CN106662690A

CN106662690A - Method for producing polarizing plate having protective films on both surfaces thereof

Info

Publication number: CN106662690A
Application number: CN201580035235.7A
Authority: CN
Inventors: 九内雄朗; 九内雄一朗
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2014-07-04
Filing date: 2015-06-16
Publication date: 2017-05-10
Anticipated expiration: 2035-06-16
Also published as: JPWO2016002504A1; CN106662690B; KR102441217B1; WO2016002504A1; KR20170023863A; TW201606360A; JP6894494B2; TWI652512B; JP2017004016A; JP2020046690A

Abstract

A method for producing a polarizing plate having protective films on both surfaces thereof, which comprises: a step for separating and removing a base film from a multilayer film that comprises the base film, an iodine-based polarizer and a first protective film in this order; and a step for bonding a second protective film on the outer surface of the iodine-based polarizer. The first and second protective films are composed of a thermoplastic resin film having a water vapor permeability of 150 g/m2/24 hr or less. The moisture percentage of the iodine-based polarizer when the second protective film is bonded thereto is less than 8% by weight. Also provided is a polarizing plate having protective films on both surfaces thereof, which is obtained by laminating thermoplastic resin films having a water vapor permeability of 150 g/m2/24 hr or less on both surfaces of an iodine-based polarizer that has a moisture percentage of less than 8% by weight.

Description

The manufacture method of the polarization plates of two sides band diaphragm

Technical field

The present invention relates to be fitted with the manufacture of the polarization plates of the two sides band diaphragm of diaphragm on the two sides of iodine system polarizer Method, more specifically, is related to successively fit the low diaphragm of moisture permeability to manufacture two sides band on the two sides of iodine system polarizer The method of the polarization plates of diaphragm.

Background technology

Polarization plates are widely used in the display devices such as liquid crystal indicator, and smart mobile phone is especially widely used in recent years Such various mobile devices.Used as polarization plates, the generally one or two sides in polarizer has been fitted guarantor using bonding agent The polarization plates of the composition of cuticula.

Its own humidity resistance of polarizer is low, and polarization characteristic is easily deteriorated under hygrothermal environment.In the past, in protection polarizer Diaphragm used in tri acetyl cellulose membrane, but tri acetyl cellulose membrane due to moisture permeability it is high, so using it for diaphragm Polarization plates particularly using iodine system polarizer as polarizer in the case of there is a problem of that humidity resistance is still insufficient.

Therefore, in order to improve the humidity resistance of polarization plates, it is proposed that replace tri acetyl cellulose membrane and will such as norborneol The low diaphragm of moisture permeability as alkene resin film fits in (for example, Japanese Unexamined Patent Publication 2004-245925 on iodine system polarizer The paragraph [0005] of publication (patent document 1)).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2004-245925 publications

The content of the invention

Invent problem to be solved

If the low diaphragm of moisture permeability is fitted in into the two sides of iodine system polarizer, due to the intrusion from outside moisture Reduce, it is possible to improving the humidity resistance of polarization plates.However, it is on the other hand, understood by the research of the present inventor：Two If face has used the polarization plates of the conventional two sides band diaphragm of the low diaphragm of such moisture permeability to implement and general moisture-proof The heat-resistance test being exposed under higher temperature environment is compared in hot test, then the light leak produced under cross Nicols (fades And polarization plates seem rubescent phenomenon from the light of polarization plates leakage red area.Also referred to as red change.) or polarization characteristic Reduce.The thickness of iodine system polarizer is less, and the bad problem of the heat resistance is more notable.

It is therefore an object of the present invention to provide fitted the low protection of penetrability on the two sides of iodine system polarizer for manufacture The polarization plates of film and have concurrently humidity resistance and heat resistance two sides band diaphragm polarization plates method and have humidity resistance concurrently With the polarization plates of the two sides band diaphragm of heat resistance.

For solving the scheme of problem

The present invention provides the inclined of the manufacture method of the polarization plates of two sides band diaphragm shown below and two sides band diaphragm Vibration plate.

[1] a kind of manufacture method of the polarization plates of two sides band diaphragm, it includes following operation：

Base material film is peeled off from the multilayer film for including base material film, iodine system polarizer and the 1st diaphragm is successively removed and is obtained To the operation of the polarization plates of one-side band diaphragm；With

The outer surface of the iodine system polarizer in the polarization plates of above-mentioned one-side band diaphragm is fitted the 2nd diaphragm and obtains two The operation of polarization plates of the face with diaphragm,

It is 150g/m that above-mentioned 1st diaphragm and above-mentioned 2nd diaphragm are moisture permeability²The thermoplastic resin film of/below 24hr,

Fit above-mentioned 2 diaphragm when above-mentioned iodine system polarizer moisture rate be less than 8 weight %.

[2] manufacture method according to [1], wherein, the above-mentioned 2nd is protected using active energy ray-curable bonding agent Cuticula fits in the outer surface of above-mentioned iodine system polarizer.

[3] manufacture method according to [1] or [2], wherein, the thickness of above-mentioned iodine system polarizer is less than 10 μm.

[4] a kind of manufacture method of the polarization plates of two sides band diaphragm, it includes：Including iodine system polarizer and be laminated in Iodine system polarizer outer surface the 2nd diaphragm of laminating in the polarization plates of the one-side band diaphragm of the 1st diaphragm of its one side, obtains The operation of the polarization plates of two sides band diaphragm,

[5] manufacture method according to [4], wherein, the above-mentioned 2nd is protected using active energy ray-curable bonding agent Cuticula fits in the outer surface of above-mentioned iodine system polarizer.

[6] manufacture method according to [4] or [5], wherein, the thickness of above-mentioned iodine system polarizer is less than 10 μm.

[7] a kind of polarization plates of two sides band diaphragm, it includes iodine system polarizer and is laminated in the diaphragm on its two sides,

The diaphragm for being laminated in two sides is moisture permeability for 150g/m²The thermoplastic resin film of/below 24hr,

The moisture rate of above-mentioned iodine system polarizer is less than 8 weight %.

[8] polarization plates of the two sides band diaphragm according to [7], wherein, the thickness of above-mentioned iodine system polarizer is 10 μm Below.

Invention effect

In accordance with the invention it is possible to provide be fitted with the low diaphragm of penetrability on the two sides of iodine system polarizer for manufacture Polarization plates and have concurrently humidity resistance and heat resistance two sides band diaphragm polarization plates method and the two of iodine system polarizer Face is fitted with the polarization plates of the low diaphragm of penetrability and has the polarization of the two sides band diaphragm of humidity resistance and heat resistance concurrently Plate.

Description of the drawings

Fig. 1 is a preferred example of the manufacture method of the polarization plates for representing two sides band diaphragm of the present invention Flow chart.

Fig. 2 is the simple sectional view of an example of the Rotating fields of the polarization plates for representing one-side band diaphragm.

Fig. 3 is the flow chart of a preferred example of the polarization plates preparatory process for representing one-side band diaphragm.

Fig. 4 is the simple section of an example of the Rotating fields for representing the stacked film obtained by resin bed formation process Figure.

Fig. 5 is the simple sectional view of an example of the Rotating fields for representing the stretched film obtained by stretching process.

Fig. 6 is the simple section of an example of the Rotating fields for representing the polarizability stacked film obtained by dyeing process Figure.

Fig. 7 is the simple sectional view of an example of the Rotating fields for representing the multilayer film obtained by bonding process.

Fig. 8 is the simple section of an example of the Rotating fields of the polarization plates for representing two sides band diaphragm of the present invention Figure.

Specific embodiment

The manufacture method of the polarization plates of two sides band diaphragm of the present invention as shown in Figure 1, can be included Following operations.

(1) polarization plates of the one-side band diaphragm comprising iodine system polarizer and the 1st diaphragm for being laminated in its one side are prepared Operation S10 (hereinafter also referred to as " the polarization plates preparatory process S10 of one-side band diaphragm ") and

(2) iodine system polarizer outer surface the 2nd diaphragm of laminating in the polarization plates of one-side band diaphragm, obtains two sides band Operation S20 (hereinafter also referred to as " the polarization plates production process S20 of two sides band diaphragm ") of the polarization plates of diaphragm.

As mentioned above in the present invention, the 1st diaphragm and the 2nd diaphragm are successively fitted relative to iodine system polarizer. Now, in order to the two sides band diaphragm obtained by improving polarization plates humidity resistance, as fitting in the one of iodine system polarizer 1st diaphragm in individual face and the 2nd diaphragm in another face is fitted in, the use of moisture permeability is 150g/m²/ below 24hr's is low The thermoplastic resin film of humidity.

Additionally, the heat resistance of the polarization plates for the two sides band diaphragm obtained by improving, will paste on iodine system polarizer The moisture rate of iodine system polarizer when closing 2 diaphragm is set at less than 8 weight %.In the present invention, in order to improve humidity resistance, Polarization plates are made in the low diaphragm of the two sides laminating moisture permeability of iodine system polarizer, but,

If a) the low diaphragm of moisture permeability is applied to into two sides, the moisture in iodine system polarizer is difficult to diffuse to outside, Moisture is lodged in iodine system polarizer,

The reduction of red change, polarization characteristic b) in heat-resistance test be because remaining in the iodine system polarizer in moisture draw Rise,

From it is above-mentioned situations such as, as mentioned above the moisture rate of iodine system polarizer during 2 diaphragm of management laminating is that have Effect.The moisture rate of iodine system polarizer is determined according to the method described in the item of embodiment.

The moisture rate of iodine system polarizer can be by the operation of the polarization plates of manufacture two sides band diaphragm and in iodine system Either phase on polarizer before the 2nd diaphragm of laminating arranges (3) implements moisture rate to the film comprising iodine system polarizer reduces Operation S30 (hereinafter also referred to as " moisture rate reduce operation S30 ") of process is reaching (with reference to Fig. 1).

Hereinafter, each operation is illustrated with reference to Fig. 2～Fig. 8.

(1) the polarization plates preparatory process S10 of one-side band diaphragm

This operation is to prepare such as Fig. 2 of (preparation) comprising iodine system polarizer 5 and the 1st diaphragm 10 for being laminated in its one side Shown in such one-side band diaphragm polarization plates 100 operation.As shown in Figure 2, the 1st diaphragm 10 is generally situated between Fitted (be adhesively fixed) in the one side of iodine system polarizer 5 by the 1st bond layer 15.

(iodine system polarizer)

Iodine system polarizer 5 is to make polarizer obtained from the iodine gas absorption quantity as dichroism pigment, specifically, can be with It is to make iodine polarizer obtained from gas absorption quantity in the polyvinyl alcohol resin (or film) of Jing uniaxial tensions.Iodine system polarizes The thickness of piece 5 for example can be less than 30 μm and then less than 20 μm, especially in mobile device use, from two sides band diaphragm Polarization plates slimming from the viewpoint of, preferably less than 10 μm, more preferably less than 8 μm.The thickness of iodine system polarizer 5 leads to It is often more than 2 μm.

If the thickness of iodine system polarizer 5 diminishes, because the concentration of iodine becomes higher, with the diaphragm for being laminated in two sides The concentration of iodo-complexes that exists of near interface also uprise, so being easily subject to the moisture from outside intrusion to be affected.Therefore, The thickness of iodine system polarizer 5 is less, and humidity resistance easily becomes lower.If additionally, the thickness of iodine system polarizer 5 diminishes and iodine Concentration becomes higher, then become easily to be subject to remain in affecting for the moisture in iodine system polarizer, heat resistance also easy step-down.Picture So, the thickness of iodine system polarizer 5 is less, then humidity resistance and the easier step-down of heat resistance, thus the present invention is polarized in iodine system It is especially advantageous in the case that the thickness of piece 5 is little.

As the polyvinyl alcohol system resin for constituting polyvinyl alcohol resin, it is possible to use by polyvinyl acetate system Resin obtained from resin saponification.As polyvinyl acetate system resin, except the homopolymers of vinylacetate is poly-vinegar acid second Beyond alkene ester, can also exemplify vinylacetate with can be with the copolymer of the other monomers of its copolymerization.As can be with acetic acid The other monomers of vinyl acetate copolymerization, for example can include unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class, (methyl) acrylic amide with ammonium etc..

" (methyl) acrylic acid " is referred to selected from least one of acrylic acid and methacrylic acid in this specification.It is so-called When " (methyl) acryloyl group " etc. similarly.

Film obtained from above-mentioned polyvinyl alcohol system resin is filmed constitutes iodine system polarizer 5.By polyvinyl alcohol It is that the method for resin masking is not particularly limited, can be filmed by known method, but it is little from thickness is readily obtained The aspect that the treatability of the iodine system polarizer 5 of the film in iodine system polarizer 5, operation is also excellent is set out, 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 scope of 80.0～100.0 moles of %, but preferably 90.0～ The scope of 99.5 moles of %, the more preferably scope of 94.0～99.0 moles of %.If saponification degree is less than 80.0 moles of %, gained The resistance to water of the polarization plates of the two sides band diaphragm for arriving and humidity resistance are reduced.When poly- more than 99.5 moles of % using saponification degree During vinyl alcohol system resin, sometimes the dyeing kinetics of iodine are slack-off, and productivity ratio is reduced, while sufficient polarization property cannot be had Iodine system polarizer 5.

So-called saponification degree is the poly-vinegar acid second of the raw material that polyvinyl alcohol system resin is denoted as with unit ratio (mole %) Acetoxy group (the acetoxyl group included in alkene ester system resin：-OCOCH₃) be changing into by saponifying process hydroxyl ratio value, with Following formula is defining：

Saponification degree (mole %)=100 × (number of hydroxyl) ÷ (number of the number+acetoxy group of hydroxyl)

Saponification degree can be obtained according to JIS K 6726-1994.Saponification degree is higher, represents that the ratio of hydroxyl is higher, because This, represents that the ratio of the acetoxy group for hindering crystallization is lower.

Polyvinyl alcohol system resin can also be the modified polyvinyl alcohol that a part is modified.For example, can include by The alkene such as polyvinyl alcohol system resin ethene, 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%.Be performed for more than 30 moles of % it is modified in the case of, existing becomes to be difficult to adsorb Iodine, it is difficult to obtain the tendency of the iodine system polarizer 5 with sufficient polarization property.

The average degree of polymerization of polyvinyl alcohol system resin is preferably 100～10000, more preferably 1500～8000, enters one Step is preferably 2000～5000.The average degree of polymerization of polyvinyl alcohol system resin can also be asked according to JIS K 6726-1994 Go out.

(the 1st diaphragm)

1st diaphragm 10 is comprising (preferably optically transparent) thermoplastic resin with translucency and moisture permeability is 150g/m²The film of/below 24hr.Moisture permeability also includes the moisture permeability of the 2nd diaphragm described later, is according to JIS Z 0208- Moisture-inhibiting under 40 DEG C of temperature, relative humidity 90% that 1976 " the moisture permeability test methods (cup type method) of water vapor proof barrier packaging material " are determined Degree.Moisture permeability is preferably 100g/m²/ below 24hr.

It is 150g/m as the moisture permeability for making the 1st diaphragm 10²The method of/below 24hr, can include and constitute film The thickness or the low stop of setting penetrability on film of the low resin of penetrability or increase film used in thermoplastic resin The method of layer.

Then it is not particularly limited as long as constituting the thermoplastic resin of the 1st diaphragm 10 and can reach above-mentioned moisture permeability, from saturating Set out in terms of moist thickness low, that the 1st diaphragm 10 can be reduced, preferably use chain polyolefin-based resins (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 diaphragm 10 can also be the diaphragm for having optical function as phase retardation film, brightness raising film concurrently.For example By the way that the film comprising above-mentioned thermoplastic resin is stretched (be stretched uniaxially or biaxially) or on the film liquid is formed Crystal layer etc., can make the phase retardation film for imparting arbitrary phase difference value.

As chain polyolefin-based resins, except the homopolymers of chain olefin as polyvinyl resin, acrylic resin In addition, the copolymer comprising chain olefin of more than two kinds can also be included.

Cyclic polyolefin hydrocarbon system resin is the general name of the resin being polymerized as polymerized unit using cyclic olefin.If including The specific example of cyclic polyolefin hydrocarbon system resin, then be open loop (common) polymers, the addition polymer of cyclic olefin, the ring of cyclic olefin Shape alkene uses unsaturated with the copolymer of chain olefin as ethene, propylene (representativeness is random copolymer) and by them Graft polymers and their hydride etc. obtained from carboxylic acid or derivatives thereof is modified.Wherein, it is preferred to use using drop ice Norbornene resin of the norborneol alkene monomer such as piece alkene or polycyclic norborneol alkene monomer as cyclic olefin.

Polyester based resin is the resin with ester bond, the polycondensation generally comprising polybasic carboxylic acid or derivatives thereof with polyalcohol The resin of thing.As polybasic carboxylic acid or derivatives thereof, it is possible to use dicarboxylic acids or derivatives thereof, for example, can include terephthaldehyde Acid, M-phthalic acid, dimethyl terephthalate (DMT), naphthalene dicarboxylic acids dimethyl ester etc..As polyalcohol, it is possible to use dihydroxylic alcohols, example Ethylene glycol, propane diols, butanediol, neopentyl glycol, cyclohexanedimethanol can such as be included.

The specific example of polyester based resin includes polyethylene terephthalate, polybutylene terephthalate (PBT), gathers (ethylene naphthalate), PBN, PTT, 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 Can also be polymer backbone is modified obtained from be referred to as resin, copolymerization polycarbonate of modified polycarbonate etc..

(methyl) acrylic resin is the tree using the compound with (methyl) acryloyl group as main composition monomer Fat.The specific example of (methyl) acrylic resin for example includes poly- (methyl) acrylic acid 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 resins Deng)；Copolymer (such as methyl methacrylate-the methyl-prop of methyl methacrylate and the compound with alicyclic alkyl Olefin(e) acid hexamethylene ester copolymer, methyl methacrylate-(methyl) acrylic acid norborneol ester copolymer etc.).Preferably use poly- (first Base) methyl acrylate is such with poly- (methyl) acrylic acid C_1-6Arrcostab as the polymer of main component, more preferably use with Methyl methacrylate of the methyl methacrylate as main component (50～100 weight %, preferably 70～100 weight %) It is resin.

The surface with the opposition side of iodine system polarizer 5 in the 1st diaphragm 10, can also form hard conating, antiglare layer, anti- Surface-treated layer (coating layer) as reflecting layer, antistatic layer, stain-proofing layer.The method of surface-treated layer is formed without especially limit It is fixed, it is possible to use known method.

1st diaphragm 10 can contain one kind or two or more lubricant, plasticizer, dispersant, heat stabilizer, ultraviolet Additive as absorbent, infrared absorbent, antistatic additive, antioxidant.

From from the viewpoint of the slimming of the polarization plates of two sides band diaphragm, the thickness of the 1st diaphragm 10 is preferably 90 μm Hereinafter, more preferably less than 50 μm, more preferably less than 30 μm.From from the viewpoint of intensity and treatability, the 1st diaphragm 10 thickness is usually more than 5 μm.

(the 1st bond layer)

1st bond layer 15 is for the layer of the 1st diaphragm 10 that is adhesively fixed on a face of iodine system polarizer 5.Make Can be containing by as ultraviolet, visible ray, electron ray, X-ray to form the bonding agent of the 1st bond layer 15 The active energy ray-curable bonding agent of the irradiation of active energy beam and the curability compound that solidifies (consolidate by preferred ultraviolet Change property bonding agent), make bonding agent composition as polyvinyl alcohol system resin be dissolved or dispersed in the water system bonding in water Agent.

Above-mentioned curability compound can be the curability compound of cationically polymerizable or free-radical polymerised solidification Property compound.Used as the curability compound of cationically polymerizable, (intramolecular has 1 can for example to include epoxy based compound The compound of the individual or epoxy radicals of more than 2), (intramolecular has the oxa- of 1 or more than 2 to oxetanes based compound The compound of cyclobutane ring) or combinations thereof.As free-radical polymerised curability compound, for example, can include (first Base) acrylic compounds (intramolecular have 1 or more than 2 (methyl) acryloxy compound), with freedom Other vinyl compounds of the double bond of base polymerism or combinations thereof.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 generally also comprising use 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 diaphragm can be pre-prepd polarization plates, or by arbitrary method The polarization plates of manufacture.As manufacture method, method below can be included.

I) single-sided lamination the 1st in the iodine system polarizer 5 comprising monomer (independent) film manufactured by known method is protected The method of cuticula 10 and

Ii) such manufacture method comprising following operations shown in Fig. 3.

By making its drying after the coating liquid that at least one face application of base material film contains polyvinyl alcohol system resin and Formed polyvinyl alcohol resin and obtain stacked film resin bed formation process S10-1,

By stacked film stretched and obtained stretched film stretching process S10-2,

The polyvinyl alcohol resin of stretched film is dyeed with iodine and iodine system polarizer is formed, polarizability layer is obtained The dyeing process S10-3 of folded film,

On the iodine system polarizer of polarizability stacked film fit the 1st diaphragm 10 and obtain the bonding process S10- of multilayer film 4 and

Base material film is peeled off from multilayer film is removed and is obtained the stripping process S10- of the polarization plates 100 of one-side band diaphragm 5。

(resin bed formation process S10-1)

With reference to Fig. 4, this operation is to form polyvinyl alcohol resin 6 at least one face of base material film 30 and obtain The operation 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 polarizer 5.Polyvinyl alcohol resin 6 can be by by the coating liquid application containing polyvinyl alcohol system resin To base material film 30 one or two sides and make its drying and formed.Polyvinyl alcohol resin is formed by such application Method be favourable at the aspect of the iodine system polarizer 5 for being readily obtained film.

Base material film 30 can include thermoplastic resin, wherein, preferably comprise the transparency, mechanical strength, heat endurance, stretching The excellent thermoplastic resins such as property.The specific example of such thermoplastic resin for example includes chain polyolefin-based resins, ring-type Polyolefin-based resins as polyolefin-based resins (norbornene resin etc.)；Polyester based resin；(methyl) acrylic acid series tree Fat；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 series resin；Polyimides system resins；And their mixture, copolymer.

Base material film 30 can be the individual layer knot being made up of 1 resin bed comprising one kind or two or more thermoplastic resin Structure, or multiple sandwich constructions being laminated will be carried out comprising the resin bed of one kind or two or more thermoplastic resin. Base material film 30 preferably is contained in stretching process S10-2 described later can be to be suitable for carrying out polyvinyl alcohol resin 6 The such resin of draft temperature stretching of stretching.

Base material film 30 can contain additive.The specific example of additive includes ultra-violet absorber, antioxidant, lubrication Agent, plasticizer, releasing agent, coloring preventing agent, fire retardant, nucleator, antistatic additive, pigment and colouring agent.

From aspects such as intensity, treatability, the thickness of base material film 30 is usually 1～500 μm, preferably 1～300 μm, More preferably 5～200 μm, more preferably 5～150 μm.

The coating liquid being coated on base material film 30 is 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 As needed can also be containing additives such as plasticizer, surfactants.

Above-mentioned coating liquid is applied the method being attached on base material film 30 can be from wire rod rubbing method；Reversely coating, intaglio plate are applied 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；Suitably select in the methods such as spray-on process.

The baking temperature of coating layer (the polyvinyl alcohol resin before being dried) and drying time wrap according in coating liquid The species of the solvent for containing and set.Baking temperature is, for example, 50～200 DEG C, preferably 60～150 DEG C.When solvent includes water, Baking temperature is preferably more than 80 DEG C.

Polyvinyl alcohol resin 6 can only be formed at a face of base material film 30, it is also possible to be formed at two sides.If shape Into the curling of the film that in two sides, then can suppress be produced in the manufacture of polarizability stacked film 400 (with reference to Fig. 6), while Due to 2 polarization plates can be obtained by 1 polarizability stacked film 400, so the aspect in production efficiency is also favourable.

The thickness of the polyvinyl alcohol resin 6 in stacked film 200 is preferably 3～30 μm, more preferably 5～20 μm. If the polyvinyl alcohol resin 6 with the thickness in the range of this, then via stretching process S10-2 described later and dyer Sequence S10-3, can obtain iodine dyeability is good and polarization property is excellent and fully thin (such as thickness is less than 10 μm ) iodine system polarizer 5.

Before the application of coating liquid, in order to improve the adaptation of base material film 30 and polyvinyl alcohol resin 6, also may be used Implemented at sided corona treatment, plasma with the surface of the base material film 30 of the side at least forming polyvinyl alcohol resin 6 Reason, flame (flame) process etc..The reasons why this external cause is same, it is also possible to form polyethylene via prime coat etc. on base material film 30 Base alcohol resin 6.

Prime coat can make its drying and shape by the way that prime coat formation coating liquid is coated on behind the surface of base material film 30 Into.The coating liquid is included and plays to a certain degree strong closing force to both base material film 30 and polyvinyl alcohol resin 6 Composition, generally comprises the resinous principle and solvent for giving such closing force.As resinous principle, the transparency, heat are preferably used The excellent hot castable resin such as stability, draftability, for example, can include (methyl) acrylic resin, polyvinyl alcohol system tree Fat etc..Wherein, the polyvinyl alcohol system resin of the closing force for giving good is preferably used.More preferably polyvinyl alcohol resin. Used as solvent, being usually used can dissolve the general organic solvent or water solvent of above-mentioned resinous principle, preferably by being made with water Coating liquid for solvent forms prime coat.

In order to improve the intensity of prime coat, it is also possible to add crosslinking agent in prime coat formation coating liquid.Crosslinking agent Specific example includes epoxy, isocyanates system, dialdehyde system, metal system (such as slaine, metal oxide, metal hydroxide Thing, organo-metallic compound), the crosslinking agent of macromolecular.Using polyvinyl alcohol system resin as the resin for forming prime coat During composition, suitably using Polyamide Epoxy, methylolated melamine resin, dialdehyde system crosslinking agent, metal-chelating materialization Compound system crosslinking agent etc..

The thickness of prime coat is preferably 0.05～1 μm or so, more preferably 0.1～0.4 μm.If becoming thinner than 0.05 μm, Then base material film 30 is little with the effect that the closing force of polyvinyl alcohol resin 6 is improved, if becoming than 1 μ m-thick, to two sides band The slimming of the polarization plates of diaphragm is unfavorable.

Method prime coat formation coating liquid being coated on base material film 30 can be with polyvinyl alcohol resin shape Into coating liquid it is same.The baking temperature of the coating layer comprising prime coat formation coating liquid is, for example, 50～200 DEG C, preferably For 60～150 DEG C.When solvent includes water, baking temperature is preferably more than 80 DEG C.

(stretching process S10-2)

With reference to Fig. 5, this operation is to be stretched stacked film 200, obtain drawn comprising base material film 30 ' and polyethylene The operation of the stretched film 300 of base alcohol resin 6 '.Stretch processing is usually uniaxial tension.

The stretching ratio of stacked film 200 can suitably be selected according to desired polarization characteristic, but preferably with respect to layer Folded film 200 it is former a length of more than 5 times and less than 17 times, more preferably more than 5 times and less than 8 times.If stretching ratio be 5 times with Under, then because polyvinyl alcohol resin 6 ' is without being fully orientated, so sometimes the degree of polarization of iodine system polarizer 5 does not have Fully uprise.On the other hand, if stretching ratio is more than 17 times, become easily to produce the fracture of film in stretching, while stretching The lower thickness of film 300 is to more than necessity, it is possible to which processability and treatability below in operation is reduced.

Stretch processing is not limited to one section of stretching, it is also possible to carried out with multistage.In this case, can be in dyeing Whole multistage stretch processings are continuously carried out before operation S10-3, it is also possible 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 with multistage like this, preferably Full section according to stretch processing amounts to the mode of the stretching ratio more than 5 times and carries out stretch processing.

Stretch processing can also be except being the longitudinal stretching stretched along film length direction (film carrying direction) The cross directional stretch stretched along film width or oblique extension etc..As longitudinal stretching mode, can include to enter using roller Stretching, compression stretching between the roller of row stretching, using the stretching etc. of chuck (clip), as cross directional stretch mode, drawing can be included Width machine method etc..Stretch processing can adopt any one in moistening type drawing process, dry-stretch process.

Draft temperature is set as that polyvinyl alcohol resin 6 and the overall degree stretching of base material film 30 show stream 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 Scope, more preferably -30 DEG C to+5 DEG C of scope, more preferably -25 DEG C to+0 DEG C of scope.When base material film 30 is comprising more During individual resin bed, above-mentioned phase transition temperature refers to the highest phase transition temperature in the phase transition temperature shown by the plurality of resin bed.

If making draft temperature less than -30 DEG C of phase transition temperature, presence be difficult to reach the high magnification stretching more than 5 times or The mobility of person's base material film 30 is too low and stretch processing becomes difficult tendency.If draft temperature exceedes+30 DEG C of phase transition temperature, The mobility that then there is base material film 30 is excessive and stretch the tendency for becoming difficult.From the high stretching times being more easily achieved more than 5 times Set out in terms of rate, draft temperature is more preferably more than 120 DEG C 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 blast and adjusting The method heated in stretch zones as the heating furnace of the whole temperature for regulation.)；In situation about being stretched using roller The lower method by roller conducting self-heating；Heater heating (is arranged infrared heater, halogen heater, panel heater etc. In the upper and lower and method that heated with radiant heat of stacked film 200) etc..Between roller in stretching mode, from the equal of draft temperature From the viewpoint of even property, preferably region heating.

Before stretching process S10-2, it is also possible to the pre-heat treatment operation that setting is preheated to stacked film 200.As Pre-heating mean, it is possible to use the method same with the heating means in stretch processing.Preheating temperature is preferably-the 50 of draft temperature DEG C to ± 0 DEG C of scope, the more preferably scope of-the 40 of draft temperature DEG C Dao -10 DEG C.

Additionally, after the stretch processing in stretching process S10-2, it is also possible to arrange thermal finalization treatment process.Thermal finalization Process be the end of stretched film 300 with the state that holds by clip is maintained into tense situation and meanwhile with crystallized temperature with On the process that is heat-treated.Processed by the thermal finalization, promote the crystallization of polyvinyl alcohol resin 6 '.At thermal finalization The temperature of reason is preferably the scope of -0 DEG C～-80 DEG C of draft temperature, the more preferably model of-the 0 of draft temperature DEG C～-50 DEG C Enclose.

(dyeing process S10-3)

With reference to Fig. 6, this operation is so that iodine is dyeed to inhale it polyvinyl alcohol resin 6 ' of stretched film 300 Attached orientation, makes the operation of iodine system polarizer 5.Obtain being laminated with iodine system in the one or two sides of base material film 30 ' via this operation The polarizability stacked film 400 of polarizer 5.

Dyeing process can be carried out by the dipping stretched film 300 in the solution containing iodine (staining solution).As dye Color solution, it is possible to use the solution being dissolved into iodine in solvent.As solvent, water is generally used, it is also possible to further add Plus there is the organic solvent of compatibility with water.The concentration of the iodine in staining solution is preferably 0.01～10 weight %, more preferably 0.02～7 weight %.

From staining efficiency aspect can be improved, iodide are further added preferably in staining solution.As iodine Compound, for example, can include KI, lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, cupric iodide, barium iodide, iodate Calcium, stannic iodide, titanium iodide etc..The concentration of the iodide in staining solution is preferably 0.01～20 weight %.In iodide, preferably Addition KI.When KI is added, the ratio of iodine and KI is preferably 1: 5～1 with weight ratio meter: 100, more preferably 1: 6～1: 80.The temperature of staining solution is preferably 10～60 DEG C, more preferably 20～40 DEG C.

Alternatively, it is also possible to dyeing process S10-3 be carried out before stretching process S10-2 or while carry out these operations, But in order that the iodine being adsorbed in polyvinyl alcohol resin is orientated well, preferably at least one is being implemented to stacked film 200 Determine to implement dyeing process S10-3 after the stretch processing of degree.

Dyeing process S10-3 can include the crosslinking Treatment operation that enforcement is processed after dyeing.Crosslinking Treatment can by Impregnate dyed film in the solution (crosslinker solution) that crosslinking agent is dissolved in solvent to carry out.As crosslinking agent, example Boron compound, glyoxal, glutaraldehyde etc. as boric acid, borax can be included.Crosslinking agent can only use a kind, it is also possible to Be two kinds or more.As the solvent of crosslinker solution, it is possible to use water, but it is also possible to further there is compatibility comprising with water Organic solvent.The concentration of the 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, can make in the face of iodine system polarizer 5 Polarization property more homogenize.The specific example of iodide is as described above.The concentration of the 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 by the way that crosslinking agent be coupled in staining solution, process with dyeing is carried out simultaneously.This Outward, it is also possible to using the different crosslinker solution of more than two kinds of composition, carry out the process impregnated in crosslinker solution of more than 2 times.

After dyeing process S10-3 and before bonding process S10-4 described later, washing procedure and back tender are preferably carried out Sequence.Washing procedure generally comprises water washing operation.Water washing can be by the pure water as ion exchange water, distilled water Middle dip dyeing process after or film after crosslinking Treatment carrying out.Water washing temperature is usually 3～50 DEG C, and preferably 4～20 ℃.Washing procedure can also be the combination of water washing operation and the washing procedure using iodide solution.As in washing procedure The drying process for carrying out afterwards, can adopt the arbitrary appropriate methods such as natural drying, air-supply drying, heat drying.For example In the case of heat drying, baking temperature is usually 20～95 DEG C.

(bonding process S10-4)

With reference to Fig. 7, this operation is by the iodine system polarizer 5 of polarizability stacked film 400, i.e. iodine system polarizer 5 Via the 1st bond layer 15 the 1st diaphragm 10 is fitted with the face of the opposition side of base material film 30 ' and obtain the operation of multilayer film 500. Bonding agent with regard to forming the 1st bond layer 15, as mentioned above.

In addition, when polarizability stacked film 400 has iodine system polarizer 5 on the two sides of base material film 30 ', generally on two sides Fit respectively on iodine system polarizer 5 the 1st diaphragm 10.In this case, these the 1st diaphragms 10 can be the guarantor of identical type Cuticula, or different types of diaphragm.

When 1 diaphragm 10 is fitted using active energy ray-curable bonding agent, via becoming the 1st bond layer After 15 active energy ray-curable bonding agent is laminated to the 1st diaphragm 10 on iodine system polarizer 5, irradiation ultraviolet radiation, can See that active energy beam as light, electron ray, X-ray solidifies bond layer.Its middle-ultraviolet lamp is suitable, used as this When light source, it is possible to use low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp, black light lamp, microwave-excitation Mercury lamp, metal halide lamp etc..During using water system bonding agent, as long as the 1st diaphragm 10 is laminated to into iodine via water system bonding agent Be on polarizer 5 after be thermally dried.

On iodine system polarizer 5 during 1 diaphragm 10 of laminating, for the 1st diaphragm 10 and/or the patch of iodine system polarizer 5 Conjunction face, in order to improve the cementability with iodine system polarizer 5, can carry out corona treatment, sided corona treatment, at ultraviolet irradiation Reason, flame (flame) process, the such surface treatment (easy bonding process) of saponification process, wherein, preferably carry out at plasma Reason, sided corona treatment or saponification process.

(stripping process S10-5)

This operation is that base material film 30 ' is peeled off into the operation of removing from multilayer film 500.Via the operation, obtain same with Fig. 2 The polarization plates 100 of the one-side band diaphragm of sample.There is iodine system polarizer on the two sides of base material film 30 ' in polarizability stacked film 400 5 and in the case of being fitted with the 1st diaphragm 10 on the two iodine system polarizers 5, by stripping process S50, by 1 partially Shaking property stacked film 400 obtains the polarization plates 100 of 2 one-side band diaphragms.

By base material film 30 ' peel off remove method be not particularly limited, can by with the common polarization with adhesive The same method of the stripping process of the barrier film (stripping film) carried out in plate is peeling off.Base material film 30 ' can be in bonding process S10-4 Directly peel off immediately afterwards, it is also possible to after bonding process S10-4, once coil into roll, in the operation after on one side Unreel while being peeled off.

(2) the polarization plates production process S20 of two sides band diaphragm

Using this operation, by the outer surface laminating of the iodine system polarizer 5 in the polarization plates 100 of one-side band diaphragm the 2 diaphragms 20, obtain the polarization plates of two sides band diaphragm.One example of the Rotating fields of the polarization plates of two sides band diaphragm is shown In Fig. 8.As the polarization plates 600 of the two sides band diaphragm shown in Fig. 8, the 2nd diaphragm 20 is generally via the 2nd bonding agent Layer 25 and fit (be adhesively fixed) on iodine system polarizer 5.The outer surface of so-called iodine system polarizer 5 is referred in iodine system polarizer 5 The face with the opposition side of the 1st diaphragm 10, peeling off the operation for removing making one-side band diaphragm via by base material film 30 ' In the case of polarization plates 100, the surface of the iodine system polarizer 5 for removing and exposing by the stripping of base material film 30 ' is referred to.

2nd diaphragm 20 is also similarly comprising (preferably optically transparent) heat with translucency with the 1st diaphragm 10 Plastic resin and moisture permeability are 150g/m²The film of/below 24hr.Can also be simultaneous as phase retardation film, brightness raising film The diaphragm of tool optical function.The surface-treated layer that can have with regard to the 2nd diaphragm 20 and thickness, the material of film etc., quote To the record above the description of the 1st diaphragm 10.1st diaphragm 10 and the 2nd diaphragm 20 can be comprising mutually the same species Resin diaphragm, or the diaphragm comprising different types of resin.

Forming the bonding agent of the 2nd bond layer 25 can be similarly active energy ray-curable with the 1st bond layer 15 Active energy ray-curable bonding agent as bonding agent or water system bonding agent, but preferably ultra-violet solidified bonding agent. If using water system bonding agent, due to becoming paired iodine system polarizer 5 moisture is supplied, thus fit sometimes 2 diaphragm 20 when The moisture rate of iodine system polarizer 5 will not become lower than 8 weight %.The bonding agent for forming the 2nd bond layer 25 can be with formation the 1st There is the bonding agent of bond layer 15 identical to constitute, it is possible to have different compositions.

(3) moisture rate reduces operation S30

In order that the moisture rate of the iodine system polarizer 5 during 2 diaphragm 20 of laminating is less than 8 weight %, it is of the present invention The manufacture method of the polarization plates of two sides band diaphragm is included in the polarization plates of manufacture two sides band diaphragm as explained above Operation in two sides band diaphragm polarization plates production process S20 before any more than 1 stage implement moisture rate Reduce operation S30.It is that the film comprising iodine system polarizer 5 is implemented to make the moisture rate of iodine system polarizer 5 that moisture rate reduces operation S30 The operation of the process of reduction.

It is as described below if including the example for implementing the opportunity that moisture rate reduces operation S30.

1) obtain one-side band in the diaphragm 10 of single-sided lamination the 1st of the iodine system polarizer 5 comprising monomer (independent) film to protect After the polarization plates 100 of cuticula fit the 2nd diaphragm 20 method in, be the 1st diaphragm 10 laminating before, laminating after (including two The front of polarization plates production process S20 of the face with diaphragm) or both.Wherein, if due to the state of monomer (independent) film Moisture rate is reduced, then iodine system polarizer 5 becomes easily cracking or ruptures, it is advantageous to after the laminating for the 1st diaphragm 10.

2) the 2nd diaphragm 20 of laminating after the polarization plates 100 that one-side band diaphragm is obtained according to the method shown in Fig. 3 It is (inclined comprising two sides band diaphragm after dyeing process S10-3, after bonding process S10-4, after stripping process S10-5 in method The front of vibration plate production process S20) or more than 2 in them stage.From being easily reduced moisture rate aspect, water Point rate reduces the stage that operation S30 preferably exposes on the surface of iodine system polarizer 5, for example before bonding process S10-4 or peel off Carry out after operation S10-5.

Such as it is above-mentioned 2) in implemented moisture rate before bonding process S10-4 and reduce the situation of operation S30 like that, no matter It is above-mentioned 1) or 2), reduce having between operation S30 and the polarization plates production process S20 of two sides band diaphragm in moisture rate long Interval when, in order in the laminating of the 2nd diaphragm 20 moisture rate will not become 8 weight % because of the moisture absorption in the interval with On, it is also possible to taking moisture absorption to suppress means or implementing moisture rate again in that interval reduces operation S30.

Suppress means as moisture absorption, can include the exposed surface in iodine system polarizer 5 fit temporarily can peel off it is damp proof Property film method, terminate with comprising with exposing surface iodine system polarizer 5 film formation operation after as far as possible Early stage by film roll be coiled into roll and suppress the method for the intrusion from outside moisture, by the film of roll with as aluminium lamination press mold Method that moistureproof film is further packed etc..It is wound into that the method for roll has base material film in the film of winding and the base material film is It is particularly advantageous in the case of the low film of penetrability.Or, it is also possible to especially do not take moisture absorption as the above to suppress means, and examine Consider the rate of moisture absorption of iodine system polarizer 5, design process is with can be real before moisture rate reaches more than 8 weight % by moisture absorption Apply the polarization plates production process S20 of two sides band diaphragm.

Additionally, for example having between moisture rate reduction operation S30 and the polarization plates production process S20 of two sides band diaphragm During long interval, it is also possible to consider the rate of moisture absorption of iodine system polarizer 5, by moisture rate in moisture rate reduces operation S30 It is reduced to more substantially low than 8 weight %.With it, not reducing the polarization of operation S30 and two sides band diaphragm in moisture rate Special means are taken between plate production process S20, it is also possible to make moisture rate during 2 diaphragm 20 of laminating be less than 8 weight %.

As described above, water system bonding agent can be used in the fitting of iodine system polarizer 5 and the 1st diaphragm 10, but by If in the supply moisture of paired iodine system polarizer 5 using water system bonding agent, is become, it is advantageous to after the 1st diaphragm 10 of fitting extremely Moisture rate is carried out during fitting till the 2nd diaphragm 20 reduces operation S30.In addition, moisture rate reduction operation S30 must not To be that initial moisture rate reduces operation S30.

From from the viewpoint of heat resistance, the moisture rate of the iodine system polarizer 5 during 2 diaphragm 20 of laminating is preferably less than 6 Below weight %, more preferably 5 weight %.Specific method for reducing moisture rate is not particularly limited, for example, can enumerate Go out to blow the method for dry air, the method in damping region by being adjusted to low humidity, by the method for hot-air drying stove, make The method heated with heater as infrared heater and combinations thereof.

The polarization plates of two sides band diaphragm of the present invention are as shown in Figure 8 comprising iodine system polarizer 5, stacking The 1st diaphragm 10 in one face and the 2nd diaphragm 20 being laminated on another face.Generally, the 1st diaphragm 10, 2 diaphragms 20 are fitted (be adhesively fixed) on iodine system polarizer 5 respectively via the 1st bond layer 15, the 2nd bond layer 25.

In the polarization plates of two sides band diaphragm of the present invention, the moisture rate of iodine system polarizer 5 is less than 8 weight %, Below preferably shorter than 6 weight %, more preferably 5 weight %.Additionally, using saturating in the 1st diaphragm 10 and the 2nd diaphragm 20 Humidity is 150g/m²/ below 24hr, preferably 100g/m²The thermoplastic resin film of/below 24hr.With regard to iodine system polarizer 5, The concrete structure of 1 diaphragm 10 and the 2nd diaphragm 20, quotes record above.

The polarization plates of two sides band diaphragm of the present invention can suitably be manufactured by method described above.This The polarization plates of bright described two sides band diaphragm are less than 8 weight % due to the moisture rate of iodine system polarizer 5, and in two sides stacking There is the diaphragm of low moisture permeability, even so little (such as thickness is less than 10 μm) situation of the thickness of iodine system polarizer 5 Under, also have humidity resistance and heat resistance concurrently.The polarization plates of two sides band diaphragm can suitably be applied to liquid crystal indicator or have Image display device as machine EL devices.In the case of suitable for liquid crystal indicator, two sides band of the present invention is protected The polarization plates of cuticula can be disposed on the polarization plates of front (visually confirming) side of liquid crystal cell, it is also possible to be disposed on the back side The polarization plates of (backlight) side.

The polarization plates of two sides band diaphragm can also possess and be laminated in the 1st diaphragm 10 or the 2nd diaphragm for fitting to The adhesive phase on other components (such as suitable for liquid crystal cell during liquid crystal indicator) on 20.Form the viscous of adhesive phase Mixture generally comprise based on (methyl) acrylic resin, phenylethylene resin series, silicon-type resin etc. polymer and The adhesive group of crosslinking agent as isocyanate compound, epoxide, nitrogen heterocycle propane compound is added wherein Compound.Further, it is also possible to make containing particulate and show light scattering adhesive phase.The thickness of adhesive phase is usually 1～ 40 μm, preferably 3～25 μm.

Additionally, the polarization plates of two sides band diaphragm can be further equipped with being laminated in the 1st diaphragm 10 or the 2nd diaphragm 20 On other optical layers.As other optical layers, can include certain polarized light transmission and will show opposite to that Property polarised light reflection reflective polarizing film；Surface has the film of the anti-dazzle function of the band of concaveconvex shape；Surface band counnter attack Penetrate the film of function；Surface has the reflectance coating of reflection function；Have the Transflective film of reflection function and transmission function concurrently；Visual angle Compensation film etc..

Embodiment

Hereinafter, illustrate that embodiment and comparative example are further specifically described to the present invention, but the present invention does not receive these examples The restriction of son.

(1) prime coat formation process

By polyvinyl alcohol powder, (" Z-200 " of Japanese synthetic chemical industry (strain) system, average degree of polymerization are 1100, soap Change degree is 99.5 moles of %) 95 DEG C of hot water is dissolved into, prepare the polyvinyl alcohol solution that concentration is 3 weight %.Institute In the aqueous solution for obtaining, relative to the weight portion of polyvinyl alcohol powder 6 with ratio mixed cross-linker (the field ridge chemistry of 5 weight portions " SumirezResin 650 " of industrial (strain) system), obtain prime coat formation coating liquid.

Then, to comprising the base material film (fusing point that polyacrylic thickness is 90 μm：163 DEG C, moisture permeability：15g/m²/24hr) One side implement sided corona treatment after, use the above-mentioned prime coat formation application of path gravure coater application in the sided corona treatment face Liquid, carries out drying in 10 minutes at 80 DEG C, is consequently formed the prime coat that thickness is 0.2 μm.

(2) making (resin bed formation process) of stacked film

By polyvinyl alcohol powder, (" PVA124 " of KURARAY CO., LTD., average degree of polymerization are 2400, saponification degree For 98.0～99.0 moles of %) 95 DEG C of hot water is dissolved into, the polyvinyl alcohol solution that concentration is 8 weight % is prepared, will It is used as polyvinyl alcohol resin formation coating liquid.

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 application After alkenyl alcohol resin formation coating liquid, drying in 20 minutes is carried out at 80 DEG C, so as to form polyethylene on prime coat Base alcohol resin, obtains the stacked film comprising base material film/prime coat/polyvinyl alcohol resin.

(3) making (stretching process) of stretched film

To the stacked film made in above-mentioned (2), using the longitudinal uniaxial stretching device for floating 5.3 times are implemented at 160 DEG C Free end uniaxial tension, obtain stretched film.The thickness of the polyvinyl alcohol resin after stretching is 5.1 μm.

(4) making (dyeing process) of polarizability stacked film

By the dyeing aqueous solution (every 100 weight portion of the stretched film made in above-mentioned (3) at containing iodine and KI 30 DEG C Water comprising 0.6 weight portion iodine, the KI of 10 weight portions) in dipping about 180 seconds and carry out polyvinyl alcohol resin Dyeing process after, fall the unnecessary dyeing aqueous solution with 10 DEG C of pure water rinsing.

Then, in the 1st crosslinking aqueous solution (boron of every 100 weight portion water comprising 10.4 weight portions for wrapping borated 78 DEG C Acid) in dipping 120 seconds, then, in 70 DEG C comprising boric acid and KI of the 2nd crosslinking aqueous solution (every 100 weight portion water bag The KI of the boric acid containing 5.7 weight portions, 12 weight portions) in dipping 60 seconds and carry out crosslinking Treatment.Afterwards, it is pure with 10 DEG C Water carries out 10 seconds washing.It is last that 60 seconds, then (moisture rate reduction work dry 60 seconds at 80 DEG C are dried at 50 DEG C Sequence), thus obtain the polarizability stacked film comprising base material film/iodine system polarizer.It is dried the polarizability stacked film institute of finish time The moisture rate of the iodine system polarizer having is 0.4 weight %.Additionally, the thickness of iodine system polarizer is 5.6 μm.

The moisture rate for suppressing iodine system polarizer in order to the moisture in absorption air rises, in iodine system polarizer On the face of base material film opposition side, after the drying laminating immediately is with the low moistureproof film (moisture permeability of releasable and moisture permeability For 30g/m²The polyolefin-based resins film of/24hr).Thus, iodine system polarizer is due to by the base material film and moisture resistance of low moisture permeability Film is clamped, it is possible to maintaining low moisture rate.

(5) making (bonding process) of multilayer film

Moistureproof film is peeled off on the polarizability stacked film with moistureproof film made from above-mentioned (4), while immediately (1 Within minute) the 1st diaphragm of fitting in the release surface.The use of moisture permeability is 16g/m in 1st diaphragm²/ 24hr and include The thickness of cyclic polyolefin hydrocarbon system resin is 23 μm of thermoplastic resin film (" ZF-14 " of Zeon Corporation).1st protects The laminating of cuticula is applied by way of becoming 1.0 μm or so according to the thickness after solidification in its one side using path gravure coater After filling ultra-violet solidified bonding agent (" KR-75T " of (strain) ADEKA), it is fitted to into above-mentioned release surface using doubling roller On, afterwards using high-pressure sodium lamp, from base material film side with 200mJ/cm²Accumulated light irradiation ultraviolet radiation make bond layer solidification come Carry out.

(6) making (the polarization plates production process of stripping process and two sides band diaphragm) of the polarization plates of two sides band diaphragm

Base material film is peeled off on the multilayer film made from above-mentioned (5), while immediately laminating the 2nd is protected in the release surface Film, obtains the inclined of the two sides band diaphragm comprising 1 diaphragm/bond layer/iodine system polarizer/bond layer/the 2nd diaphragm Vibration plate.The use of moisture permeability is 16g/m in 2nd diaphragm²/ the 24hr and thickness comprising cyclic polyolefin hydrocarbon system resin is 23 μm Thermoplastic resin film (" ZF-14 " of Zeon Corporation).The laminating of the 2nd diaphragm by its one side according to solidification Thickness afterwards becomes 1.0 μm or so of mode and uses path gravure coater application ultra-violet solidified bonding agent ((strain) ADEKA " KR-75T " of system) after, it is fitted in above-mentioned release surface using doubling roller, afterwards using high-pressure sodium lamp, from the 2nd diaphragm Side is with 200mJ/cm²Accumulated light irradiation ultraviolet radiation make bond layer solidification carrying out.Fit 2 diaphragm when iodine system it is inclined Shake piece moisture rate be 0.5 weight %.

Except 60 seconds at the condition of the last dried process of dyeing process (moisture rate reduction operation) is set as into 50 DEG C, Then at 65 DEG C 60 seconds in addition, the polarization plates of two sides band diaphragm are made similarly to Example 1.Fit 2 diaphragm when Iodine system polarizer moisture rate be 4.6 weight %.

The polarization plates of two sides band diaphragm are made similarly to Example 2.Fit 2 diaphragm when iodine system polarizer Moisture rate is 4.4 weight %, and the visibility amendment degree of polarization Py of the polarization plates of two sides band diaphragm is 99.995%, it is seen that degree is repaiied Positive monomer transmissivity Ty is 40.9%.

The use of moisture permeability is 63g/m as the 1st diaphragm and the 2nd diaphragm²/ 24hr and comprising acrylic resin Thickness is 80 μm of thermoplastic resin film, using ultra-violet solidified bonding agent (" KR-15P " of (strain) ADEKA), except this with Outward, the polarization plates of two sides band diaphragm are made similarly to Example 2.Fit 2 diaphragm when iodine system polarizer moisture Rate is 4.2 weight %, and the visibility amendment degree of polarization Py of the polarization plates of two sides band diaphragm is 99.994%, it is seen that degree amendment is single Body transmissivity Ty is 41.4%.

The use of moisture permeability is 63g/m as the 1st diaphragm²/ 24hr and the thickness comprising acrylic resin are 80 μm Thermoplastic resin film, the use of moisture permeability is 16g/m as the 2nd diaphragm²/ 24hr and comprising cyclic polyolefin hydrocarbon system resin Thickness is 23 μm of thermoplastic resin film (" ZF-14 " of Zeon Corporation).1st diaphragm uses ultraviolet curing Property bonding agent (" KR-15P " of (strain) ADEKA), the 2nd diaphragm is using ultra-violet solidified bonding agent (strain) ADEKA " KR-75T ", makes similarly to Example 2 in addition the polarization plates of two sides band diaphragm.Fit 2 diaphragm when iodine The moisture rate for being polarizer is 4.8 weight %, and the visibility amendment degree of polarization Py of the polarization plates of two sides band diaphragm is 99.994%, it is seen that degree amendment monomer transmissivity Ty is 41.4%.

Except 60 seconds at the condition of the last dried process of dyeing process (moisture rate reduction operation) is set as into 40 DEG C, Then at 50 DEG C 60 seconds in addition, the polarization plates of two sides band diaphragm are made similarly to Example 1.Fit 2 diaphragm when Iodine system polarizer moisture rate be 10.7 weight %.

Except 120 seconds at the condition of the last dried process of dyeing process (moisture rate reduction operation) is set as into 40 DEG C In addition, the polarization plates of two sides band diaphragm are made similarly to Example 1.Fit 2 diaphragm when iodine system polarizer water Rate is divided to be 12.5 weight %.

Do not fit after the last dried process of dyeing process (moisture rate reduction operation) moistureproof film, and at 25 DEG C Take care of about 2 days in the environment of 55%RH and the moisture rate of iodine system polarizer is risen near equilibrium moisture content, afterwards laminating the 1st And the 2nd diaphragm, make the polarization plates of two sides band diaphragm similarly to Example 2 in addition.Fit 2 diaphragm when The moisture rate of iodine system polarizer is 15.3 weight %.

The moisture permeability of the film in each embodiment and comparative example and the moisture rate of iodine system polarizer are carried out by method below Determine.

(1) moisture permeability

According to JIS Z 0208-1976 " the moisture permeability test method (cup type method) of water vapor proof barrier packaging material " temperature of the measurement 40 DEG C, the moisture permeability under relative humidity 90%.

(2) moisture rate of iodine system polarizer

Obtained in advance by two moisture rates obtained with regard to the different multiple iodine system polarizer samples of moisture rate and represented with 1 formula The moisture rate determined by near infrared moisture rate meter (" IRMA1100S " of Chino Corporation) is heavy with by being dried The calibration curve of the relation of the moisture rate that amount method is obtained, by the moisture rate determined by near infrared moisture rate meter above-mentioned standard is used Curve is converted into using the moisture rate of dry weight method, as the moisture rate of iodine system polarizer.In addition, with regard to utilizing drying The moisture rate of gravimetric method, when the weight for setting the sample before being dried is as W0, if the sample is dried with the condition of 105 DEG C, 1 hour Weight be W1 when, defined with following formula：

Moisture rate (weight %)=100 × (W0-W1)/W0

(humidity resistance of the polarization plates of two sides band diaphragm and the evaluation of heat resistance)

(1) evaluation of humidity resistance

For the polarization plates of the two sides band diaphragm made in embodiment 1 and 2, comparative example 1～3, using extinction photometer After (" V7100 " of Japanese light splitting (strain) system) determines the humidity resistance test for standing 500 hours in the environment of 65 DEG C of 90%RH Visibility amendment degree of polarization Py and test before Py, evaluate resistance to by both poor Δ Py (Py- before test test after Py) Humid.The more little then humidity resistance of the absolute value of Δ Py is higher.In showing the result in table 1.In the measure of Py, according to the 2nd The mode of diaphragm side irradiation incident light disposes the polarization plates sample of two sides band diaphragm.In addition, humidity resistance test after can Degree of opinion amendment degree of polarization Py is measured after humidity resistance test, after standing about 12 hours in the environment of 23 DEG C of 55%RH.

Py before humidity resistance test (and following heat-resistance tests) is with regard to each embodiment and comparative example 99.995%.Additionally, for visibility amendment monomer transmissivity Ty determined using the extinction photometer, each embodiment and ratio Compared with being 41.6% in example.

(2) evaluation of heat resistance

For the polarization plates of the two sides band diaphragm made in embodiment 1 and 2, comparative example 1～3, by carrying out at 85 DEG C The heat-resistance test of 500 hours is stood under dry environment, in the same manner as the evaluation with above-mentioned humidity resistance by Δ Py (before test Py after Py- tests) evaluate heat resistance.The more little then heat resistance of the absolute value of Δ Py is higher.In showing the result in table 1.

(3) evaluation of the humidity resistance under the conditions of promoting

For the polarization plates of the two sides band diaphragm made in embodiment 3～5, by commenting with above-mentioned (1) humidity resistance The same method of valency carries out the humidity resistance test for standing 48 hours in the environment of 80 DEG C, 90%RH.Show the result in table 2 In.

(4) evaluation of the heat resistance under the conditions of promoting

For the polarization plates of the two sides band diaphragm made in embodiment 3～5, by 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.In showing the result in table 2.

Additionally, for the polarization plates of the two sides band diaphragm after heat-resistance test, light leak (red change) is confirmed by visual observation Degree.Specifically, the sample of 2 10cm × 20cm is cut out in the polarization plates of the two sides band diaphragm from after heat-resistance test These samples are fitted to the two sides of glass plate using adhesive by piece.Now, the 2nd diaphragm side is made to become glass plate side, and And, make the coupons for being configured at two sides become the position relationship of cross Nicols.Then, from a polarization plates side patch in darkroom Nearly backlight, according to following metewands the visual valuation of red change is carried out.In showing the result in table 1 and table 2.

A：Keep pitch-black state, by visual observation None- identified red change,

B：See obvious red change.

[table 1]

[table 2]

Symbol description

5 iodine system polarizers, 6 polyvinyl alcohol resins, the polyvinyl alcohol resin of 6 ' drawns, 10 the 1st are protected Cuticula, 15 the 1st bond layers, 20 the 2nd diaphragms, 25 the 2nd bond layers, 30 base material films, the base material film of 30 ' drawns, 100 lists Polarization plates of the face with diaphragm, 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

1. a kind of manufacture method of the polarization plates of two sides band diaphragm, it includes following operation：

Base material film is peeled off from the multilayer film for including base material film, iodine system polarizer and the 1st diaphragm is successively removed, obtain one side The operation of the polarization plates with diaphragm；With

Outer surface the 2nd diaphragm of laminating of the iodine system polarizer in the polarization plates of the one-side band diaphragm, obtains two sides band The operation of the polarization plates of diaphragm,

1st diaphragm and the 2nd diaphragm are the thermoplastic resin film that moisture permeability is below 150g/m2/24hr,

Fit 2 diaphragm when iodine system polarizer moisture rate be less than 8 weight %.

2. manufacture method according to claim 1, wherein,

The 2nd diaphragm is fitted in the outer surface of iodine system polarizer using active energy ray-curable bonding agent.

3. manufacture method according to claim 1 and 2, wherein,

The thickness of iodine system polarizer is less than 10 μm.

4. a kind of manufacture method of the polarization plates of two sides band diaphragm, it includes following operation：

In the polarization comprising iodine system polarizer and the one-side band diaphragm of the 1st diaphragm of the one side for being laminated in the iodine system polarizer Iodine system polarizer outer surface in plate, the 2nd diaphragm of fitting, obtains the operation of the polarization plates of two sides band diaphragm,

It is 150g/m that 1st diaphragm and the 2nd diaphragm are moisture permeability²The thermoplastic resin film of/below 24hr,

5. manufacture method according to claim 4, wherein,

6. the manufacture method according to claim 4 or 5, wherein,

The thickness of iodine system polarizer is less than 10 μm.

7. a kind of polarization plates of two sides band diaphragm, it includes iodine system polarizer and is laminated in the diaphragm on its two sides,

The diaphragm for being laminated in two sides is the thermoplastic resin film that moisture permeability is below 150g/m2/24hr,

The moisture rate of iodine system polarizer is less than 8 weight %.

8. polarization plates of two sides band diaphragm according to claim 7, wherein,

The thickness of iodine system polarizer is less than 10 μm.