a thickness of 13 μm.
(B) production of polarization plates
The polarizing film for continuously transporting long size shape obtained in above-mentioned (A), simultaneously continuously transports long size shape The first thermoplastic resin film (Nippon Paper (strain) system the trade name " COP25ST-HC " as clear hard coat film, in ring-type Be formed with film, the thickness of transparent hard-coating layer on polyolefin-based resins film: 29 μm) and long size shape the second thermoplastic resin film (trade name " ZRG20SL " as triacetyl cellulose (TAC) film of Fuji Photo Film (Ltd.), thickness: 20 μm), on one side to inclined It shakes between piece and the first thermoplastic resin film and injects water system bonding agent between polarizing film and the second thermoplastic resin film, one Between side passes through a pair of of doubling roller, obtain by the first thermoplastic resin film/water system adhesive layer/polarizing film/water system adhesive layer/the The stacked film that two thermoplastic resin films are constituted.
Next, transporting resulting stacked film, the heat treatment of 80 DEG C, 300 seconds is carried out across air drier, thus Keep water system adhesive layer dry, obtains the polarization plates of long size shape.
As above-mentioned water system bonding agent, used by pva powder (Japanese synthetic chemical industry (strain) system Trade name " GOHSEFIMER ", average degree of polymerization: 1100) it is dissolved in the poly- second of 3 weight % of concentration obtained by 95 DEG C of hot water Relative to 10 parts by weight of pva powder with ratio mixed cross-linker (Japan's synthesis chemistry of 1 parts by weight in enol aqueous solution The sodiam glyoxlate of industrial (strain) system) obtained by aqueous solution.Resulting polarization plates with a thickness of 62 μm.
(C) production of polarization plates of the long size shape with protective film
The polarization plates of long size shape obtained in above-mentioned (B) are continuously transported, simultaneously continuously transports and has removed diaphragm Long size shape protective film (by being laminated on biaxial stretch-formed polyethylene terephthalate (thickness: 38 μm) The trade name " AY-4212 " of rattan lumber industry (strain) system of (methyl) acrylic adhesive layer (thickness: 15 μm)), by their weights Between passing through a pair of of doubling roller foldedly, thus from the upper and lower laminated body for pushing protective film and polarization plates, it is continuously manufactured by out long size Shape has the polarization plates of protective film.
Protective film is pressed from both sides to the first thermoplastic resin film (clear hard coat film) face that polarization plates are fitted in across its adhesive phase.
It should be noted that the pressure (clamping is pressed) assigned using laminated body of the doubling roller to protective film and polarization plates is 0.1MPa.At this point, the fitting forward pull on the direction MD of polarization plates is 151N/m, the fitting forward pull on the direction MD of protective film For 327N/m.
The manufacturing method of polarization plates of the long size shape of Examples 1 to 3 and comparative example 1~2 with protective film is in addition to institute Protective film is different, and (commodity are identical, however batch is different.) identical in addition.
(D) production of long size shape optical laminate
The face with protective film opposite side of the polarization plates of the polarization plates with protective film obtained in above-mentioned (C), according to It is secondary to be laminated by liquid crystal curing type phase separation layer/5 μm of the thickness of 5 μm of thickness 2 μm of (methyl) acrylic adhesive layer/thickness Liquid crystal curing type phase separation layer/25 μm of thickness (methyl) acrylic acid series of 1 μm of (methyl) acrylic adhesive layer/thickness is viscous The diaphragm that mixture layer/polyethylene terephthalate film is formed, produces long size shape optical laminate.
Oriented layer and liquid crystal curing type phase separation layer are formed on the base material film formed by triacetyl cellulose (TAC) film Afterwards, which is pressed from both sides to the face that above-mentioned opposite side is fitted in across 5 μm of thickness (methyl) acrylic adhesive layer, so Afterwards, oriented layer and base material film are removed, the stacking of 2 μm of thickness of liquid crystal curing type phase separation layer has thus been carried out.
Similarly, oriented layer and liquid crystal curing type phase are formed on the base material film formed by triacetyl cellulose (TAC) film After potential difference layer, the liquid crystal that laminated body folder is fitted in 2 μm of thickness across 5 μm of thickness (methyl) acrylic adhesive layer is solid Then oriented layer and base material film are removed, 1 μm of thickness of liquid crystal curing type phase has thus been carried out in the surface of change type phase separation layer The stacking of poor layer.
Thereafter, 25 μm of thickness (methyl) acrylic adhesive layer is formed with by polyethylene terephthalate film Diaphragm laminated body fit in 1 μm of thickness liquid crystal curing type phase separation layer surface, produce long size shape optical layer Stack.
Resulting long size shape optical laminate (removing other than diaphragm) with a thickness of 100 μm.
(E) measurement of the elastic modulus difference of protective film
From the width direction central portion of resulting long size shape optical laminate, long side is cut out using super cutting machine The rectangular small pieces of 100mm × short side 25mm.So that the direction TD of the long side of small pieces and long size shape optical laminate is flat Row, the mode that the short side of small pieces is parallel with the direction MD of long size shape optical laminate are cut out.It is shelled from the small pieces It from protective film and takes out, the test sample as the first elasticity modulus.
In addition, similarly, cutting out long side 100mm × short side using super cutting machine from long size shape optical laminate The rectangular small pieces of 25mm.Wherein, so that the long side of small pieces is parallel with the direction MD of long size shape optical laminate, small pieces The short side mode parallel with the direction TD of long size shape optical laminate cut out.In addition, for cutting out the small pieces Position, keep the position of the width direction of long size shape optical laminate identical as the test sample of the first elasticity modulus. Protective film is removed from the small pieces and is taken out, the test sample as the second elasticity modulus.
It should be noted that for the first elasticity modulus and the second elasticity modulus of long size shape protective film, as long as wide Degree direction cuts out that position difference is identical, then no matter on length direction how all identical cut out position.
The test sample of test sample and the second elasticity modulus for the first elasticity modulus, according to above-mentioned method Find out the first elasticity modulus, the second elasticity modulus and elastic modulus difference.It the results are shown in Table 1.
(F) production of the monolithic body of optical laminate
As shown in fig. 6, from long size shape optical laminate 60 obtained in above-mentioned (D), from protective film side When make the absorption axiss 61 of polarization plates relative to 45 degree of longer side and a shorter side of mode, it is (long to cut out rectangle using super cutting machine Side 140mm × short side 70mm) monolithic body 70, obtain the monolithic body of optical laminate.Central portion cuts out monolithic in the width direction Body 70.It should be noted that the first elasticity modulus of protective film possessed by the monolithic body 70, the second elasticity modulus be respectively with The first elasticity modulus when cutting out test sample according to the above method from long size shape optical laminate and measure, second The identical value of elasticity modulus.
(G) measurement of the MD amount of curl of the monolithic body of optical laminate
To the monolithic body 70 of resulting optical laminate, MD amount of curl is determined according to the following method.Result is indicated In table 1.After producing long size shape optical laminate soon, it is carried out in the environment of 23 DEG C, relative humidity 55% single Sheet body 70 is cut out.
By monolithic body 70 with the face of concave side be above be placed on datum level (horizontal platform).In this state to monolithic body 70 Two diagonal lines in, two angles on a diagonal line small with the angle of the absorption axis direction of the polarization plates of monolithic body 70 80 measure the height relative to datum level respectively, and being averaged for the height as the two angles 80 finds out MD amount of curl (mm).
The concave state in protective film side is that have the state of just crimp, and the state of protective film side protrusion has inverse curling State.
In table 1, indicate to belong to just crimp in the case where the value that the value of MD amount of curl is positive, in the case where the value being negative Expression belongs to inverse curling.So-called MD amount of curl is 0mm, refers to no matter be upper with the protective film side of monolithic body 70, or with its phase Anti- side be it is upper, will not all become the state that above-mentioned two angle 80 is lifted.
[table 1]
The inverse curling for having the monolithic body of the optical laminate of the Examples 1 to 3 for the protective film for meeting formula (I) is pressed down System has flat state.After removing removes diaphragm in the monolithic body of Examples 1 to 3, side identical with above-mentioned (G) is utilized Method determines MD amount of curl, as a result, not showing inverse curling.
The explanation of symbol
1 protective film, 2,2a, 2b polarization plates, 3 first phase difference layers, the first adhesive layer of 3a, 4 second phase difference layers, 4a second Adhesive layer, 5 first adhesive phases, 6 diaphragms, 7 have the polarization plates of protective film, 8 doubling rollers, 10 polarizing films, 20 first thermoplasticity Resin film, 30 second thermoplastic resin films, 40 base material films, 50 second adhesive phases, 60 long size shape optical laminates, 61 partially The absorption axiss of vibration plate, 70 monolithic bodies, the angle of 80 monolithic bodies.

Claims (5)

1. a kind of optical laminate,
It successively includes protective film, polarization plates, one layer or more of phase separation layer and adhesive phase,
The protective film meets lower formula (I):
First the-the second elasticity modulus of elasticity modulus >=300MPa (I)
In formula, so-called first elasticity modulus is the absorption axiss with the polarization plates at 23 DEG C of temperature, relative humidity 55%RH Tensile modulus of elasticity on orthogonal direction, so-called second elasticity modulus, be at 23 DEG C of temperature, relative humidity 55%RH with Tensile modulus of elasticity on the parallel direction of the absorption axiss of the polarization plates.
2. optical laminate according to claim 1, wherein
The polarization plates with a thickness of 110 μm or less.
3. optical laminate according to claim 1 or 2, wherein
Described one layer or more of phase separation layer includes the phase separation layer being made of the solidfied material of liquid-crystal compounds.
4. a kind of manufacturing method of optical laminate is the side of optical laminate described in any one of manufacturing claims 1~3 Method,
This method comprises:
The protective film layer in the region comprising meeting lower formula (I) is laminated on the one side of polarization plates by first step;
The second step folds one layer or more of phase separation layer and viscous in the surface layer of the polarization plates and the one side opposite side Mixture layer;
The third step cuts out the optical laminate from the region;
First the-the second elasticity modulus of elasticity modulus >=300MPa (I)
In formula, so-called first elasticity modulus is the absorption axiss with the polarization plates at 23 DEG C of temperature, relative humidity 55%RH Tensile modulus of elasticity on orthogonal direction, so-called second elasticity modulus, be at 23 DEG C of temperature, relative humidity 55%RH with Tensile modulus of elasticity on the parallel direction of the absorption axiss of the polarization plates.
5. manufacturing method according to claim 4, wherein
The second step include by include base material film and phase separation layer laminate layers be laminated on the opposite side after remove The process of the base material film.
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