CN106662690B - The manufacturing method of the polarization plates of two sides band protective film - Google Patents

The manufacturing method of the polarization plates of two sides band protective film Download PDF

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CN106662690B
CN106662690B CN201580035235.7A CN201580035235A CN106662690B CN 106662690 B CN106662690 B CN 106662690B CN 201580035235 A CN201580035235 A CN 201580035235A CN 106662690 B CN106662690 B CN 106662690B
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film
protective film
polarization plates
iodine system
polarizing film
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CN106662690A (en
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九内雄一朗
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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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

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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

The present invention provides a kind of manufacturing method of the polarization plates of two sides band protective film; it includes the process for removing substrate film stripping from the multilayer film successively comprising base material film, iodine system polarizing film and the 1st protective film and the process in the 2nd protective film of the outer surface of iodine system polarizing film fitting; wherein, it is 150g/m that the 1st and the 2nd protective film, which is moisture permeability,2/ r thermoplastic resin film below, the moisture rate of iodine system polarizing film when being bonded 2 protective film are lower than 8 weight % for 24 hours；And a kind of polarization plates of two sides band protective film, being laminated with moisture permeability on the two sides of iodine system polarizing film of the moisture rate lower than 8 weight % is 150g/m2/ r thermoplastic resin film below for 24 hours.

Description

The manufacturing method of the polarization plates of two sides band protective film
Technical field
The present invention relates to the manufactures of the polarization plates for the two sides band protective film that protective film is fitted on the two sides of iodine system polarizing film Method more specifically is related to successively being bonded the low protective film of moisture permeability on the two sides of iodine system polarizing film to manufacture two sides band The method of the polarization plates of protective film.
Background technique
Polarization plates are widely used in the display devices such as liquid crystal display device, are especially widely used in smart phone in recent years Such various mobile devices.As polarization plates, guarantor has generally been bonded using bonding agent in the one or two sides of polarizing film The polarization plates of the composition of cuticula.
Its own humidity resistance of polarizing film is low, and polarization characteristic is easy deterioration under hygrothermal environment.In the past, in protection polarizing film Protective film in use tri acetyl cellulose membrane, but tri acetyl cellulose membrane due to moisture permeability height, so being used for protective film Polarization plates especially there is a problem of that humidity resistance is still insufficient in the case where using iodine system polarizing film as polarizing film.
Therefore, in order to improve the humidity resistances of polarization plates, propose instead of tri acetyl cellulose membrane and will such as norborneol The low protective film of moisture permeability as alkene resin film fits on iodine system polarizing film (for example, Japanese Unexamined Patent Publication 2004-245925 The paragraph [0005] of bulletin (patent document 1)).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2004-245925 bulletin
Summary of the invention
Problems to be solved by the invention
If the low protective film of moisture permeability to be fitted in the two sides of iodine system polarizing film, due to the intrusion from external moisture It reduces, so can be improved the humidity resistance of polarization plates.However, its another aspect, the research of people is understood through the invention: two If the polarization plates of the previous two sides band protective film for the protective film that face has used such moisture permeability low are implemented and general moisture-proof Compared to the heat-resistance test being exposed under higher temperature environment, then the light leakage generated under cross Nicols (fades for hot test And from polarization plates leakage red area light and polarization plates seem rubescent phenomenon.Also referred to as red change.) or polarization characteristic It reduces.The thickness of iodine system polarizing film is smaller, and the bad problem of the heat resistance is more significant.
Therefore, the purpose of the present invention is to provide be bonded the low protection of penetrability on the two sides of iodine system polarizing film for manufacturing The polarization plates of film and have both humidity resistance and heat resistance two sides band protective film polarization plates method and have both humidity resistance With the polarization plates of the two sides band protective film of heat resistance.
Solution for solving the problem
The present invention provide the polarization plates of two sides band protective film as shown below manufacturing method and two sides band protective film it is inclined Vibration plate.
[1] a kind of manufacturing method of the polarization plates of two sides band protective film comprising following process:
Substrate film stripping is removed from the multilayer film successively comprising base material film, iodine system polarizing film and the 1st protective film and is obtained To the process of the polarization plates of one-side band protective film；With
The outer surface of iodine system polarizing film in the polarization plates of above-mentioned one-side band protective film is bonded the 2nd protective film and obtains two The process of polarization plates of the face with protective film,
It is 150g/m that above-mentioned 1st protective film and above-mentioned 2nd protective film, which are moisture permeability,2/ r thermoplastic resin film below for 24 hours,
The moisture rate of above-mentioned iodine system polarizing film when being bonded above-mentioned 2 protective film is lower than 8 weight %.
[2] manufacturing method according to [1], wherein protected using active energy ray-curable bonding agent by the above-mentioned 2nd Cuticula fits in the outer surface of above-mentioned iodine system polarizing film.
[3] manufacturing method according to [1] or [2], wherein above-mentioned iodine system polarizing film with a thickness of 10 μm or less.
[4] a kind of manufacturing method of the polarization plates of two sides band protective film comprising: comprising iodine system polarizing film and it is being laminated in Iodine system polarizing film outer surface in the polarization plates of the one-side band protective film of 1st protective film of its single side is bonded the 2nd protective film, obtains The process of the polarization plates of two sides band protective film,
It is 150g/m that above-mentioned 1st protective film and above-mentioned 2nd protective film, which are moisture permeability,2/ r thermoplastic resin film below for 24 hours,
The moisture rate of above-mentioned iodine system polarizing film when being bonded above-mentioned 2 protective film is lower than 8 weight %.
[5] manufacturing method according to [4], wherein protected using active energy ray-curable bonding agent by the above-mentioned 2nd Cuticula fits in the outer surface of above-mentioned iodine system polarizing film.
[6] manufacturing method according to [4] or [5], wherein above-mentioned iodine system polarizing film with a thickness of 10 μm or less.
[7] a kind of polarization plates of two sides band protective film, it includes iodine system polarizing film and the protective film for being laminated in its two sides,
It is 150g/m that the protective film for being laminated in two sides, which is moisture permeability,2/ r thermoplastic resin film below for 24 hours,
The moisture rate of above-mentioned iodine system polarizing film is lower than 8 weight %.
[8] polarization plates of the two sides band protective film according to [7], wherein above-mentioned iodine system polarizing film with a thickness of 10 μm Below.
Invention effect
The low protective film of penetrability is fitted on the two sides of iodine system polarizing film for manufacturing in accordance with the invention it is possible to provide Polarization plates and have both humidity resistance and heat resistance two sides band protective film polarization plates method and the two of iodine system polarizing film Face is fitted with the polarization plates of the low protective film of penetrability and has both the polarization of the two sides band protective film of humidity resistance and heat resistance Plate.
Detailed description of the invention
Fig. 1 is a preferred example for the manufacturing method for the polarization plates for indicating two sides band protective film of the present invention Flow chart.
Fig. 2 is the simple sectional view of an example of the layer structure for the polarization plates for indicating one-side band protective film.
Fig. 3 is the flow chart for indicating a preferred example for polarization plates preparatory process for one-side band protective film.
Fig. 4 is the simple section for indicating an example of layer structure for the stacked film obtained by resin layer formation process Figure.
Fig. 5 is the simple sectional view for indicating an example of layer structure for the stretched film obtained by stretching process.
Fig. 6 is the simple section for indicating an example of layer structure for the polarizability stacked film obtained by dyeing process Figure.
Fig. 7 is the simple sectional view for indicating an example of layer structure for the multilayer film obtained by bonding process.
Fig. 8 is the simple section of an example of the layer structure for the polarization plates for indicating two sides band protective film of the present invention Figure.
Specific embodiment
<manufacturing methods of the polarization plates of two sides band protective film>
The manufacturing method of the polarization plates of two sides band protective film of the present invention is as shown in Figure 1, may include Following processes.
(1) prepare the polarization plates of the one-side band protective film comprising iodine system polarizing film and the 1st protective film for being laminated in its single side Process S10 (hereinafter also referred to as " the polarization plates preparatory process S10 of one-side band protective film ") and
(2) the iodine system polarizing film outer surface in the polarization plates of one-side band protective film is bonded the 2nd protective film, obtains two sides band The process S20 of the polarization plates of protective film (hereinafter also referred to as " the polarization plates production process S20 of two sides band protective film ").
As described above in the present invention, the 1st protective film and the 2nd protective film are successively bonded relative to iodine system polarizing film. At this point, in order to improve the humidity resistance of the polarization plates of obtained two sides band protective film, as fitting in the one of iodine system polarizing film 1st protective film in a face and the 2nd protective film for fitting in another face are 150g/m using moisture permeability2/ for 24 hours r it is below low The thermoplastic resin film of humidity.
In addition, will be pasted on iodine system polarizing film to improve the heat resistance of the polarization plates of obtained two sides band protective film The moisture rate of iodine system polarizing film when closing 2 protective film is set to be lower than 8 weight %.In the present invention, in order to improve humidity resistance, The low protective film of moisture permeability is bonded on the two sides of iodine system polarizing film and polarization plates are made, still,
If the low protective film of moisture permeability a) is suitable for two sides, the moisture in iodine system polarizing film is difficult to diffuse to outside, Moisture lodges in iodine system polarizing film,
B) draw due to the red change in heat-resistance test, the reduction of polarization characteristic are the moisture because remaining in the iodine system polarizing film It rises,
From it is above-mentioned situations such as, the moisture rate of iodine system polarizing film when 2 protective film of management fitting is that have as described above Effect.The moisture rate of iodine system polarizing film is measured according to the method recorded in the item of embodiment.
The moisture rate of iodine system polarizing film can be by the process of the polarization plates of manufacture two sides band protective film and in iodine system Either phase setting (3) before being bonded the 2nd protective film on polarizing film implements moisture rate reduction to the film comprising iodine system polarizing film Process S30 (hereinafter also referred to as " moisture rate reduces process S30 ") Lai Dacheng (referring to Fig.1) of processing.
Hereinafter, being illustrated referring to Fig. 2~Fig. 8 to each process.
(1) the polarization plates preparatory process S10 of one-side band protective film
This process is to prepare such as Fig. 2 of (preparation) comprising iodine system polarizing film 5 and the 1st protective film 10 for being laminated in its single side Shown in such one-side band protective film polarization plates 100 process.As shown in Figure 2, the 1st protective film 10 is usually situated between It is bonded and (is adhesively fixed) in the single side of iodine system polarizing film 5 by the 1st adhesive layer 15.
(iodine system polarizing film)
Iodine system polarizing film 5 is polarizing film obtained from the iodine gas absorption quantity made as dichroism pigment, specifically, can be with It is to make iodine polarizing film obtained from gas absorption quantity in the polyvinyl alcohol resin (or film) through being uniaxially stretched.Iodine system polarization The thickness of piece 5 for example can for 30 μm or less, and then 20 μm hereinafter, especially mobile device use in, from two sides band protective film Polarization plates slimming from the perspective of, preferably 10 μm hereinafter, more preferably 8 μm or less.The thickness of iodine system polarizing film 5 is logical It is often 2 μm or more.
If the thickness of iodine system polarizing film 5 becomes smaller, since the concentration of iodine becomes higher, with the protective film that is laminated in two sides The concentration of the neighbouring existing iodo-complexes in interface also get higher, so being easy to be influenced by from the moisture of outside intrusion.Therefore, The thickness of iodine system polarizing film 5 is smaller, and humidity resistance is easy to become lower.In addition, if the thickness of iodine system polarizing film 5 becomes smaller and iodine Concentration becomes higher, then becomes easy the influence by the moisture remained in iodine system polarizing film, and heat resistance is also easy to be lower.Picture In this way, the thickness of iodine system polarizing film 5 is smaller, then humidity resistance and heat resistance is easier is lower, thus the present invention is polarized in iodine system It is especially advantageous in the case that the thickness of piece 5 is small.
As the polyvinyl alcohol system resin for constituting polyvinyl alcohol resin, can be used polyvinyl acetate system Resin obtained from resin saponification.As polyvinyl acetate system resin, in addition to homopolymer, that is, poly-vinegar acid second of vinylacetate Other than enester, the copolymer of vinylacetate with the other monomers that can be copolymerized with it can be also exemplified.As can be with acetic acid Vinyl acetate copolymerization other monomers, such as can enumerate unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class, (methyl) acrylic amide with ammonium etc..
" (methyl) acrylic acid " refers to selected from least one of acrylic acid and methacrylic acid in this specification.It is so-called It is also the same whens " (methyl) acryloyl group " etc..
Film obtained from above-mentioned polyvinyl alcohol system resin is filmed constitutes iodine system polarizing film 5.By polyvinyl alcohol It is that the method that resin is film-made is not particularly limited, can be filmed by well known method, but small from thickness is easy to get Iodine system polarizing film 5, film in process the treatability of iodine system polarizing film 5 also excellent aspect is set out, it is preferably aftermentioned such The solution of polyvinyl alcohol system resin is coated on the method being filmed on base material film.
The saponification degree of polyvinyl alcohol system resin can be the range of 80.0~100.0 moles of %, but preferably 90.0~ The range of 99.5 moles of %, the range of more preferably 94.0~99.0 moles %.If saponification degree is lower than 80.0 moles of %, gained The water resistance and humidity resistance of the polarization plates of the two sides band protective film arrived reduce.When use saponification degree is more than the poly- of 99.5 moles of % When vinyl alcohol system resin, the dyeing kinetics of iodine are slack-off sometimes, and productivity reduces, while cannot have sufficient polarization property Iodine system polarizing film 5.
So-called saponification degree is that the poly-vinegar acid second as the raw material of polyvinyl alcohol system resin is indicated using unit ratio (mole %) Acetoxy group (the acetoxyl group :-OCOCH for including in enester system resin3) be changing by saponifying process hydroxyl ratio value, with Following formula defines:
Saponification degree (mole %)=100 × (number of hydroxyl) ÷ (number+acetoxy group number of hydroxyl)
Saponification degree can be found out according to JIS K 6726-1994.Saponification degree is higher, indicates that the ratio of hydroxyl is higher, because This, indicates to hinder the ratio of the acetoxy group of crystallization lower.
Polyvinyl alcohol system resin is also possible to the modified polyvinyl alcohol that a part is modified.For example, can enumerate by The alkene such as polyvinyl alcohol system resin ethylene, propylene；The unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid；It is unsaturated Modified polyvinyl alcohol obtained from the Arrcostab of carboxylic acid, (methyl) acrylamide etc. are modified.Modified ratio is preferably less than 30 moles of %, again more preferably less than 10%.In the case where being performed for more than the modification of 30 moles of %, exists and become difficult to adsorb Iodine is difficult to obtain the tendency of the iodine system polarizing film 5 with sufficient polarization property.
The average degree of polymerization of polyvinyl alcohol system resin is preferably 100~10000, and more preferably 1500~8000, into one Step preferably 2000~5000.The average degree of polymerization of polyvinyl alcohol system resin can also be asked according to JIS K 6726-1994 Out.
(the 1st protective film)
1st protective film 10 is comprising (preferably optically transparent) thermoplastic resin with translucency and moisture permeability is 150g/m2/ r film below for 24 hours.Moisture permeability also includes the moisture permeability of aftermentioned 2nd protective film, is according to JIS Z 0208- 40 DEG C of the temperature of 1976 " the moisture permeability test methods (cup type method) of water vapor proof barrier packaging material " measurement, the moisture-inhibiting under relative humidity 90% Degree.Moisture permeability is preferably 100g/m2/ r or less for 24 hours.
As the moisture permeability 150g/m for making the 1st protective film 102/ r the following method for 24 hours can enumerate and constitute film The thickness or the low blocking of setting penetrability on film of the low resin of penetrability or increase film are used in thermoplastic resin The method of layer.
The thermoplastic resin for constituting the 1st protective film 10 is not particularly limited as long as it can reach above-mentioned moisture permeability, from saturating It sets out in terms of moist thickness low, that the 1st protective film 10 can be reduced, it is preferable to use chain polyolefin-based resins are (polypropylene-based Resin etc.), polyolefin-based resins as cyclic polyolefin hydrocarbon system resin (norbornene resin etc.)；Poly terephthalic acid second two Polyester based resin as alcohol ester system resin；Polycarbonate-based resin；(methyl) acrylic resin；Polystyrene resin； Or their mixture, copolymer etc..
1st protective film 10 is also possible to phase difference film, brightness improves the protective film that optical function is had both as film.Such as By will include that the film of above-mentioned thermoplastic resin is stretched and (is stretched uniaxially or biaxially) or forms liquid on the film The phase difference film for imparting arbitrary phase difference value can be made in crystal layer etc..
As chain polyolefin-based resins, in addition to the homopolymer of chain olefin as polyvinyl resin, acrylic resin In addition, the copolymer comprising chain olefin of more than two kinds can also be enumerated.
Cyclic polyolefin hydrocarbon system resin is the general name for the resin being polymerized using cyclic olefin as polymerized unit.If enumerating The specific example of cyclic polyolefin hydrocarbon system resin is then the open loop of cyclic olefin (total) polymers, the addition polymer of cyclic olefin, ring Shape alkene is used unsaturated with the copolymer (representativeness is random copolymer) of chain olefin as ethylene, propylene and by them Graft polymers and their hydride etc. obtained from carboxylic acid or derivatives thereof is modified.Wherein, it is preferred to use use drop ice Norbornene resin of the orbornene-baseds monomer such as piece alkene or polycyclic orbornene-based monomer as cyclic olefin.
Polyester based resin is the resin with ester bond, generally the polycondensation comprising polybasic carboxylic acid or derivatives thereof with polyalcohol The resin of object.As polybasic carboxylic acid or derivatives thereof, dicarboxylic acids or derivatives thereof can be used, such as terephthaldehyde can be enumerated Acid, M-phthalic acid, dimethyl terephthalate (DMT), naphthalene dicarboxylic acids dimethyl ester etc..As polyalcohol, dihydric alcohol, example can be used Ethylene glycol, propylene glycol, butanediol, neopentyl glycol, cyclohexanedimethanol can such as be enumerated.
The specific example of polyester based resin includes polyethylene terephthalate, polybutylene terephthalate (PBT), gathers (ethylene naphthalate), polybutylene naphthalate, polypropylene terephthalate, polytrimethylene naphthalate, Polycyclohexylene's dimethyl ester, poly- naphthalenedicarboxylic acid cyclohexane dicarboxylates.
Polycarbonate-based resin includes the polymer that monomeric unit is bonded with via carbonate group.Polycarbonate-based resin It is also possible to be referred to as resin, the copolymerization polycarbonate etc. of modified polycarbonate obtained from modifying polymer backbone.
(methyl) acrylic resin is the tree using the compound with (methyl) acryloyl group as main composition monomer Rouge.The specific example of (methyl) acrylic resin is for example comprising (methyl) acrylic acid poly- as polymethyl methacrylate Ester；Methyl methacrylate-(methyl) acrylic copolymer；Methyl methacrylate-(methyl) acrylate copolymer；Methyl Methyl acrylate-acrylic acid ester-(methyl) acrylic copolymer；(methyl) acrylate-styrene copolymer (MS resin Deng)；Copolymer (such as methyl methacrylate-methyl-prop of methyl methacrylate and the compound with alicyclic alkyl Olefin(e) acid hexamethylene ester copolymer, methyl methacrylate-(methyl) acrylic acid norbornyl ester copolymer etc.).It is preferable to use poly- (first Base) methyl acrylate is such with poly- (methyl) acrylic acid C1-6Arrcostab makees polymer as main component, more preferable use with Methyl methacrylate of the methyl methacrylate as main component (50~100 weight %, preferably 70~100 weight %) It is resin.
The surface with 5 opposite side of iodine system polarizing film in the 1st protective film 10 can also form hard conating, antiglare layer, anti- Surface-treated layer as reflecting layer, antistatic layer, stain-proofing layer (coating layer).The method for forming surface-treated layer does not limit especially It is fixed, well known method can be used.
1st protective film 10 can contain one kind or two or more lubricant, plasticizer, dispersing agent, heat stabilizer, ultraviolet light Additive as absorbent, infrared absorbent, antistatic agent, antioxidant.
From the viewpoint of the slimming of the polarization plates of two sides band protective film, the thickness of the 1st protective film 10 is preferably 90 μm Hereinafter, more preferably 50 μm hereinafter, further preferably 30 μm or less.From the viewpoint of intensity and treatability, the 1st protective film 10 thickness is usually 5 μm or more.
(the 1st adhesive layer)
1st adhesive layer 15 is the layer for the 1st protective film 10 that is adhesively fixed on a face of iodine system polarizing film 5.Make For the bonding agent for forming the 1st adhesive layer 15, can be containing by as ultraviolet light, visible light, electron ray, X-ray (preferably ultraviolet light is solid for the active energy ray-curable bonding agent of the irradiation of active energy beam and cured curability compound Change property bonding agent), be dissolved or dispersed in bonding agent ingredient as polyvinyl alcohol system resin in water made of water system be bonded Agent.
Above-mentioned curability compound can be the curability compound or free-radical polymerised solidification of cationically polymerizable Property compound.As the curability compound of cationically polymerizable, for example, can enumerate epoxy compound (intramolecular have 1 A or 2 or more epoxy groups compound), (intramolecular has 1 or 2 or more oxa- to oxetanes based compound The compound of cyclobutane ring) or their combination.As free-radical polymerised curability compound, such as (first can be enumerated Base) acrylic compounds (compound of the intramolecular with 1 or 2 or more (methyl) acryloxy), have freely The other vinyl compounds or their combination of the double bond of base polymerism.It can also be by the solidification of cationically polymerizable Property compound is used in combination with free-radical polymerised curability compound.Active energy ray-curable bonding agent is usually also comprising using In the cationic polymerization initiators and/or radical polymerization initiator of the curing reaction for causing above-mentioned curability compound.
The polarization plates 100 of one-side band protective film can be pre-prepd polarization plates, be also possible to pass through arbitrary method The polarization plates of manufacture.As manufacturing method, following method can be enumerated.
I) it is protected in the single-sided lamination the 1st of the iodine system polarizing film 5 comprising monomer (independent) film manufactured by well known method The method of cuticula 10 and
Ii) such manufacturing method comprising following processes shown in Fig. 3.
And being made it dry after the coating liquid that at least one face coating in base material film contains polyvinyl alcohol system resin Formed polyvinyl alcohol resin and obtain stacked film resin layer formation process S10-1,
Stacked film is stretched obtain stretched film stretching process S10-2,
The polyvinyl alcohol resin of stretched film is dyed with iodine and forms iodine system polarizing film, obtains polarizability layer The dyeing process S10-3 of folded film,
The 1st protective film 10 is bonded on the iodine system polarizing film of polarizability stacked film and obtains the bonding process S10- of multilayer film 4 and
Substrate film stripping is removed from multilayer film and obtains the stripping process S10- of the polarization plates 100 of one-side band protective film 5。
(resin layer formation process S10-1)
Referring to Fig. 4, this process is to form polyvinyl alcohol resin 6 at least one face of base material film 30 and obtain The process of stacked film 200.The polyvinyl alcohol resin 6 is become via stretching process S10-2 and dyeing process S10-3 The layer of iodine system polarizing film 5.Polyvinyl alcohol resin 6 can be by that will contain the coating liquid coating of polyvinyl alcohol system resin To base material film 30 one or two sides and make it dry and formed.Coating in this way forms polyvinyl alcohol resin Method be advantageous in terms of iodine system polarizing film 5 for being easy to get film.
Base material film 30 may include thermoplastic resin, wherein preferably comprise the transparency, mechanical strength, thermal stability, stretching The excellent thermoplastic resins such as property.The specific example of such thermoplastic resin is for example comprising chain polyolefin-based resins, ring-type Polyolefin-based resins as polyolefin-based resins (norbornene resin etc.)；Polyester based resin；(methyl) acrylic acid series tree Rouge；Cellulose esters system resin as Triafol T, cellulose diacetate；Polycarbonate-based resin；Polyvinyl alcohol system Resin；Polyvinyl acetate system resin；Polyarylate system resin；Polystyrene resin；Polyether sulfone system resin；Polysulfones system resin； Polyamide resin；Polyimides system resins；And their mixture, copolymer.
Base material film 30 can be the single layer knot being made of 1 resin layer comprising one kind or two or more thermoplastic resin Structure is also possible to the resin layer comprising one kind or two or more thermoplastic resin carrying out multiple multilayered structures being laminated. Base material film 30 preferably is contained in aftermentioned stretching process S10-2 can be to be suitable for carrying out polyvinyl alcohol resin 6 The draft temperature of stretching stretches such resin.
Base material film 30 can contain additive.The specific example of additive includes ultraviolet absorbing agent, antioxidant, lubrication Agent, plasticizer, release agent, coloring agent, fire retardant, nucleating agent, antistatic agent, pigment and colorant.
From intensity, treatability etc., the thickness of base material film 30 is usually 1~500 μm, and preferably 1~300 μm, More preferably 5~200 μm, further preferably 5~150 μm.
The coating liquid being coated on base material film 30 preferably makes the powder of polyvinyl alcohol system resin be dissolved into good solvent (example Such as water) in obtained from polyvinyl alcohol system resin solution.The details of polyvinyl alcohol system resin is as described above.Coating liquid The additives such as plasticizer, surfactant can also be contained as needed.
Above-mentioned coating liquid is applied the method being attached on base material film 30 can be from wire rod rubbing method；Reversed coating, intaglio plate apply Rolling method as cloth；Die coating method；Comma rubbing method；Lip rubbing method；Spin-coating method；Silk screen rubbing method；Jetting type rubbing method；Leaching Stain method；It is suitably selected in the methods of spray-on process.
The drying temperature of coating layer (the polyvinyl alcohol resin before dry) and drying time wrap according in coating liquid The type of the solvent contained and set.Drying temperature is, for example, 50~200 DEG C, and preferably 60~150 DEG C.When solvent includes water, Drying temperature is preferably 80 DEG C or more.
Polyvinyl alcohol resin 6 can only be formed in a face of base material film 30, can also be formed in two sides.If shape At the curling in two sides, being then able to suppress the film that can produce in the manufacture of polarizability stacked film 400 (referring to Fig. 6), simultaneously Since 2 polarization plates can be obtained by 1 polarizability stacked film 400, so also advantageous in terms of production efficiency.
The thickness of polyvinyl alcohol resin 6 in stacked film 200 is preferably 3~30 μm, and more preferably 5~20 μm. If the polyvinyl alcohol resin 6 with the thickness within the scope of this, then via aftermentioned stretching process S10-2 and dyer Sequence S10-3, can obtain iodine dyeability is good and polarization property is excellent and sufficiently thin (such as with a thickness of 10 μm or less ) iodine system polarizing film 5.
It, can also in order to improve the adaptation of base material film 30 Yu polyvinyl alcohol resin 6 before the coating of coating liquid At the surface implementation sided corona treatment of the base material film 30 to the side at least forming polyvinyl alcohol resin 6, plasma Reason, flame (flame) processing etc..The same reason of this external cause can also form polyethylene via prime coat etc. on base material film 30 Base alcohol resin 6.
Prime coat can be made it dry and shape after prime coat formation is coated on the surface of base material film 30 with coating liquid At.The coating liquid includes to play both base material film 30 and polyvinyl alcohol resin 6 closing force strong to a certain degree Ingredient generally comprises the resin component and solvent for assigning such closing force.As resin component, it is preferable to use the transparency, heat The excellent hot castable resin such as stability, draftability, such as (methyl) acrylic resin, polyvinyl alcohol system tree can be enumerated Rouge etc..Wherein, it is preferable to use giving the polyvinyl alcohol system resin of good closing force.More preferably polyvinyl alcohol resin. As solvent, usually using the general organic solvent or water solvent that can dissolve above-mentioned resin component, preferably by being made with water Prime coat is formed for the coating liquid of solvent.
It, can also be in prime coat formation with adding crosslinking agent in coating liquid in order to improve the intensity of prime coat.Crosslinking agent Specific example includes epoxy, isocyanates system, dialdehyde system, metal system (such as metal salt, metal oxide, metal hydroxide Object, organo-metallic compound), the crosslinking agent of macromolecular.Use polyvinyl alcohol system resin as the resin for forming prime coat It is suitable for using Polyamide Epoxy, methylolated melamine resin, dialdehyde system crosslinking agent, metal-chelating materialization when ingredient Close object system crosslinking agent etc..
The thickness of prime coat is preferably 0.05~1 μm or so, and more preferably 0.1~0.4 μm.If becoming thinner than 0.05 μm, The effect that then closing force of base material film 30 and polyvinyl alcohol resin 6 improves is small, if becoming than 1 μ m-thick, to two sides band The slimming of the polarization plates of protective film is unfavorable.
Prime coat formation is coated on the method on base material film 30 with coating liquid can be with polyvinyl alcohol resin shape At coating liquid it is same.The drying temperature of coating layer comprising prime coat formation coating liquid is, for example, 50~200 DEG C, preferably It is 60~150 DEG C.When solvent includes water, drying temperature is preferably 80 DEG C or more.
(stretching process S10-2)
Referring to Fig. 5, this process is to stretch stacked film 200, and obtain drawn includes base material film 30 ' and polyethylene The process of the stretched film 300 of base alcohol resin 6 '.Stretch processing is usually to be uniaxially stretched.
The stretching ratio of stacked film 200 can as expected polarization characteristic and suitably select, but preferably with respect to layer The original of folded film 200 it is a length of more than 5 times and 17 times hereinafter, more preferably more than 5 times and 8 times or less.If stretching ratio be 5 times with Under, then since polyvinyl alcohol resin 6 ' is without being sufficiently orientated, so the degree of polarization of iodine system polarizing film 5 does not have sometimes Sufficiently get higher.On the other hand, if stretching ratio is more than 17 times, become the fracture for being easy to produce film when stretching, stretch simultaneously The thickness of film 300 is thinned to necessity or more, it is possible to which the processability in process and treatability reduce below.
Stretch processing is not limited to one section of stretching, can also be carried out with multistage.In this case, it can dye Whole multistage stretch processings is continuously carried out before process S10-3, can also at the dyeing in dyeing process S10-3 Reason and/or crosslinking Treatment carry out the later stretch processing of second stage simultaneously.When carrying out stretch processing like this with multistage, preferably Stretch processing is carried out in the way of the stretching ratio that the full section of stretch processing is amounted to more than 5 times.
Stretch processing can also be in addition to can be the longitudinal stretching stretched along film length direction (film carry direction) The cross directional stretch stretched along film width direction or oblique extension etc..As longitudinal stretching mode, can enumerate using roller into Stretching, compression stretching between the roller that row stretches as cross directional stretch mode can enumerate drawing using stretching of chuck (clip) etc. Width machine method etc..Stretch processing can use any one of moistening type drawing process, dry-stretch process.
Draft temperature is set as polyvinyl alcohol resin 6 and the whole degree display stream can stretch of base material film 30 It is more than the temperature of dynamic property, preferably -30 DEG C to+30 DEG C of the phase transition temperature (fusing point or glass transition temperature) of base material film 30 Range, more preferably -30 DEG C to+5 DEG C of range, further preferably -25 DEG C to+0 DEG C of range.When base material film 30 includes more When a resin layer, above-mentioned phase transition temperature refers to the highest phase transition temperature in phase transition temperature shown by multiple resin layer.
If draft temperature is made to be lower than -30 DEG C of phase transition temperature, exist the high magnification for being difficult to reach more than 5 times stretch or The mobility of person's base material film 30 is too low and tendency that stretch processing becomes difficult.If draft temperature is more than+30 DEG C of phase transition temperature, The mobility that then there is base material film 30 is excessive and stretches the tendency become difficult.From the high stretching times being more easily achieved more than 5 times It sets out in terms of rate, draft temperature is further preferably 120 DEG C or more in above range.
As the heating means of the stacked film 200 in stretch processing, there is region heating (for example, being blown into hot wind and adjusting The method heated in stretch zones as the whole heating furnace for defined temperature.)；The case where being stretched using roller The lower method by roller conducting self-heating；Heater heating (infrared heater, halogen heater, panel heater etc. is arranged In the method that the upper and lower of stacked film 200 is heated with radiant heat) etc..Between roller in stretching mode, from the equal of draft temperature From the perspective of even property, preferably region heating.
Before stretching process S10-2, the pre-heat treatment process preheated to stacked film 200 also can be set.As Method same as the heating means in stretch processing can be used in pre-heating mean.Preheating temperature is preferably-the 50 of draft temperature DEG C ± 0 DEG C of range is arrived, -10 DEG C of range is arrived in more preferably-the 40 of draft temperature DEG C.
In addition, thermal finalization treatment process also can be set after the stretch processing in stretching process S10-2.Thermal finalization Processing be with while the end of stretched film 300 is maintained tense situation with the state that holds by clip crystallized temperature with On the processing that is heat-treated.It is handled by the thermal finalization, promotes the crystallization of polyvinyl alcohol resin 6 '.At thermal finalization The temperature of reason is preferably -0 DEG C~-80 DEG C of range of draft temperature, the more preferably model of-the 0 of draft temperature DEG C~-50 DEG C It encloses.
(dyeing process S10-3)
Referring to Fig. 6, this process is by the polyvinyl alcohol resin 6 ' of stretched film 300 so that iodine is dyed and makes its suction Attached orientation, the process that iodine system polarizing film 5 is made.It obtains being laminated with iodine system in the one or two sides of base material film 30 ' via this process The polarizability stacked film 400 of polarizing film 5.
Dyeing process can be carried out by impregnating stretched film 300 in the solution (staining solution) containing iodine.As dye Solution made of iodine is dissolved into solvent can be used in color solution.As solvent, water is generally used, can also further be added Add the organic solvent that there is compatibility with water.The concentration of iodine in staining solution is preferably 0.01~10 weight %, more preferably 0.02~7 weight %.
From can be improved dyeing efficiency aspect, iodide are preferably further added in staining solution.As iodine Compound, such as potassium iodide, lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, cupric iodide, barium iodide, iodate can be enumerated Calcium, stannic iodide, titanium iodide etc..The concentration of iodide in staining solution is preferably 0.01~20 weight %.In iodide, preferably Add potassium iodide.When adding potassium iodide, the ratio of iodine and potassium iodide is preferably 1: 5~1: 100 with weight ratio meter, more preferably 1: 6~1: 80.The temperature of staining solution is preferably 10~60 DEG C, and more preferably 20~40 DEG C.
Alternatively, it is also possible to carry out dyeing process S10-3 before stretching process S10-2 or carry out these processes simultaneously, But in order to be orientated the iodine being adsorbed in polyvinyl alcohol resin well, at least one preferably is being implemented to stacked film 200 Implement dyeing process S10-3 after determining the stretch processing of degree.
Dyeing process S10-3 may include the crosslinking Treatment process implemented after dyeing processing.Crosslinking Treatment can by The film through dyeing is impregnated in solution made of crosslinking agent is dissolved in solvent (crosslinker solution) to carry out.As crosslinking agent, example Boron compound, glyoxal, glutaraldehyde etc. as can enumerate boric acid, borax.Crosslinking agent can be used only a kind, can also be with It is two kinds or more.As the solvent of crosslinker solution, water can be used, but can also further include with water with compatibility Organic solvent.The concentration of crosslinking agent in crosslinker solution is preferably 1~20 weight %, more preferably 6~15 weight %.
Crosslinker solution can further include iodide.By the addition of iodide, in the face that iodine system polarizing film 5 can be made Polarization property more uniformization.The specific example of iodide is as described above.The concentration of iodide in crosslinker solution is preferred For 0.05~15 weight %, more preferably 0.5~8 weight %.The temperature of crosslinker solution is preferably 10~90 DEG C.
In addition, crosslinking Treatment can also be carried out by the way that crosslinking agent to be cooperated in staining solution with dyeing processing simultaneously.This Outside, it also can be used and form different crosslinker solutions of more than two kinds, progress 2 times or more the processing impregnated in crosslinker solution.
After dyeing process S10-3 and before aftermentioned bonding process S10-4, washing procedure and back tender are preferably carried out Sequence.Washing procedure generally comprises water washing process.Water washing can pass through the pure water as ion exchange water, distilled water Film of the middle dip dyeing after treated or crosslinking Treatment carries out.Water washing temperature is usually 3~50 DEG C, preferably 4~20 ℃.Washing procedure is also possible to the combination of water washing process and the washing procedure using iodide solution.As in washing procedure The drying process carried out later, can be using arbitrary methods appropriate such as natural drying, air-supply drying, heat dryings.Such as In the case where heat drying, drying temperature is usually 20~95 DEG C.
(bonding process S10-4)
Referring to Fig. 7, this process is by the iodine system polarizing film 5 of polarizability stacked film 400, i.e. iodine system polarizing film 5 With the process for being bonded the 1st protective film 10 via the 1st adhesive layer 15 on the face of 30 ' opposite side of base material film and obtaining multilayer film 500. About the bonding agent for forming the 1st adhesive layer 15, as described above.
In addition, when polarizability stacked film 400 is when the two sides of base material film 30 ' has iodine system polarizing film 5, usually on two sides It is bonded the 1st protective film 10 respectively on iodine system polarizing film 5.In this case, these the 1st protective films 10 can be the guarantor of identical type Cuticula is also possible to different types of protective film.
When using active energy ray-curable bonding agent to be bonded 1 protective film 10, via as the 1st adhesive layer After 1st protective film 10 is laminated on iodine system polarizing film 5 by 15 active energy ray-curable bonding agent, irradiation ultraviolet light, can Active energy beam as light-exposed, electron ray, X-ray solidifies adhesive layer.Its middle-ultraviolet lamp be it is suitable, as this When light source, low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp, black light lamp, microwave-excitation can be used Mercury lamp, metal halide lamp etc..When using water system bonding agent, as long as the 1st protective film 10 is laminated to iodine via water system bonding agent Be on polarizing film 5 after be thermally dried.
When being bonded 1 protective film 10 on iodine system polarizing film 5, for the patch of the 1st protective film 10 and/or iodine system polarizing film 5 Conjunction face can carry out corona treatment, sided corona treatment, at ultraviolet light irradiation to improve the cementability with iodine system polarizing film 5 Reason, flame (flame) processing, the such surface treatment (easy bonding processing) of saponification process, wherein preferred to carry out at plasma Reason, sided corona treatment or saponification process.
(stripping process S10-5)
This process is the process for removing the removing of base material film 30 ' from multilayer film 500.Via the process, obtain same with Fig. 2 The polarization plates 100 of the one-side band protective film of sample.There is iodine system polarizing film on the two sides of base material film 30 ' in polarizability stacked film 400 5 and in the case where being fitted with the 1st protective film 10 on the two iodine system polarizing films 5, by stripping process S50, partially by 1 Vibration property stacked film 400 obtains the polarization plates 100 of 2 one-side band protective films.
By base material film 30 ' removing remove method be not particularly limited, can by with the common polarization with adhesive The same method of stripping process of the diaphragm (stripping film) carried out in plate is removed.Base material film 30 ' can be in bonding process S10-4 It directly removes immediately later, can also once coil into roll after bonding process S10-4, in subsequent process on one side It unreels and is removed on one side.
(2) the polarization plates production process S20 of two sides band protective film
Using this process, pass through the outer surface fitting of the iodine system polarizing film 5 in the polarization plates 100 of one-side band protective film the 2 protective films 20, obtain the polarization plates of two sides band protective film.One example of the layer structure of the polarization plates of two sides band protective film is shown In Fig. 8.As the polarization plates 600 of two sides band protective film shown in fig. 8, the 2nd protective film 20 is usually via the 2nd bonding agent Layer 25 and be bonded and (be adhesively fixed) on iodine system polarizing film 5.The outer surface of so-called iodine system polarizing film 5 refers in iodine system polarizing film 5 The face with 10 opposite side of the 1st protective film, making one-side band protective film via the process for removing the removing of base material film 30 ' In the case where polarization plates 100, refer to the surface that the iodine system polarizing film 5 exposed is removed by the removing of base material film 30 '.
2nd protective film 20 is also similarly comprising (preferably optically transparent) heat with translucency with the 1st protective film 10 Plastic resin and moisture permeability are 150g/m2/ r film below for 24 hours.It is also possible to simultaneous as phase difference film, brightness raising film Has the protective film of optical function.About thickness, the material of surface-treated layer and film etc. that the 2nd protective film 20 can have, reference Record to the upper surface of the 1st protective film 10 description.1st protective film 10 and the 2nd protective film 20 can be comprising mutually the same type Resin protective film, be also possible to the protective film comprising different types of resin.
The bonding agent for forming the 2nd adhesive layer 25 can be similarly active energy ray-curable with the 1st adhesive layer 15 Bonding agent or water system bonding agent, but active energy ray-curable bonding agent as preferably ultra-violet solidified bonding agent. If using water system bonding agent, due to becoming to supply moisture to iodine system polarizing film 5, so when being bonded 2 protective film 20 sometimes The moisture rate of iodine system polarizing film 5 will not become lower than 8 weight %.The bonding agent for forming the 2nd adhesive layer 25 can be with formation the 1st The bonding agent of adhesive layer 15 composition having the same, it is possible to have different compositions.
(3) moisture rate reduces process S30
It is of the present invention in order to make the moisture rate of the iodine system polarizing film 5 when being bonded 2 protective film 20 lower than 8 weight % The manufacturing method of the polarization plates of two sides band protective film is included in the polarization plates of manufacture two sides band protective film as explained above Process in two sides band protective film polarization plates production process S20 before any 1 or more stage implement moisture rate Reduce process S30.It is the moisture rate for implementing to make iodine system polarizing film 5 to the film comprising iodine system polarizing film 5 that moisture rate, which reduces process S30, The process of reduced processing.
If enumerating the example for implementing the opportunity that moisture rate reduces process S30, as described below.
1) one-side band is obtained in the 1st protective film 10 of single-sided lamination of the iodine system polarizing film 5 comprising monomer (independent) film to protect Be bonded after the polarization plates 100 of cuticula in the method for the 2nd protective film 20, be the 1st protective film 10 fitting before, (including two after fitting The front of polarization plates production process S20 of the face with protective film) or the two.Wherein, if due to the state of monomer (independent) film Moisture rate is reduced, then iodine system polarizing film 5 becomes easy cracking or fracture, and it is advantageous to after the fitting for the 1st protective film 10.
2) the 2nd protective film 20 is bonded after the polarization plates 100 for obtaining one-side band protective film according to method shown in Fig. 3 In method, (to include the inclined of two sides band protective film after dyeing process S10-3, after bonding process S10-4, after stripping process S10-5 The front of vibration plate production process S20) or 2 or more stages in them.From being easily reduced moisture rate aspect, water Point rate reduces the stage that process S30 preferably exposes on the surface of iodine system polarizing film 5, for example before bonding process S10-4 or removes It is carried out after process S10-5.
Such as it is above-mentioned 2) in front of bonding process S10-4 implement moisture rate reduce process S30 the case where it is such, no matter It is above-mentioned 1) or 2), moisture rate reduce between the process S30 and polarization plates production process S20 of two sides band protective film have it is long Interval when, in order in the fitting of the 2nd protective film 20 moisture rate will not become because of the moisture absorption in the interval 8 weight % with On, it can also take moisture absorption that means or the moisture rate implemented in that interval again is inhibited to reduce process S30.
Inhibit means as moisture absorption, can enumerate the exposed surface in iodine system polarizing film 5 be temporarily bonded can remove it is damp proof Property film method, terminate with the film comprising the iodine system polarizing film 5 with exposing surface formation process after as far as possible Film roll is coiled into roll and inhibits the method for the intrusion from external moisture by early stage, by the film of roll as aluminum layer The method etc. that moistureproof film is further packed.The method for being wound into roll has base material film in the film of winding and the base material film is It is particularly advantageous in the case where the low film of penetrability.Alternatively, above such moisture absorption can not also especially be taken to inhibit means, and examine The rate of moisture absorption for considering iodine system polarizing film 5, design process is before moisture rate reaches 8 weight % or more by moisture absorption with can be real Apply the polarization plates production process S20 of two sides band protective film.
In addition, for example reducing between the process S30 and polarization plates production process S20 of two sides band protective film in moisture rate has When long interval, it is also contemplated that the rate of moisture absorption of iodine system polarizing film 5, reduces in process S30 in moisture rate by moisture rate It is reduced to more substantially low than 8 weight %.In this way, not reducing the polarization of process S30 and two sides band protective film in moisture rate Special means are taken between plate production process S20, can also make moisture rate when being bonded 2 protective film 20 lower than 8 weight %.
As described above, it can be used water system bonding agent in being bonded of iodine system polarizing film 5 and the 1st protective film 10, but by If in using water system bonding agent, become to iodine system polarizing film 5 supply moisture, it is advantageous to after being bonded the 1st protective film 10 extremely Carrying out moisture rate during until being bonded the 2nd protective film 20 reduces process S30.Must not in addition, the moisture rate reduces process S30 Process S30 is reduced for initial moisture rate.
From the viewpoint of heat resistance, the moisture rate of the iodine system polarizing film 5 when being bonded 2 protective film 20 is preferably less than 6 Weight %, more preferably 5 weight % or less.It is not particularly limited, such as can enumerate for reducing the specific method of moisture rate The method of dry air is blowed out, the method by adjusting the damping region for low humidity, the method by hot-air drying stove, is made The method and their combination that the heating device as infrared heater is heated.
<polarization plates of two sides band protective film>
The polarization plates of two sides band protective film of the present invention include iodine system polarizing film 5, stacking as shown in Figure 8 In the 1st protective film 10 in one face and the 2nd protective film 20 being laminated on another face.In general, the 1st protective film 10, 2 protective films 20 are bonded and (are adhesively fixed) on iodine system polarizing film 5 via the 1st adhesive layer 15, the 2nd adhesive layer 25 respectively.
In the polarization plates of two sides band protective film of the present invention, the moisture rate of iodine system polarizing film 5 is lower than 8 weight %, Preferably shorter than 6 weight %, more preferably 5 weight % or less.In addition, using saturating in the 1st protective film 10 and the 2nd protective film 20 Humidity is 150g/m2/ for 24 hours r or less, preferably 100g/m2/ r thermoplastic resin film below for 24 hours.About iodine system polarizing film 5, The specific structure of 1 protective film 10 and the 2nd protective film 20, quotes record above.
The polarization plates of two sides band protective film of the present invention can be suitable for manufacture by method described above.This hair The polarization plates of the bright two sides band protective film are laminated since the moisture rate of iodine system polarizing film 5 is lower than 8 weight % on two sides There is the protective film of low moisture permeability, even so small (such as below with a thickness of 10 μm) situation of the thickness of iodine system polarizing film 5 Under, also have both humidity resistance and heat resistance.The polarization plates of two sides band protective film can be suitable for suitable for liquid crystal display device or having Image display device as machine EL device.In the case where being suitable for liquid crystal display device, two sides band of the present invention is protected The polarization plates of cuticula can be disposed on the polarization plates of front (visual confirmation) side of liquid crystal cell, be also possible to configuration overleaf The polarization plates of (backlight) side.
The polarization plates of two sides band protective film, which can also have, is laminated in the 1st protective film 10 or the 2nd protective film for fitting to The adhesive phase on other components (such as liquid crystal cell when suitable for liquid crystal display device) on 20.Form the viscous of adhesive phase Mixture is generally comprised using (methyl) acrylic resin, phenylethylene resin series, organic silicon-type resin etc. as basic polymer, simultaneously In the adhesive group that wherein joined crosslinking agent as isocyanate compound, epoxide, nitrogen heterocycle propane compound Close object.In turn, it can also be made containing particle and show light scattering adhesive phase.The thickness of adhesive phase is usually 1~ 40 μm, preferably 3~25 μm.
In addition, the polarization plates of two sides band protective film, which can be further equipped with, is laminated in the 1st protective film 10 or the 2nd protective film 20 On other optical layers.As other optical layers, it can enumerate certain polarized light transmission and will show opposite to that Property polarised light reflection reflective polarizing film；Surface has the film with anti-dazzle function of concaveconvex shape；Surface band counnter attack Penetrate the film of function；Surface has the reflectance coating of reflection function；Have both the Transflective film of reflection function and transmission function；Visual angle Compensation film etc..
Embodiment
Further progress of the present invention is illustrated hereinafter, showing Examples and Comparative Examples, but the present invention is not by these examples The restriction of son.
<embodiment 1>
(1) prime coat formation process
By polyvinyl alcohol powder (" Z-200 ", the average degree of polymerization 1100, soap of Japanese synthetic chemical industry (strain) system Change degree is 99.5 moles of %) it is dissolved into 95 DEG C of hot water, the polyvinyl alcohol solution that preparation concentration is 3 weight %.Institute In obtained aqueous solution, relative to 6 parts by weight of polyvinyl alcohol powder with ratio mixed cross-linker (the field ridge chemistry of 5 parts by weight " SumirezResin 650 " of industrial (strain) system), obtain prime coat formation coating liquid.
Then, to including the polyacrylic base material film (fusing point: 163 DEG C, moisture permeability: 15g/m with a thickness of 90 μm2/24hr) Single side implement sided corona treatment after, use the above-mentioned prime coat formation coating of path gravure coater coating in the sided corona treatment face Liquid carries out drying in 10 minutes at 80 DEG C, the prime coat with a thickness of 0.2 μm is consequently formed.
(2) production (resin layer formation process) of stacked film
By polyvinyl alcohol powder (" PVA124 ", the average degree of polymerization 2400, saponification degree of KURARAY CO., LTD. It is dissolved into 95 DEG C of hot water for 98.0~99.0 moles of %), the polyvinyl alcohol solution that preparation concentration is 8 weight % will It uses coating liquid as the formation of polyvinyl alcohol resin.
The primer coat surface of the base material film with prime coat made in above-mentioned (1) uses the above-mentioned poly- second of die coating machine coating After alkenyl alcohol resin formation coating liquid, drying in 20 minutes is carried out at 80 DEG C, to form polyethylene on prime coat Base alcohol resin is obtained comprising base material film/prime coat/polyvinyl alcohol resin stacked film.
(3) production (stretching process) of stretched film
To the stacked film made in above-mentioned (2), implement 5.3 times at 160 DEG C using longitudinal uniaxial stretching device of floating Free end be uniaxially stretched, obtain stretched film.Polyvinyl alcohol resin after stretching with a thickness of 5.1 μm.
(4) production (dyeing process) of polarizability stacked film
By the stretched film made in above-mentioned (3) in 30 DEG C of dyeing aqueous solution (every 100 parts by weight containing iodine and potassium iodide Water includes the potassium iodide of the iodine of 0.6 parts by weight, 10 parts by weight) in dipping about 180 seconds and carry out polyvinyl alcohol resin Dyeing processing after, extra dyeing aqueous solution is fallen with 10 DEG C of pure water rinsing.
Then, in the 1st crosslinking aqueous solution of 78 DEG C comprising boric acid, (every 100 parts by weight water includes the boron of 10.4 parts by weight Acid) middle dipping 120 seconds, then, the in 70 DEG C comprising boric acid and potassium iodide the 2nd is crosslinked aqueous solution (every 100 parts by weight water packet The potassium iodide of boric acid, 12 parts by weight containing 5.7 parts by weight) in dipping 60 seconds and carry out crosslinking Treatment.Later, pure with 10 DEG C Water wash within 10 seconds.It is finally 60 seconds dry, then 60 seconds dry at 80 DEG C at 50 DEG C that (moisture rate reduces work Sequence), it thus obtains comprising base material film/iodine system polarizing film polarizability stacked film.The polarizability stacked film institute of dry finish time The moisture rate for the iodine system polarizing film having is 0.4 weight %.In addition, iodine system polarizing film with a thickness of 5.6 μm.
The moisture rate of iodine system polarizing film is inhibited to rise in order to absorb the moisture in air, in iodine system polarizing film On the face of base material film opposite side, fitting immediately has releasable and the low moistureproof film (moisture permeability of moisture permeability after the drying For 30g/m2The polyolefin-based resins film of/r for 24 hours).Iodine system polarizing film is due to by the base material film and moisture resistance of low moisture permeability as a result, Film clamping, so being able to maintain that low moisture rate.
(5) production (bonding process) of multilayer film
Moistureproof film is removed on the polarizability stacked film with moistureproof film made from above-mentioned (4), while immediately (1 Within minute) the 1st protective film is bonded in the release surface.It the use of moisture permeability is 16g/m in 1st protective film2/ r and include for 24 hours Cyclic polyolefin hydrocarbon system resin with a thickness of 23 μm of thermoplastic resin film (" ZF-14 " of Zeon Corporation).1st protects The fitting of cuticula in such a way that its single side becomes 1.0 μm or so according to the thickness after solidification using path gravure coater being applied After filling ultra-violet solidified bonding agent (" KR-75T " of (strain) ADEKA), it is fitted into above-mentioned release surface using doubling roller On, high-pressure sodium lamp is used later, from base material film side with 200mJ/cm2Accumulated light irradiation ultraviolet light make adhesive layer solidification come It carries out.
(6) production (the polarization plates production process of stripping process and two sides band protective film) of the polarization plates of two sides band protective film
By substrate film stripping from the multilayer film made in above-mentioned (5), while the 2nd protection of fitting in the release surface immediately Film obtains inclined comprising 1 protective film/adhesive layer/iodine system polarizing film/adhesive layer/the 2nd protective film two sides band protective film Vibration plate.It the use of moisture permeability is 16g/m in 2nd protective film2/ r and include cyclic polyolefin hydrocarbon system resin with a thickness of 23 μm for 24 hours Thermoplastic resin film (" ZF-14 " of Zeon Corporation).The fitting of 2nd protective film by its single side according to solidification Thickness afterwards uses the ultra-violet solidified bonding agent of path gravure coater coating ((strain) ADEKA as 1.0 μm or so of mode " KR-75T " of system) after, it is fitted in above-mentioned release surface using doubling roller, high-pressure sodium lamp is used later, from the 2nd protective film Side is with 200mJ/cm2Accumulated light irradiation ultraviolet light make adhesive layer solidify to carry out.Iodine system when being bonded 2 protective film is inclined The moisture rate of vibration piece is 0.5 weight %.
<embodiment 2>
In addition to by the condition of the last drying process of dyeing process (moisture rate reduction process) be set as at 50 DEG C 60 seconds, Then at 65 DEG C other than 60 seconds, the polarization plates of two sides band protective film are made similarly to Example 1.When being bonded 2 protective film Iodine system polarizing film moisture rate be 4.6 weight %.
<embodiment 3>
The polarization plates of two sides band protective film are made similarly to Example 2.Iodine system polarizing film when being bonded 2 protective film Moisture rate is 4.4 weight %, and the visibility amendment degree of polarization Py of the polarization plates of two sides band protective film is 99.995%, it is seen that degree is repaired Positive monomer transmissivity Ty is 40.9%.
<embodiment 4>
It the use of moisture permeability is 63g/m as the 1st protective film and the 2nd protective film2/ r and include acrylic resin for 24 hours With a thickness of 80 μm of thermoplastic resin film, using ultra-violet solidified bonding agent (" KR-15P " of (strain) ADEKA), except this with Outside, the polarization plates of two sides band protective film are made similarly to Example 2.The moisture of iodine system polarizing film when being bonded 2 protective film Rate is 4.2 weight %, and the visibility amendment degree of polarization Py of the polarization plates of two sides band protective film is 99.994%, it is seen that degree amendment is single Body transmissivity Ty is 41.4%.
<embodiment 5>
It the use of moisture permeability is 63g/m as the 1st protective film2/ r and include acrylic resin with a thickness of 80 μm for 24 hours Thermoplastic resin film as the 2nd protective film the use of moisture permeability is 16g/m2/ r and include cyclic polyolefin hydrocarbon system resin for 24 hours With a thickness of 23 μm of thermoplastic resin films (" ZF-14 " of Zeon Corporation).1st protective film uses ultraviolet curing Property bonding agent (" KR-15P " of (strain) ADEKA), the 2nd protective film is using ultra-violet solidified bonding agent (strain) ADEKA " KR-75T " makes the polarization plates of two sides band protective film similarly to Example 2 in addition to this.It is bonded iodine when 2 protective film The moisture rate for being polarizing film is 4.8 weight %, and the visibility amendment degree of polarization Py of the polarization plates of two sides band protective film is 99.994%, it is seen that degree amendment monomer transmissivity Ty is 41.4%.
<comparative example 1>
In addition to by the condition of the last drying process of dyeing process (moisture rate reduction process) be set as at 40 DEG C 60 seconds, Then at 50 DEG C other than 60 seconds, the polarization plates of two sides band protective film are made similarly to Example 1.When being bonded 2 protective film Iodine system polarizing film moisture rate be 10.7 weight %.
<comparative example 2>
In addition to the condition of the last drying process of dyeing process (moisture rate reduction process) is set as at 40 DEG C 120 seconds In addition, the polarization plates of two sides band protective film are made similarly to Example 1.The water of iodine system polarizing film when being bonded 2 protective film Dividing rate is 12.5 weight %.
<comparative example 3>
In the last drying process of dyeing process (moisture rate reduction process) afterwards without fitting moistureproof film, and at 25 DEG C It is taken care of about 2 days in the environment of 55%RH and rises to the moisture rate of iodine system polarizing film near equilibrium moisture content, be bonded the 1st later And the 2nd protective film, make the polarization plates of two sides band protective film similarly to Example 2 in addition to this.When being bonded 2 protective film The moisture rate of iodine system polarizing film is 15.3 weight %.
The moisture permeability of film in each Examples and Comparative Examples and the moisture rate of iodine system polarizing film are carried out by following method Measurement.
(1) moisture permeability
According to JIS Z 0208-1976 " the moisture permeability test method (cup type method) of water vapor proof barrier packaging material " measuring temperature 40 DEG C, the moisture permeability under relative humidity 90%.
(2) moisture rate of iodine system polarizing film
Being found out in advance by two moisture rates that the multiple iodine system polarizing film samples different about moisture rate obtain is indicated with 1 formula By the moisture rate of near infrared moisture rate meter (" IRMA1100S " of Chino Corporation) measurement and by dry heavy The moisture rate measured by near infrared moisture rate meter is used above-mentioned standard by the standard curve of the relationship for the moisture rate that amount method obtains Curve is converted into the moisture rate using dry weight method, as the moisture rate of iodine system polarizing film.In addition, about drying is utilized The moisture rate of gravimetric method, the weight of the sample before setting drying is W0, if when the sample is dry with the condition of 105 DEG C, 1 hour Weight when being W1, defined with following formula:
Moisture rate (weight %)=100 × (W0-W1)/W0
(humidity resistance of the polarization plates of two sides band protective film and the evaluation of heat resistance)
(1) evaluation of humidity resistance
Polarization plates for the two sides band protective film made in embodiment 1 and 2, comparative example 1~3, use extinction photometer After the humidity resistance test that (" V7100 " of Japan's light splitting (strain) system) measurement stands 500 hours in the environment of 65 DEG C of 90%RH Visibility amendment degree of polarization Py and test before Py, by the two poor Δ Py (before test Py- test after Py) evaluation it is resistance to Humid.The smaller then humidity resistance of the absolute value of Δ Py is higher.It shows the result in table 1.In the measurement of Py, according to the 2nd The mode of protective film side irradiation incident light disposes the polarization plate sample of two sides band protective film.In addition, humidity resistance test after can Degree of opinion correct degree of polarization Py humidity resistance test after, in 23 DEG C of 55%RH in the environment of stand about 12 hours after be measured.
Humidity resistance test (and following heat-resistance tests) before Py be about each Examples and Comparative Examples 99.995%.In addition, for the visibility amendment monomer transmissivity Ty measured using the extinction photometer, each embodiment and ratio Compared with being 41.6% in example.
(2) evaluation of heat resistance
Polarization plates for the two sides band protective film made in embodiment 1 and 2, comparative example 1~3, by carrying out at 85 DEG C The heat-resistance test for standing 500 hours under dry environment, in the same manner as the evaluation of above-mentioned humidity resistance by Δ Py (before test Py after Py- test) evaluation heat resistance.The smaller then heat resistance of the absolute value of Δ Py is higher.It shows the result in table 1.
(3) evaluation of the humidity resistance under the conditions of promoting
Polarization plates for the two sides band protective film made in embodiment 3~5, by being commented with above-mentioned (1) humidity resistance The same method of valence carries out the humidity resistance for standing 48 hours in the environment of 80 DEG C, 90%RH test.Show the result in table 2 In.
(4) evaluation of the heat resistance under the conditions of promoting
Polarization plates for the two sides band protective film made in embodiment 3~5 pass through the evaluation with above-mentioned (2) heat resistance Same method carries out the heat-resistance test for standing 48 hours under 105 DEG C, dry environment.It shows the result in table 2.
In addition, confirming by visual observation light leakage (red change) for the polarization plates of the two sides band protective film after heat-resistance test Degree.Specifically, cutting out the sample of 2 10cm × 20cm from the polarization plates of the two sides band protective film after heat-resistance test These samples are fitted to the two sides of glass plate by piece using adhesive.At this point, the 2nd protective film side is made to become glass plate side, and And make positional relationship of the coupons as cross Nicols for being configured at two sides.Then, it is pasted in darkroom from a polarization plates side Nearly backlight carries out the visual valuation of red change according to following evaluation criteria.It shows the result in table 1 and table 2.
A: keeping pitch-black state, can not identify by visual observation it is red become,
B: apparent red change is seen.
[table 1]
[table 2]
Symbol description
5 iodine system polarizing films, 6 polyvinyl alcohol resins, the polyvinyl alcohol resin of 6 ' drawns, 10 the 1st are protected Cuticula, 15 the 1st adhesive layers, 20 the 2nd protective films, 25 the 2nd adhesive layers, 30 base material films, the base material film of 30 ' drawns, 100 lists Polarization plates of the face with protective film, 200 stacked films, 300 stretched films, 400 polarizability stacked films, 500 multilayer films, 600 two sides bands are protected The polarization plates of cuticula.

Claims (8)

1. a kind of manufacturing method of the polarization plates of two sides band protective film comprising following process:
Substrate film stripping is removed from the multilayer film successively comprising base material film, iodine system polarizing film and the 1st protective film, obtains single side The process of polarization plates with protective film；With
The outer surface of iodine system polarizing film in the polarization plates of the one-side band protective film is bonded the 2nd protective film, obtains two sides band The process of the polarization plates of protective film,
It is 150g/m that 1st protective film and the 2nd protective film, which are moisture permeability,2/ r thermoplastic resin film below for 24 hours,
The moisture rate of iodine system polarizing film when being bonded 2 protective film is 4.8 weight % or less.
2. the manufacturing method according to claim 1, wherein
2nd protective film is fitted in the outer surface of iodine system polarizing film using active energy ray-curable bonding agent.
3. manufacturing method according to claim 1 or 2, wherein
Iodine system polarizing film with a thickness of 10 μm or less.
4. a kind of manufacturing method of the polarization plates of two sides band protective film comprising following process:
In the polarization of the one-side band protective film comprising iodine system polarizing film and the 1st protective film of the single side for being laminated in the iodine system polarizing film Iodine system polarizing film outer surface in plate, the 2nd protective film of fitting, the process for obtaining the polarization plates of two sides band protective film,
It is 150g/m that 1st protective film and the 2nd protective film, which are moisture permeability,2/ r thermoplastic resin film below for 24 hours,
The moisture rate of iodine system polarizing film when being bonded 2 protective film is 4.8 weight % or less.
5. manufacturing method according to claim 4, wherein
2nd protective film is fitted in the outer surface of iodine system polarizing film using active energy ray-curable bonding agent.
6. manufacturing method according to claim 4 or 5, wherein
Iodine system polarizing film with a thickness of 10 μm or less.
7. a kind of polarization plates of two sides band protective film, it includes iodine system polarizing film and the protective film for being laminated in its two sides,
It is 150g/m that the protective film for being laminated in two sides, which is moisture permeability,2/ r thermoplastic resin film below for 24 hours,
The moisture rate of iodine system polarizing film is 4.8 weight % or less.
8. the polarization plates of two sides band protective film according to claim 7, wherein
Iodine system polarizing film with a thickness of 10 μm or less.
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