CN105717572A - Polarizing plate with protective film and laminate comprising the same - Google Patents
Polarizing plate with protective film and laminate comprising the same Download PDFInfo
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- CN105717572A CN105717572A CN201510964081.1A CN201510964081A CN105717572A CN 105717572 A CN105717572 A CN 105717572A CN 201510964081 A CN201510964081 A CN 201510964081A CN 105717572 A CN105717572 A CN 105717572A
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- protecting film
- polarization plates
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- polaroid
- adhesive phase
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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
Abstract
The invention provides a polarizing plate with a protective film, which has a polarizing plate having a polaroid, and a protective film laminated on one surface. The protective film has a moisture permeability less than 15g/(m<2>*24hr) with the temperature of 40 DEG C and a relative humidity of 90%, and provides the laminate comprising the polarizing plate with the protective film.
Description
Technical field
The present invention relates at the polarization plates with protecting film of polarization plates surface stacking protecting film and the duplexer that comprises it.
Background technology
In recent years, for the mobile terminal of smart mobile phone etc, from the viewpoint of design, Portability, large screen, slenderization continue to advance hastily.In order to realize driving for a long time with limited thickness, the polarization plates for using also requires that high brightness, thin light.
What commonly used as polarization plates is utilize polyethenol series bonding agent to fit the polarization plates of the protecting film comprising triacetyl cellulose on the two sides of polyethenol series polaroid in the past.But; consider from viewpoints such as filming, durability, cost, productivity ratio; in recent years; following protecting film is begun to use as protecting film; namely; except triacetyl cellulose, also comprise the diversified resins such as (methyl) acrylic resin, chain polyolefin-based resins, cyclic polyolefin hydrocarbon system resin, and be thin film (referring for example to Japanese Unexamined Patent Publication 2004-245925 publication [0005] section).
Summary of the invention
As it has been described above, in recent years, have and use trend that is thin and that do not have elastic polarization plates.But, this polarization plates, for the change of its environment being placed, especially variations in temperature and humidity sensitive, has easily along with environmental change produces the trend of the deformation being representative with curling (warpage).Generally speaking polarization plates is taken as being pasted with the protecting film that can peel off for protecting its surface (also referred to as surface protection film.) the polarization plates with protecting film commercially circulate, but trend above-mentioned in the polarization plates with protecting film is also identical.
Thus, it is an object of the invention to, it is provided that be difficult to the duplexer producing the curling polarization plates with protecting film along with variations in temperature and humidity change and comprising it.
The present invention provides the polarization plates with protecting film shown below and image display device.
[1] a kind of polarization plates with protecting film, it possesses the polarization plates comprising polaroid and is laminated in the protecting film of one surface,
The described protecting film moisture permeability M when temperature 40 DEG C, relative humidity 90% is 15g/ (m224hr) below.
[2] according to the polarization plates with protecting film recorded in [1], wherein, the thickness of described polarization plates is less than 125 μm.
[3] according to the polarization plates with protecting film recorded in [1] or [2], wherein, another surface of described polarization plates is made up of the surface of the first adhesive phase.
[4] polarization plates with protecting film recorded any one of [1]～[3], wherein, described protecting film is made up of the second adhesive phase being laminated in one surface and the base material film being laminated in monolayer thereon.
[5] polarization plates with protecting film recorded any one of [1]～[4], wherein, described polarization plates is also included at least one clip surface protecting film across the solidfied material layer stackup of active energy ray-curable bonding agent of described polaroid.
[6] polarization plates with protecting film recorded any one of [1]～[5], wherein, another surface of described polarization plates is made up of the surface of the first adhesive phase,
It is also equipped with being laminated in the isolating membrane on another surface of described polarization plates.
[7] polarization plates with protecting film recorded any one of [1]～[6], wherein, described polarization plates also comprises the blooming beyond described polaroid,
At protecting film described in the surface stacking of described blooming.
[8] according to the polarization plates with protecting film recorded in [7], wherein, described blooming is brightness enhancement film.
[9] polarization plates with protecting film recorded any one of [1]～[8], wherein, the thickness of described polaroid is less than 15 μm.
[10] a kind of duplexer, it comprises image-displaying member and is laminated in the polarization plates with protecting film recorded any one of [1] thereon～[9].
According to the present invention it is possible to provide the duplexer being difficult to produce the curling polarization plates with protecting film along with variations in temperature and humidity change and comprise it.Should go in image display device with the polarization plates of protecting film and the duplexer comprising it.
Accompanying drawing explanation
Fig. 1 is the summary section of an example of the layer composition of the polarization plates with protecting film schematically showing the present invention.
Fig. 2 indicates that the summary section of an example of the layer composition of the polarization plates with protecting film of the present invention.
Fig. 3 indicates that the summary section of another example of the layer composition of the polarization plates with protecting film of the present invention.
Fig. 4 indicates that the summary section of another example of the layer composition of the polarization plates with protecting film of the present invention.
Detailed description of the invention
<polarization plates with protecting film>
(1) with the composition of the polarization plates of protecting film
Fig. 1 is the summary section of an example of the layer composition of the polarization plates with protecting film schematically showing the present invention.With reference to Fig. 1, an example of the polarization plates with protecting film of the present invention is illustrated.The polarization plates with protecting film of the present invention possesses the polarization plates 100 comprising polaroid (not shown in Fig. 1) and is laminated in the protecting film 60 of one surface.The surface of protecting film 60 side of polarization plates 100 (surface of laminating protecting film 60) can be such as the surface of protecting film, other blooming or the layer that is attached on film.
Another surface of polarization plates 100, namely it is not particularly limited with the surface of the face opposite side of stacked guard film 60, but can also be as shown in Figure 1, for instance it is made up of the surface of the first adhesive phase 31.In this situation, it is also possible to outside (another surface of the polarization plates 100) stacking at the first adhesive phase 31 is used for the interim isolating membrane 70 that can peel off protecting this face.
Protecting film 60 is by base material film 61 and is laminated in the second adhesive phase 62 thereon and constitutes, and folder is stacked in polarization plates 100 across this adhesive phase laminating layer.
In the present invention, so-called polarization plates 100 is the polarizer including at least polaroid, generally also comprises the protecting film fitting in its one or both sides.Except protecting film, can also also comprise the layer being attached on film of other the blooming or optical layers etc with the film of optical function different from polaroid etc.The various bloomings comprising protecting film can press from both sides fits across bond layer or adhesive phase.The most top layer of of polarization plates 100 is the first adhesive phase 31, outside it when stacking isolating membrane 70, it is believed that this isolating membrane 70 is not included in polarization plates 100.
As protecting film 60, use the moisture permeability M as entirety also including the second adhesive phase 62 when temperature 40 DEG C, relative humidity 90% for 15g/ (m224hr) film below.Moisture permeability M is preferably 12g/ (m224hr) below.Thus just can effectively suppress the polarization plates with protecting film along with variations in temperature and humidity change curling.Suppressing of curling (warpage) is favourable for suppressing following not good situation, i.e. 1) at in-process because applying stress and the polarization plates that fractures；2) between protecting film and polarization plates, foreign body it is mixed into because of curling caused deformation (warpage)；3) when polarization plates is fitted on image-displaying member, occur laminating mistake or gassing to laminating interface in being mixed into.Moisture permeability M utilizes the cup type method (cupmethod) of regulation in JISZ0208 to measure.Moisture permeability M is generally 0g/ (m2More than 24hr), more typical situation is greater than 0g/ (m2·24hr)。
The thickness T of polarization plates 100 is generally less than 200 μm, from the viewpoint of filming, it is preferred to less than 150 μm, more preferably less than 125 μm, more preferably less than 100 μm.Although thickness T is more little, more easily produce curling, but according to the present invention, even if can also effectively suppress curling in such cases.Thickness T is generally more than 50 μm.
Polarization plates with protecting film preferably meets following formula (1):
M≤T/15+10(1)
Thus, it becomes possible to effectively suppress corresponding with the thickness T of polarization plates 100, curling along with variations in temperature and humidity change.In preferred 1 embodiment, the polarization plates with protecting film meets M≤15 and T≤100, and meets above-mentioned formula (1).
It addition, the humidity expansion coefficient of polarization plates 100 is being set to C1, the humidity expansion coefficient of protecting film 60 is set to C2Time, the absolute value of their difference is preferably 50 (ppm %RH-1) below, more preferably 30 (ppm %RH-1) below.Thus, it becomes possible to more efficiently suppress the polarization plates with protecting film along with variations in temperature and humidity change curling.The absolute value of this difference is more than 0, it is also possible to be 10 (ppm %RH-1) more than.Humidity expansion coefficient C1And C2It is that the record of item according to embodiment described later measures.
The polarization plates with protecting film of the present invention is generally individual body of the polarization plates with protecting film.This individual body can be obtained by following operation; namely; the raw material film transported relative to rolling out continuously from film roll cylinder; the other raw material film that stacking similarly rolls out continuously from film roll cylinder; stacked film tubular wound into a roll by the long size shape of gained; after utilizing this kind of so-called volume to volume mode to produce the polarization plates with protecting film of long size, it is cut and obtains.
The shape of individual body above-mentioned is not particularly limited, but is preferably the square configuration with long limit and minor face, typically rectangle.The length of longer side and a shorter side is not particularly limited, but generally the long limit of individual body is more than 50mm, and minor face is more than 30mm.The size of individual body is more big, more easily produces curling.When size (long limit and/or minor face) is too little, curling problem is inherently difficult to occur.
Below, illustrate with reference to Fig. 2～Fig. 4 example that the layer of polarization plates 100 is constituted, but layer composition is not limited to these examples.Such as, polarization plates another surface, be namely not limited to the first adhesive phase 31 with the surface of the face opposite side of stacked guard film 60, it is also possible to be made up of the surface of the bloomings such as protecting film or the layer that is attached on film.
The polarization plates that the polarization plates with protecting film shown in Fig. 2 has comprises polaroid 10, fit in the protecting film 21 of one face, fit in the protecting film 22 in another face and be laminated in first adhesive phase 31 of outside of protecting film 22.The polarization plates that the polarization plates with protecting film shown in Fig. 3 has comprises polaroid 10, fits in the protecting film 21 of one face, fits in the protecting film 22 in another face, is laminated in the first adhesive phase 31 of the outside of protecting film 22 and presss from both sides the brightness enhancement film 50 as blooming across the 3rd adhesive phase 32 stacking in the outside of protecting film 21.The polarization plates that the polarization plates with protecting film shown in Fig. 4 has eliminates protecting film 21, at the direct stacking the 3rd in the surface of polaroid 10 adhesive phase 32, has the layer identical with the polarization plates shown in Fig. 3 in addition and constitutes.
Although the diagram of eliminating, but the laminating of polaroid 10 and protecting film 21,22 can use bonding agent to carry out.
(2) polaroid
Polaroid 10 is to have to absorb to have to be parallel to it and absorb rectilinearly polarized light of vibration plane of axle, transmission and have the absorptive-type polaroid of the character with the rectilinearly polarized light absorbing axle orthogonal (parallel with the axis of homology) vibration plane, it is possible to make polyvinyl alcohol resin film gas absorption quantity dichromatic pigment suitably and the polarizing coating that obtains.Polaroid 10 such as can utilize and include: by the operation of polyvinyl alcohol resin film uniaxial tension；By by polyvinyl alcohol resin film dichromatic pigment dyeing so as to adsorb the operation of dichromatic pigment；The operation that the polyvinyl alcohol resin film boric acid aqueous solution having adsorbed dichromatic pigment is processed；And the method for operation carrying out after by the process of boric acid aqueous solution washing manufactures.
As polyvinyl alcohol resin, it is possible to use the resin that the resin saponification of polyvinyl acetate system is obtained.As polyvinyl acetate system resin, except the polyvinyl acetate as the homopolymer of vinyl acetate, it is also possible to enumerate with can with the copolymer etc. of other monomers of vinyl acetate copolymerization.Unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class can be included with the example of other monomers of vinyl acetate copolymerization and there is (methyl) acrylic amide etc. of ammonium.
The saponification degree of polyvinyl alcohol resin is generally 85～100mol%, it is preferred to more than 98mol%.Polyvinyl alcohol resin can also be modified, for instance can also use the polyvinyl formal modifiied with aldehydes or polyvinyl acetal etc..The average degree of polymerization of polyvinyl alcohol resin is generally 1000～10000, it is preferred to 1500～5000.The average degree of polymerization of polyvinyl alcohol resin can be obtained according to JISK6726.
The material this kind of polyvinyl alcohol resin masking obtained is taken as the former material film of polaroid 10 (polarizing coating) and uses.The method of polyvinyl alcohol resin masking is not particularly limited, it is possible to adopt known method.The thickness of the former material film of polyethenol series is not particularly limited, but in order to the thickness of polaroid 10 is set to less than 15 μm, it is common to use the film of 5～35 μm.It is more preferably less than 20 μm.If it is intended to stretched by former for the thickness polyethenol series more than 35 μm material film and obtain the polaroid 10 of thickness less than 15 μm, then needing raising stretching ratio, when being set to below 15 μm by the thickness of polaroid 10, the dimensional contraction under hot environment also can become big.It addition, when thickness is less than 5 μm, disposal during because stretching reduces and the easy not good situation producing cut-out etc when polaroid manufactures.
The uniaxial tension of polyvinyl alcohol resin film or can carry out after dyeing with dyeing before the dyeing of dichromatic pigment simultaneously.When carrying out uniaxial tension after dyeing, this uniaxial tension can also carry out before boric acid processes or in boric acid process.Alternatively, it is also possible to carry out uniaxial tension in these multiple stages.
When uniaxial tension, both can stretch between the roller that peripheral speed is different, it is possible to use hot-rolling single shaft ground stretches single shaft.It addition, uniaxial tension both can be the dry type stretching carrying out in an atmosphere stretching, it is also possible to be stretch in the wet type using solvent, water to carry out when making polyvinyl alcohol resin film swelling stretching.Stretching ratio is generally 3～8 times.
As by the polyvinyl alcohol resin film method with dichromatic pigment dyeing, for instance can adopt this film immersion method in the aqueous solution containing dichromatic pigment.As dichromatic pigment, it is possible to use iodine or dichroic organic dye.And, polyvinyl alcohol resin film is implemented in the impregnation process in water before processing preferably in dyeing in advance.
Process as the dyeing by iodine, be typically employed in the aqueous solution containing iodine and potassium iodide impregnate polyvinyl alcohol resin film method.The content of the iodine in this aqueous solution is in every 100 weight parts waters, is generally 0.01～1 weight portion.The content of potassium iodide is in every 100 weight parts waters, is generally 0.5～20 weight portion.It addition, the temperature of this aqueous solution is generally 20～40 DEG C.On the other hand, process as the dyeing by dichroic organic dye, be typically employed in the aqueous solution containing dichroic organic dye impregnate polyvinyl alcohol resin film method.Aqueous solution containing dichroic organic dye can also contain the inorganic salts such as sodium sulfate as dyeing assistant.The content of the dichroic organic dye in this aqueous solution is in every 100 weight parts waters, is generally 1 × 10-4～10 weight portion.The temperature of this aqueous solution is generally 20～80 DEG C.
Process as the boric acid after the dyeing by dichromatic pigment, generally adopt the polyvinyl alcohol resin film immersion that has been colored containing the method in boron aqueous acid.When using iodine as dichromatic pigment, potassium iodide should be preferably comprised containing boron aqueous acid.Amount containing the boric acid in boron aqueous acid is in every 100 weight parts waters, is generally 2～15 weight portions.The amount of the potassium iodide in this aqueous solution is in every 100 weight parts waters, is generally 0.1～15 weight portion.The temperature of this aqueous solution can be more than 50 DEG C, for instance is 50～85 DEG C.
Polyvinyl alcohol resin film after boric acid process is generally carried out washing process.Washing processes such as can by carrying out the polyvinyl alcohol resin film immersion having carried out boric acid process in water.The temperature of the water in washing process is generally 5～40 DEG C.
After washing, implement dried and obtain polaroid 10.Dried can use air drier or far infra-red heater to carry out.The thickness of polaroid 10 is preferably less than 15 μm, more preferably less than 10 μm.The thickness of polaroid 10 is set to 15 μm of slimmings below for polarization plates 100 and then the slimming for image display device is favourable.The thickness of polaroid 10 is generally more than 2 μm.According to the present invention, though the thickness of polaroid 10 be thinned to less than 15 μm can also suppress the polarization plates with protecting film along with variations in temperature and humidity change curling.
Utilize dried, the moisture rate of polaroid 10 is reduced to practical level.Its moisture rate is generally 5～20 weight %, it is preferred to 8～15 weight %.If moisture rate is at below 5 weight %, then can lose the flexibility of polaroid 10, thus having the polaroid 10 situation in this damage after drying, fracture.If it addition, moisture rate is at more than 20 weight %, then having the situation of the poor heat stability of polaroid 10.
(3) protecting film
The protecting film 21,22 that can be laminated in the one or both sides of polaroid 10 can be the polyolefin-based resins comprising and having light transmission (preferably in optically transparent) thermoplastic resin, such as chain polyolefin-based resins (polypropylene-based resin etc.), cyclic polyolefin hydrocarbon system resin (norbornene resin etc.) etc；The cellulose-based resin of triacetyl cellulose, diacetyl cellulose etc；The polyester based resin of polyethylene terephthalate, polybutylene terephthalate (PBT) etc；Polycarbonate-based resin；(methyl) acrylic resin of methyl methacrylate system resin etc；Polystyrene resin；Polyvinyl chloride resin；Acrylonitrile/butadiene/styrene system resin；Acrylonitrile/phenylethylene resin series；Polyvinyl acetate system resin；Polyvinylidene chloride resin；Polyamide series resin；Polyacetals system resin；Noryl system resin；Polysulfones system resin；Polyether sulfone system resin；Polyarylate system resin；Polyamidoimide system resin；The film of polyimides system resin etc..Wherein, it is preferred to use polyolefin-based resins, cellulose-based resin.And so-called in this manual " (methyl) acrylic resin ", represent at least one in acrylic resin and metha crylic resin.In other the term with " (methyl) " also identical.
As chain polyolefin-based resins, except the homopolymer of the chain olefin of polyvinyl resin, acrylic resin etc, it is also possible to enumerate the copolymer comprising chain olefin of more than two kinds.
Cyclic polyolefin hydrocarbon system resin is the general name of the resin being polymerized as polymerized unit using cyclic olefin.If enumerating the concrete example of cyclic polyolefin hydrocarbon system resin, then for open loop (being total to) polymer of cyclic olefin, the addition polymer of cyclic olefin, the copolymer (representational is random copolymer) of chain olefin of cyclic olefin and ethylene, propylene etc and the graft polymers that they have been modifiied with unsaturated carboxylic acid or derivatives thereof and their hydride etc..Wherein, it is preferred to use employ the norbornene resin of the norborneol alkene monomer such as norborene or condensed ring norborneol alkene monomer as cyclic olefin.
So-called cellulose-based resin, refers to part or all of cellulose organic ester that instead of with acetyl group, propiono and/or bytyry or cellulose mixed organic acid ester of the hydrogen atom in the cellulosic hydroxyl obtained by raw celluloses such as velveteen or wood pulps (broad leaf tree wood pulp, coniferous tree wood pulp).For example, it is possible to enumerate the resin comprising cellulosic acetas, propionic ester, butyrate and their mixed ester etc..Wherein, it is preferable that triacetyl cellulose, diacetyl cellulose, cellulose-acetate propionate, cellulose acetate-butyrate.
(methyl) acrylic resin is the polymer containing the Component units coming from (methyl) acrylic monomer.This polymer is the polymer containing methacrylate in the typical case.The ratio being preferably the construction unit coming from methacrylate is the polymer containing more than 50 weight % relative to entire infrastructure unit.(methyl) acrylic resin both can be the homopolymer of methacrylate, it is also possible to be the copolymer of Component units containing the polymerizable monomer coming from other.In this situation, the ratio of the Component units coming from other polymerizable monomer is less than 50% preferably with respect to entire infrastructure unit.
As the methacrylate that may be constructed (methyl) acrylic resin, it is preferable that alkyl methacrylate.As alkyl methacrylate, it is possible to enumerate the alkyl methacrylate that carbon number is 1～8 of the alkyl of methyl methacrylate, ethyl methacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, Tert-butyl Methacrylate, 2-Ethylhexyl Methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate etc.The carbon number of alkyl contained in alkyl methacrylate is preferably 1～4.In (methyl) acrylic resin, methacrylate both can be used alone or two or more kinds may be used.
As other the polymerizable monomer above-mentioned that may be constructed (methyl) acrylic resin, it is possible to enumerate acrylate and other the compound in molecule with polymerism carbon-to-carbon double bond.Other polymerizable monomer both can be used alone or two or more kinds may be used.As acrylate, it is preferable that alkyl acrylate.As alkyl acrylate, it is possible to enumerate the alkyl acrylate etc. that carbon number is 1～8 of the alkyl of acrylic acid methyl ester., ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, Isobutyl 2-propenoate, tert-butyl acrylate, 2-EHA, cyclohexyl acrylate, acrylic acid 2-hydroxy methacrylate etc.The carbon number of alkyl contained in alkyl acrylate is preferably 1～4.In (methyl) acrylic resin, acrylate both can be used alone or two or more kinds may be used.
The compound in molecule with polymerism carbon-to-carbon double bond as other, it is possible to enumerate the vinyl cyanide compound of the vinyl compounds or acrylonitrile etc such as ethylene, propylene, styrene.Other the compound in molecule with polymerism carbon-to-carbon double bond both can be used alone or two or more kinds may be used.
The value controlling the phase difference value of protecting film 21,22 for being suitable for the image display devices such as liquid crystal indicator is also useful.Such as, in the liquid crystal indicator of face internal conversion (IPS) pattern, phase difference value is preferably used as protecting film 22 and is essentially the film of zero.So-called phase difference value is essentially zero, phase difference value R in face when referring to wavelength 590nm0For below 10nm, thickness direction phase difference value R during wavelength 590nmthAbsolute value be below 10nm, thickness direction phase difference value R during wavelength 480～750nmthAbsolute value be below 15nm.
According to the pattern of liquid crystal indicator, protecting film 21,22 can also be stretched and/or shrinks processing, give suitable phase difference value.For example, it is possible to for the purpose compensating visual angle, use the phase separation layer (or film) of single or multiple lift structure as protecting film 22.In this situation, polarization plates 100 can be the elliptical polarization plate of the stepped construction comprising polaroid 10 and phase separation layer or circularly polarizing plate or the polarization plates etc. having viewing angle compensation function concurrently comprising phase separation layer.
The thickness of protecting film 21,22 is generally 1～100 μm, but considers to be preferably 5～60 μm from viewpoints such as intensity, the property disposed, more preferably 5～50 μm.If the thickness within the scope of this, it is possible to polaroid 10 is carried out mechanical protection, if exposed to polaroid under hygrothermal environment 10 without contraction, it is possible to the optical characteristics remained stable for.Although making protecting film 21,22 more thin, more easily produce along with variations in temperature and humidity change curling; but according to the present invention; even if the thickness of protecting film 21,22 is such as thinned to less than 30 μm, it is also possible to suppress along with variations in temperature and humidity change curling.
From the viewpoint of filming, polarization plates 100 can be at least any one the composition without protecting film 21,22, but at least one face preferably in polaroid 10 possesses protecting film.Although when only easily produce when the folded protecting film of a surface layer of polaroid 10 along with variations in temperature and humidity change curling, but according to the present invention, though can also suppress in such cases along with variations in temperature and humidity change curling.
When only when the folded protecting film of a surface layer of polaroid 10; in the face of the face opposite side with stacked guard film of polaroid 10, the actinic energy ray curable resion composition identical with active energy ray-curable bonding agent described later the protective layer formed can also be set.By arranging protective layer, even only there is the composition of protecting film at a mask of polaroid 10, it is also possible to more efficiently suppress the deterioration of the curling or polaroid 10 changed along with variations in temperature and humidity.
When protecting film is fitted on the two sides of polaroid 10, these protecting film both can be made up of thermoplastic resin of the same race, it is also possible to is made up of thermoplastic resin not of the same race.It addition, thickness both can be identical, it is also possible to different.Additionally, both can have identical phase difference characteristics, it is possible to have different phase difference characteristics.
At least any one party of protecting film 21,22 can also be that (face with polaroid 10 opposite side) possesses the surface-treated layer (coating) of hard conating, antiglare layer, light diffusion layer, phase separation layer (having the phase separation layer etc. of the phase difference value of 1/4 wavelength), anti-reflection layer, anti-static electricity interference layer, stain-proofing layer etc or the protecting film of optical layers outside it.
If be laminated in the protecting film on the two sides of polaroid 10 composition (resin types, thickness, surface-treated layer presence or absence etc.) different from each other; then easily produce along with variations in temperature and humidity change curling; but according to the present invention, can also suppress in such cases along with variations in temperature and humidity change curling.
Protecting film 21,22 such as can press from both sides and be fitted on polaroid 10 across bond layer.As the bonding agent forming bond layer, it is possible to use water system bonding agent, active energy ray-curable bonding agent or Thermocurable bonding agent, it is preferred to water system bonding agent, active energy ray-curable bonding agent.
As water system bonding agent, it is possible to enumerate and comprise the bonding agent of polyvinyl alcohol resin aqueous solution, water system two-component-type carbamate system emulsion adhesive etc..Wherein it is suitable for using the water system bonding agent comprising polyvinyl alcohol resin aqueous solution.As polyvinyl alcohol resin, except the saponifying polyvinyl acetate of the homopolymer as vinyl acetate is processed and except the alcotex that obtain, it is also possible to use polyvinyl alcohol based copolymer vinyl acetate and the copolymer saponification process of other monomers that can be copolymerized therewith obtained or by the modified polyvinylalcohol based polymer etc. that modifiied of their hydroxylic moiety ground.Water system bonding agent can contain the cross-linking agent such as aldehyde compound (Biformyl etc.), epoxide, tripolycyanamide based compound, methylol compound, isocyanate compound, amines, multivalent metal salt.
When using water system bonding agent, it is preferable that after being fitted with protecting film 21,22 by polaroid 10, implement the drying process for removing water contained in water system bonding agent.Can also after drying process, for instance be arranged on the temperature of 20～45 DEG C and carry out the curing step of ripening.
Above-mentioned so-called active energy ray-curable bonding agent, refer to the bonding agent being occurred to solidify by the active energy beam of irradiation ultraviolet radiation or electron beam etc, for instance the solidification compound containing polymerizable compound and Photoepolymerizationinitiater initiater, the solidification compound containing light reactive resin, the solidification compound etc. containing adhesive resin and photoreactivity cross-linking agent can be enumerated.It is preferably ultra-violet solidified bonding agent.As polymerizable compound, it is possible to enumerate the photopolymerization monomer of photo-curable epoxy monomer, photo-curable (methyl) acrylic monomer, photo-curable carbamate system monomer etc or come from the oligomer of photopolymerization monomer.As Photoepolymerizationinitiater initiater, it is possible to enumerate the Photoepolymerizationinitiater initiater of the material of the spike producing Neutral radical, radical anion, radical cation etc containing the irradiation because of active energy beam.As the active energy ray-curable bonding agent containing polymerizable compound and Photoepolymerizationinitiater initiater, it may be preferred to use the mixture containing photo-curable epoxy monomer and the solidification compound of light cationic polymerization initiators, the solidification compound containing photo-curable (methyl) acrylic monomer and optical free radical polymerization initiator or these solidification compounds.
As photo-curable epoxy monomer, it is preferable that cycloaliphatic epoxy.So-called cycloaliphatic epoxy, refers to that the carbon atom with ester ring type ring in molecule with more than 1 collectively forms the compound of the structure of oxirane ring.Cycloaliphatic epoxy both can be used alone or two or more kinds may be used.So-called " with the structure that the carbon atom of ester ring type ring collectively forms oxirane ring ", (CH from structure as shown below2)mIn remove one or more hydrogen atoms and the group of form that obtains.In following formula, m is the integer of 2～5.
[changing 1]
Thus, (CH2)mIn remove one or more hydrogen atoms and the compound that is bonded with other chemical constitution of the group of form that obtains just can become cycloaliphatic epoxy.(CH2)mIn one or more hydrogen atom can also be replaced rightly by the straight-chain alkyl such as methyl, ethyl.In cycloaliphatic epoxy, from the viewpoint of demonstrating excellent cementability, it is preferable that have oxabicyclohexane ring (in above-mentioned formula the material of m=4) or the cycloaliphatic epoxy of oxabicyclo heptane ring (in above-mentioned formula the material of m=5).Exemplify the cycloaliphatic epoxy being preferably used in detail below.
[changing 2]
When using active energy ray-curable bonding agent; after polaroid 10 is fitted with protecting film 21,22; it is dried operation as required, then carries out the curing process making active energy ray-curable bonding agent solidify by irradiating active energy beam.Thus, when using active energy ray-curable bonding agent, bond layer is this solidification nitride layer.The light source of active energy beam is not particularly limited, but have preferably in below wavelength 400nm and send out ultraviolet photodistributed, specifically, it is possible to use low pressure mercury lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, black light lamp, microwave-excitation finsen lamp, metal halide lamp etc..
When by polaroid 10 with protecting film 21,22 laminating, in order to improve cementability, it is possible to their at least any one binding face is implemented saponification process, sided corona treatment, Cement Composite Treated by Plasma etc..
When protecting film is fitted on the two sides of polaroid 10 for bonding agent that the bonding agent of these protecting film of fitting both can be of the same race, it is also possible to be bonding agent not of the same race.Although easily produce when using bonding agent not of the same race along with variations in temperature and humidity change curling, but according to the present invention, can also suppress in such cases along with variations in temperature and humidity change curling.
(4) other bloomings
Polarization plates 100 can comprise other bloomings beyond polaroid 10 and protecting film 21,22, and its typical example is brightness enhancement film 50 and phase retardation film.When polarization plates 100 comprises other bloomings, protecting film 60 can also be laminated in the surface of this blooming.
Brightness enhancement film 50, also referred to as reflective polarizing film, uses the polarization conversion device with the function that the emergent light from light source (backlight) is separated into transmission-polarizing light and polarization by reflection light or scattering polarization light.By being arranged on polaroid 10 by brightness enhancement film 50, it is possible to utilize the return light as polarization by reflection light or scattering polarization light, the outgoing efficiency of the rectilinearly polarized light of injection from polaroid 10 is made to improve.Brightness enhancement film 50 can be pressed from both sides and is laminated on polaroid 10 across adhesive phase (the 3rd adhesive phase 32).Can also between polaroid 10 and brightness enhancement film 50 other the film of sandwiched protecting film etc.
Brightness enhancement film 50 can be such as anisotropic emission polaroid.One example of anisotropic emission polaroid is the rectilinearly polarized light of one direction of vibration of transmission and reflects the multiple thin film of anisotropy of rectilinearly polarized light of another direction of vibration, and its concrete example is 3M company system " DBEF " (with reference to Japanese Unexamined Patent Publication 4-268505 publication etc.).An other example of anisotropic emission polaroid is the complex of cholesteric crystal layer and λ/4 plate, and its concrete example is " PCF " (with reference to the Japanese Unexamined Patent Publication 11-231130 publication etc.) of day east electrician.Another example of anisotropic emission polaroid is reflecting grating polaroid, and its concrete example is the metal gate reflecting polarizer (with reference to No. 6288840 description of U.S. Patent No. etc.) that also can penetrate polarization by reflection light after metal is implemented microfabrication in visible region, the film (with reference to Japanese Unexamined Patent Publication 8-184701 publication etc.) adding in polymer matrix by metal particle and stretching and obtain.
The binding face with the 3rd adhesive phase 32 in brightness enhancement film 50 can also be carried out surface activation process in advance.Thus, it is possible to polarization plates 100 that be formed under hygrothermal environment to be difficult to the stripping that produces between the 3rd adhesive phase 32 and brightness enhancement film 50, that wet heat durability is excellent.Process as surface activation, it is possible to enumerate the dry process of sided corona treatment, Cement Composite Treated by Plasma, discharge process (glow discharge process etc.), flame treatment, ozonization, UV ozonization, ionization activity Irradiation (UV treatment, electron beam treatment etc.) etc；Employ water or the wet processed of the ultrasonic Treatment of acetone equal solvent, alkali process, tackifier coating process etc.These process both can carry out individually, it is also possible to combines two or more.Wherein, from the viewpoint of the film processing drum continuously, it is preferable that sided corona treatment, Cement Composite Treated by Plasma.
Outside in brightness enhancement film 50, it is also possible to surface-treated layer (coating) or the optical layers of hard conating, antiglare layer, light diffusion layer, phase separation layer (having the phase separation layer etc. of the phase difference value of 1/4 wavelength), anti-reflection layer, anti-static electricity interference layer, stain-proofing layer etc are set.Utilize the formation of this layer, it is possible to improve the homogeneity of the adaptation with backlight adhesive tape, display image.The thickness of brightness enhancement film 50 is generally 10～100 μm, but from the viewpoint of the filming of polarization plates 100, it is preferred to 10～50 μm, more preferably 10～30 μm.
(5) adhesive phase (pressure sensitive bond layer)
First adhesive phase 31 may be used for being fitted on image-displaying member (such as liquid crystal cells) or other optical components the polarization plates with protecting film.3rd adhesive phase 32 is to (other bloomings of such as brightness enhancement film 50 etc and polaroid 10 or protecting film 21) laminating between the blooming of composition polarization plates 100 be used.First adhesive phase the 31, the 3rd adhesive phase 32 can be constituted as the adhesive composition of main constituent in order to the resin of (methyl) acrylic acid series, rubber series, carbamate system, ester system, silicone-based, polyvingl ether system etc.Wherein, the adhesive composition of polymer based on (methyl) acrylic resin of the excellences such as the transparency, weatherability, thermostability it is suitably for.Adhesive composition can also be active energy ray curable, thermohardening type.
As (methyl) acrylic resin (base polymer) used in adhesive composition, for instance be suitable for using the one kind or two or more polymer as monomer or the copolymer of (methyl) acrylate using (methyl) butyl acrylate, (methyl) ethyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA etc.In base polymer, it is preferable that make polar monomer copolymerization.As polar monomer, such as can enumerate the monomer with carboxyl, hydroxyl, amide groups, amino, epoxy radicals etc. of (methyl) acrylic acid, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) Hydroxyethyl Acrylate, (methyl) acrylamide, N, N-dimethyl aminoethyl (methyl) acrylate, (methyl) glycidyl acrylate etc.
Adhesive composition can also contain only above-mentioned base polymer, but generally possibly together with cross-linking agent.As cross-linking agent, it is possible to exemplify the metal ion belonging to more than divalent and form the cross-linking agent of carboxylic metallic salt between carboxyl；Belong to polyamino compound and between carboxyl, form the cross-linking agent of amido link；Belong to polyepoxides or polyhydric alcohol and between carboxyl, form the cross-linking agent of ester bond；Belong to polyisocyanate compounds and between carboxyl, form the cross-linking agent of amido link.Wherein, it is preferable that polyisocyanate compounds.
So-called active energy ray curable adhesive composition, the character being that there is the irradiation of the active energy beam being subject to ultraviolet or electron beam etc and solidify, have at active energy beam pre-irradiation, also there is cohesive and can bur be closely sealed, can solidify the adhesive composition of the character adjusting closing force because of the irradiation of active energy beam with film etc..Active energy ray curable adhesive composition is preferably ultraviolet hardening.Active energy ray curable adhesive composition is except base polymer, cross-linking agent, possibly together with active energy beam polymerizable compound.Further according to needs, sometimes also contain Photoepolymerizationinitiater initiater, photosensitizer etc..
Adhesive composition can contain for giving the additives such as resin beyond light scattering microgranule, pearl (resin bead, bead etc.), glass fibre, base polymer, viscosifier, filler (metal powder or other inorganic powder etc.), antioxidant, UV absorbent, dyestuff, pigment, coloring agent, defoamer, preservative, Photoepolymerizationinitiater initiater.
First adhesive phase 31 and the 3rd adhesive phase 32 by being coated on base material by the organic solvent diluting liquid of above-mentioned adhesive composition and so as to can dry and be formed.Base material can be polaroid 10, protecting film 21,22, other bloomings of brightness enhancement film 50 etc, isolating membrane (such as isolating membrane 70) etc..When employing active energy ray curable adhesive composition, it is possible to make the solidfied material with required curing degree by the adhesive phase formed is irradiated active energy beam.
The thickness of the first adhesive phase 31 and the 3rd adhesive phase 32 is usually 1～40 μm, but from the viewpoint of the viewpoint of the filming of polarization plates 100 and suppress the change in size of polarization plates 100 while keeping good processability, it is preferable that it is set to 3～25 μm (they are such as 3～20 μm, are more preferably 3～15 μm).
3rd adhesive phase 32 is preferably in the store elastic modulus demonstrating 0.15～1MPa in the temperature range of 23～80 DEG C.Thus, it is possible to suppress the change in size easily produced along with the contraction of polaroid 10 under hygrothermal environment, improve the durability of polarization plates 100.Further, since when the image display device being equipped with polarization plates 100 is positioned under hygrothermal environment, it is also possible to suppress the movement of polarization plates 100, therefore can improve the reliability of image display device.
So-called " demonstrating the store elastic modulus of 0.15～1MPa in the temperature range of 23～80 DEG C ", refers to that store elastic modulus is all the value in above-mentioned scope under the arbitrary temp of this scope.Due to store elastic modulus generally along with temperature raise be gradually reduced, if therefore 23 DEG C and 80 DEG C time store elastic modulus both fall within above-mentioned scope, then can be considered as the store elastic modulus demonstrating in above-mentioned scope at the temperature of this scope.The store elastic modulus of the 3rd adhesive phase 32 can use commercially available determination of viscoelasticity device, the determination of viscoelasticity device " DYNAMICANALYZERRDAII " of such as REOMETRIC company measures.
As the method being used for store elastic modulus is adjusted to above-mentioned scope, can enumerate in base polymer, or to possibly together with in the adhesive composition of cross-linking agent, add oligomer again, specifically add the oligomer of carbamate (methyl) acrylic ester again and make active energy ray curable adhesive composition (being preferably ultraviolet-curing adhesive composition).More preferably irradiate active energy beam and make adhesive phase moderately solidify.
The store elastic modulus of the first adhesive phase 31 both can be identical with the 3rd adhesive phase 32, it is also possible to different.
(6) isolating membrane
Isolating membrane 70 is the film temporarily attached to protect its surface before being fitted in by the first adhesive phase 31 on image-displaying member (such as liquid crystal cells) or other optical component.Isolating membrane 70 is generally made up of the thermoplastic resin film that one side implements demoulding process, and this demoulding processes face and is fitted on the first adhesive phase 31.The thermoplastic resin constituting isolating membrane 70 can be such as the polyester based resin etc. of the polyethylene-based resin of polyethylene etc, the polypropylene-based resin of polypropylene, polyethylene terephthalate or PEN etc.Surface at the 3rd adhesive phase 32, it is also possible to protect this surface in order to interim before laminating brightness enhancement film 50 blooming such as grade, and attach isolating membrane same as described above.The thickness of isolating membrane 70 is such as 10～50 μm.
(7) protecting film
Protecting film 60 is by base material film 61 and is laminated in the second adhesive phase 62 thereon and constitutes.Protecting film 60 is the film on the surface for protecting polarization plates 100, peels off removing together with the second adhesive phase 62 being had with it after the polarization plates with protecting film of generally fitting on such as image-displaying member or other optical component.
Also the moisture permeability as entirety including the second adhesive phase 62 of protecting film 60 described above is 15g/ (m when temperature 40 DEG C, relative humidity 90%224hr) below, it is preferred to 12g/ (m224hr) below.As the method moisture permeability of protecting film 60 being adjusted in above-mentioned scope, it is possible to enumerate the constituent material as base material film 61 and use the material of low-moisture permeability.The example of low-moisture permeability material is the resin of low-moisture permeability, it is preferred to thermoplastic resin, specifically can enumerate the polyolefin-based resins of polyethylene-based resin, polypropylene-based resin etc；Cyclic polyolefin hydrocarbon system resin；The polyester based resin of polyethylene terephthalate or PEN etc；Polycarbonate-based resin；(methyl) acrylic resin etc..
Base material film 61 both can be single layer structure can also be multiple structure.Such as, even if when using the resin molding with higher moisture permeability, it is also possible to by the film of stacking low-moisture permeability thereon or layer, the moisture permeability of protecting film 60 is adjusted in above-mentioned scope.Considering from the viewpoint such as ease of manufacturing and manufacturing cost, base material film 61 is preferably single layer structure.
Alternatively, it is also possible to the moisture permeability of protecting film 60 is adjusted in above-mentioned scope by increasing the thickness of base material film 61.The thickness of base material film 61 can be 20～190 μm (such as 30～140 μm), and the thickness of protecting film 60 can be 60～200 μm (such as 70～150 μm).If the thickness of protecting film 60 is more than 200 μm, then cost, roller conveyance property, protecting film 60 re-workability in unfavorable.
Composition for the second adhesive phase 62; substantially can quote the aforesaid description about the first adhesive phase the 31, the 3rd adhesive phase 32, but or can also make the moisture permeability of protecting film 60 is adjusted in above-mentioned scope containing hygroscopic matter (hygroscopic particle etc.) by the second adhesive phase 62 by increasing the thickness of the second adhesive phase 62.Methods described above can also be combined multiple and the moisture permeability of protecting film 60 is adjusted in above-mentioned scope.
The present invention includes in the polarization plates with protecting film contained polarization plates 100 and has, for benchmark, the situation etc. that asymmetrical layer is constituted with polaroid 10, when have that easily generation causes by variations in temperature and humidity change curling when constituting especially advantageous.Easily produce to be changed the curling example constituted caused by variations in temperature and humidity as follows.
(a) polaroid 10 and/or the thin composition of protecting film 21,22；
B bond layer that () is located between polaroid 10 and protecting film is the composition of the solidification nitride layer of active energy ray-curable bonding agent；
C () is only fitted with the composition of protecting film in the one side of polaroid 10；
D () be fitted with protecting film in a face of polaroid 10, be fitted with the composition of blooming (brightness enhancement film etc.) beyond protecting film in another face；
(e) fit in the protecting film on the two sides of polaroid 10 composition (resin types, thickness, surface-treated layer presence or absence etc.) composition different from each other；
(f) for the two sides of polaroid 10 fit protecting film bond layer by constituting that the bonding agent of kind different from each other is formed；
G () is fitted with protecting film and is fitted with other the composition of blooming on a protecting film on the two sides of polaroid 10；
(h) in addition with polaroid 10 be benchmark, the film of side and the total number of the layer composition different from the total number of the film of opposite side and layer.
<duplexer, liquid crystal panel and image display device>
The polarization plates with protecting film of the present invention goes for comprising image-displaying member and being laminated in thereon with in the duplexer of the polarization plates of protecting film.This duplexer can press from both sides with the polarization plates of protecting film and fit on image-displaying member across adhesive phase (such as the first adhesive phase 31) (after being peeled off removing when having the isolating membrane of isolating membrane 70 etc).After being fitted on image-displaying member by the polarization plates with protecting film, it is stripped removing at required moment protecting film 60.This duplexer can be liquid crystal panel or its manufacture intermediate of the polarization plates comprising image-displaying member with being laminated in its one or both sides.Protecting film 60 after constructing duplexer, construct protecting film 60 of having fitted state liquid crystal panel after or be stripped removing after using the liquid crystal panel of state of protecting film 60 of having fitted to construct image display device etc..Generally as in the final products of image display device, protecting film 60 is stripped removing.
Image display device can be the device that liquid crystal indicator, organic EL display etc. are any, but is preferably liquid crystal indicator.Liquid crystal indicator possesses liquid crystal panel and backlight, and described liquid crystal panel possesses the liquid crystal cells as image-displaying member.When constructing liquid crystal indicator, the polarization plates with protecting film of the present invention both may be used for being arranged in the polarization plates of viewable side; can be used for being arranged in the polarization plates of backlight side; can be also used in the polarization plates of both viewable side and backlight side, but preferably the polarization plates with protecting film of the present invention is at least used in the polarization plates of backlight side.
[embodiment]
Hereinafter, embodiment and comparative example will be provided and the present invention will be carried out more specific description, but the present invention will not be limited by these examples.In the following examples, the moisture permeability of film, humidity expansion coefficient, thickness, phase difference value R in face0And thickness direction phase difference value Rth, adhesive phase store elastic modulus and be measure according to method below with the amount of curl of the polarization plates of protecting film.
(1) moisture permeability
Utilize in JISZ0208 the cup type method of regulation, the moisture permeability (g/ (m of protecting film when determining temperature 40 DEG C, relative humidity 90%2·24hr)〕。
(2) humidity expansion coefficient
Humidity expansion coefficient (the ppm %RH of polarization plates and protecting film-1) it is measure according to method below.Membrane sample is cut into 100mm × 100mm, the length of film conveyance direction when determining 23 DEG C of 50%RH and during 23 DEG C of 90%RH, measure humidity expansion coefficient (ppm %RH according to following formula-1),
Humidity expansion coefficient=(L90-L50)/(L50 × Δ H)
Herein, L50 is the length (mm) of film conveyance direction during 23 DEG C of 50%RH, and L90 is the length (mm) of film conveyance direction during 23 DEG C of 90%RH, and Δ H is 40 (=90-50) %RH.
(3) thickness
The digital micrometer machine " MH-15M " using (strain) NIKON measures.
(4) phase difference value R in faceeAnd thickness direction phase difference value Rth
The prince as the phase contrast instrument being principle with parallel-nicol circumgyration is used to measure " KOBRA-ADH " that machine (strain) is made, 23 DEG C of light measurements with wavelength 590nm, 483nm or 755nm.
(5) store elastic modulus
The store elastic modulus G ' of adhesive phase measures according to following (I)～(III).
(I) from adhesive phase, each 25 ± 1mg takes out 2 samples in ground, is formed separately as approximate sphericity.(II) sample of the approximate sphericity of gained is attached to the top and bottom of I type fixture, top and bottom are all sandwiched with L-type fixture.The composition measuring sample is L-type fixture/binding agent/I type fixture/binding agent/L-type fixture.
(III) use IT measurement to control the Measurement of Dynamic Viscoelasticity device " DVA-220 " that (strain) makes, measure the store elastic modulus G ' of the sample so made when temperature 23 DEG C or 80 DEG C, frequency 1Hz, initial stage strain 1N.
(6) amount of curl
From the polarization plates with protecting film, cut out individual body of 221mm × 139mm size, peel the isolating membrane on the first adhesive phase being laminated in this individual body, be fitted on the alkali-free glass of 225mm × 145mm, thick 0.4mm, obtain measuring sample.After being stood 5 hours under 80 DEG C of 90%RH environment by this mensuration sample, return to room temperature (23 DEG C of 50%RH).Thereafter, its polarization plates side is made to be placed on upward on the mensuration platform of two-dimentional analyzer " NEXIVVMR-12072 " of (strain) NIKON by measuring sample.Then, focus is directed at the surface of the central part of polarization plates, with this place for benchmark, focus is directed at 4 corners of polarization plates, determine the distance of the difference of height relative to the focus as benchmark.Using the average distance in 4 corners as amount of curl.
(making of polaroid)
Utilize dry type stretching longitudinal direction uniaxial tension for about 5 times the polyvinyl alcohol films (average degree of polymerization about 2400,99.9 moles of more than % of saponification degree) of thick 20 μm, after keeping tensioned state to impregnate 1 minute in the pure water of 60 DEG C unchangeably again, impregnate 60 seconds in the aqueous solution of weight ratio is 0.05/5/100 28 DEG C of iodine/potassium iodide/water.Thereafter, impregnate 300 seconds in the aqueous solution of weight ratio is 8.5/8.5/100 72 DEG C of potassium iodide/boric acid/water.Next, after cleaning 20 seconds with the pure water of 26 DEG C, it is dried process at 65 DEG C, obtains the polaroid that gas absorption quantity on polyvinyl alcohol film has the thickness 7 μm of iodine.
(preparation of protecting film)
Prepare following 3 kind protecting film:
Protecting film A: the second adhesive phase by the base material film of the thickness comprising polyethylene terephthalate 75 μm and thickness 13 μm and for acrylic acid series constitutes (moisture permeability 8g/ (m224hr), humidity expansion coefficient 6.4ppm %RH-1, gross thickness 88 μm),
Protecting film B: the second adhesive phase by the base material film of the thickness comprising polyethylene terephthalate 75 μm and thickness 18 μm and for acrylic acid series constitutes (moisture permeability 10g/ (m224hr), humidity expansion coefficient 6.8ppm %RH-1, gross thickness 93 μm)
Protecting film C: the second adhesive phase by the base material film of the thickness comprising polyethylene terephthalate 38 μm and thickness 20 μm and for acrylic acid series constitutes (moisture permeability 17g/ (m224hr), humidity expansion coefficient 6.4ppm %RH-1, gross thickness 58 μm)
(preparation of the first protecting film)
Prepare in the upper stacking of KonicaMinolta (strain) tri acetyl cellulose membrane (thickness 25 μm, trade name " KC2UA ") made the film of the hard conating of the acrylic acid series of thickness 7 μm.
(preparation of the second protecting film)
Prepare cyclic polyolefin resin film that Japanese Zeon (strain) makes (phase difference value R in face when thickness 13 μm, wavelength 590nmeThickness direction phase difference value R when=0.8nm, wavelength 590nmthThickness direction phase difference value R when=3.4nm, wavelength 483nmthThickness direction phase difference value R when=3.5nm, wavelength 755nmth=2.8nm).
(preparation of the first adhesive phase)
Prepare processed, by the demoulding implementing the isolating membrane comprising polyethylene terephthalate of the thickness 38 μm that the demoulding processes, the commercially available adhesive phase with isolating membrane that face is provided with the acrylic adhesive layer of thick 20 μm as the first adhesive phase with isolating membrane.The store elastic modulus of this adhesive phase is 0.05MPa at 23 DEG C, is 0.04MPa at 80 DEG C.
(preparation of water system bonding agent)
Relative to water 100 weight portion, dissolve carboxy-modified polyvinyl alcohol (" KL-318 " of (strain) Kuraray) 3 weight portions, prepare polyvinyl alcohol water solution.In the aqueous solution of gained be 1.5 weight portions relative to water 100 weight portion ratio mixing water soluble polyamide epoxy resin (" SumirezResin650 (30) ", solid component concentration 30 weight % that ridge, field chemical industry (strain) is made), obtain water system bonding agent.
<embodiment 1>
Utilize below step, produce and there is the polarization plates with protecting film that the layer identical with Fig. 2 is constituted.First, in the one side of above-mentioned polaroid 10, use above-mentioned water system bonding agent to make the mode that hard conating is the side away from polaroid 10 fit above-mentioned first protecting film 21, at opposite face, similarly use above-mentioned water system bonding agent to fit the second protecting film 22.Thereafter, at 80 DEG C so as to dry 5 minutes, 40 DEG C of ripenings 168 hours.The humidity expansion coefficient of the polarization plates of gained is 28ppm %RH-1。
Then, the second protecting film 22 with the face of polaroid 10 side opposite side on fit the first above-mentioned adhesive phase 31 (there is isolating membrane 70 outside).Again at the outside of the hard conating of the first protecting film 21 folder across its second adhesive phase above-mentioned protecting film A of laminating, obtain the polarization plates with protecting film.The polarization plates with protecting film to gained, determines amount of curl according to above-mentioned method.The results are shown in Table 1.
<embodiment 2>
Except replacing protecting film A and employ protecting film B, produce the polarization plates with protecting film and individual body thereof identically with embodiment 1, determine amount of curl.The results are shown in Table 1.
<comparative example 1>
Except replacing protecting film A and employ protecting film C, produce the polarization plates with protecting film and individual body thereof identically with embodiment 1, determine amount of curl.The results are shown in Table 1.
(preparation of the first protecting film (B))
Prepare tri acetyl cellulose membrane that KonicaMinolta (strain) makes (phase difference value R in face when thickness 25 μm, trade name " KC2TW ", wavelength 590nmeThickness direction phase difference value R when=1.2nm, wavelength 590nmth=1.3nm).
(preparation of the 3rd adhesive phase)
The organic solvent solution die coating machine of urethane acrylate oligomer and isocyanate-based cross-linking agent of with the addition of in butyl acrylate and acrylic acid copolymer is implemented on the demoulding process face of the isolating membrane comprising polyethylene terephthalate of the thickness 38 μm that the demoulding processes making the mode that dried thickness is 5 μm be coated on, so as to dry, thus prepare the 3rd adhesive phase with isolating membrane.The store elastic modulus of the 3rd adhesive phase is 0.40MPa at 23 DEG C, is 0.18MPa at 80 DEG C.
<embodiment 3>
First, in the one side of above-mentioned polaroid 10, use above-mentioned water system bonding agent, fit above-mentioned first protecting film (B) as the first protecting film 21, at opposite face, above-mentioned 3rd adhesive phase (there is isolating membrane outside) of fitting.Then, after the isolating membrane of the 3rd adhesive phase is peeled off removing, on the surface of the 3rd adhesive phase exposed because of stripping, the brightness enhancement film (" AdvancedPolarizedFilm, the Version3 " of 3M company) that laminating is thick 26 μm.The humidity expansion coefficient of the polarization plates of gained is 9.3ppm %RH-1。
Then, at the outside of brightness enhancement film folder across its second adhesive phase laminating said protection film A, the polarization plates with protecting film is obtained.The polarization plates with protecting film to gained, determines amount of curl according to above-mentioned method.The results are shown in Table 1.
<comparative example 2>
Except replacing protecting film A and employ protecting film C, produce the polarization plates with protecting film and individual body thereof identically with embodiment 3, determine amount of curl.The results are shown in Table 1.
[table 1]
Claims (10)
1. with a polarization plates for protecting film,
Possess the polarization plates comprising polaroid and be laminated in the protecting film of one surface,
The described protecting film moisture permeability when temperature 40 DEG C, relative humidity 90% is 15g/ (m224hr) below.
2. the polarization plates with protecting film according to claim 1, wherein,
The thickness of described polarization plates is less than 125 μm.
3. the polarization plates with protecting film according to claim 1, wherein,
Another surface of described polarization plates is made up of the surface of the first adhesive phase.
4. the polarization plates with protecting film according to claim 1, wherein,
Described protecting film is made up of the second adhesive phase being laminated in one surface and the base material film being laminated in monolayer thereon.
5. the polarization plates with protecting film according to claim 1, wherein,
Described polarization plates is also included at least one clip surface protecting film across the solidfied material layer stackup of active energy ray-curable bonding agent of described polaroid.
6. the polarization plates with protecting film according to claim 1, wherein,
Another surface of described polarization plates is made up of the surface of the first adhesive phase,
It is also equipped with being laminated in the isolating membrane on another surface of described polarization plates.
7. the polarization plates with protecting film according to claim 1, wherein,
Described polarization plates also comprises the blooming beyond described polaroid,
At protecting film described in the surface stacking of described blooming.
8. the polarization plates with protecting film according to claim 7, wherein,
Described blooming is brightness enhancement film.
9. the polarization plates with protecting film according to claim 1, wherein,
The thickness of described polaroid is less than 15 μm.
10. a duplexer, it comprises image-displaying member and is laminated in the polarization plates with protecting film according to any one of claim 1～9 thereon.
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| JP2014-258644 | 2014-12-22 | ||
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| JP2015-238367 | 2015-12-07 | ||
| JP2015238367A JP6258911B2 (en) | 2014-12-22 | 2015-12-07 | Polarizing plate with protective film and laminate including the same |
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