CN109870757A - The manufacturing method of polarization plates monolithic body with protective film - Google Patents

Abstract

The present invention provides a kind of manufacturing method of polarization plates monolithic body with protective film comprising the protective film in the region comprising meeting following formula is fitted in the one side of polarization plates and obtains the process for having the process of the polarization plates of protective film and cutting out the monolithic body of the polarization plates with protective film from the region.Formula: TD elasticity modulus-MD elasticity modulus >=300MPa.In formula, so-called TD elasticity modulus is the tensile modulus of elasticity on the direction TD under 23 DEG C of temperature, relative humidity 55%RH, and so-called MD elasticity modulus is the tensile modulus of elasticity on the direction MD under 23 DEG C of temperature, relative humidity 55%RH.

Description

The manufacturing method of polarization plates monolithic body with protective film

Technical field

The manufacturing method for the polarization plates monolithic body with protective film that the present invention relates to a kind of.In addition, the invention further relates to bands There are the polarization plates of polarization plates monolithic body and strip with protective film of protective film.

Background technique

In recent years, the shifting of the image display devices, such as smart phone etc such as liquid crystal display device, organic EL display device Dynamic terminal hastily promotes large screen, very thinization from design, portability aspect.In order to limited thickness It realizes prolonged driving, high brightness, slim lightweight is also required for used polarization plates.

As polarization plates, the protection that will be formed by triacetyl cellulose (TAC) using bonding agent was generally used in the past Film fits in polarization plates obtained by the polarizing film formed as polyvinyl alcohol resin.But in recent years, from filming, durability, The viewpoints such as cost, productivity consider that the protective film formed by the resin other than TAC is also gradually obtained using (such as Japanese Unexamined Patent Publication 2004-245925 bulletin (patent document 1)).

Summary of the invention

Problem to be solved by the invention

Along with the requirement of the slimming of polarization plates, the slimming of polarizing film and protective film is being promoted.Can by from The monolithic body of polarization plates obtained from cutting out in the thin polarization plates without stiffness, particularly the polarization plates from strip is easy to Generation bends to bowed deformation.In this specification, also the deformation referred to as " is crimped ".

Polarization plates are generally by as being fitted with, for protecting the protective film that can be removed on its surface, (also referred to as surface is protected Cuticula.) the polarization plates with protective film circulate on the market.Even if in the polarization plates with protective film, if thinning, Similarly have the tendency that being easy to generate curling when monolithic body is made.

In the curling of the polarization plates monolithic body with protective film, have two kinds of " just crimp " and " inverse curling ".By polarizing In the polarization plates monolithic body with protective film that the laminated body of plate and protective film is constituted, so-called " just crimp " makes polarization plates side The curling of face protrusion, so-called " inverse curling " is the curling for making the face protrusion of protective film side.

Once generating inverse curling, in the polarization plates side for the polarization plates monolithic body that will have protective film, folder is pasted across adhesive phase When together in image-displaying members such as liquid crystal cells, organic EL elements, makes it easy to cause to generate fitting mistake or bubble is mixed into bonding The not good situation at the interface of oxidant layer and image-displaying member.

Polarization plates with protective film are another across adhesive phase, adhesive layer stacking sometimes through pressing from both sides again in its polarization plates side 1 or more outer optical functional layer etc. and the multilayer structure making for being made into more layers.In this case, to inclined with protective film Being attached on the direction for making the inverse curling of above-mentioned multilayer structure making for more layers on vibration plate plays a role.

Thus, when considering that above-mentioned multilayer structure making is made, it is desirable to which the polarization plates monolithic body with protective film has enough Big just crimp.This is because being fitted in image-displaying member if above-mentioned multilayer structure making has inverse curling When, it is prone to above-mentioned not good situation.

On the other hand, it is mounted directly on image above-mentioned multilayer structure making not being made in the polarization plates with protective film and shows In the case where showing element, its big just crimp will not interfere the fitting to image-displaying member.

The object of the present invention is to provide one kind can manufacture the polarization plates with protective film with biggish just crimp The method of monolithic body.

Another object of the present invention is to provide a kind of polarization plates with protective film that can have biggish just crimp Monolithic body.

Another object of the present invention is to provide the polarization plates that a kind of strip has protective film, and can provide has The polarization plates monolithic body with protective film of biggish just crimp.

The present invention provides the manufacturing method of the polarization plates monolithic body with protective film as shown below, with the inclined of protective film Vibration plate monolithic body and strip have the polarization plates of protective film.

[1] a kind of manufacturing method of the polarization plates monolithic body with protective film, which includes: will be comprising under satisfaction The protective film in the region of formula (I) fit in the one side of polarization plates and obtain with protective film polarization plates process and

The process of the monolithic body of the polarization plates with protective film is cut out from the region.

TD elasticity modulus-MD elasticity modulus >=300MPa (I)

[in formula, so-called TD elasticity modulus is the tensile elasticity on the direction TD under 23 DEG C of temperature, relative humidity 55%RH Modulus, so-called MD elasticity modulus are the tensiles modulus of elasticity on the direction MD under 23 DEG C of temperature, relative humidity 55%RH.]

[2] according to the manufacturing method recorded in [1], wherein sandwich the polarization plates and the protective film between a pair of rolls And it is bonded.

[3] according to the manufacturing method recorded in [2], wherein the polarization plates are strip, and the protective film is strip Shape.

[4] according to the manufacturing method recorded in [3], wherein the fitting forward pull of the polarization plates be 200N/m hereinafter,

The fitting forward pull of the protective film is 300N/m or more.

[5] manufacturing method recorded according to any one of [1]~[4], wherein so that the absorption axiss of the polarization plates and institute The parallel mode in the direction MD for stating protective film is bonded.

[6] manufacturing method recorded according to any one of [1]~[5], wherein the polarization plates with a thickness of 70 μm with Under.

[7] a kind of polarization plates monolithic body with protective film, it includes polarization plates and the protective film for being laminated in its one side,

The protective film meets lower formula (II).

First the-the second elasticity modulus of elasticity modulus >=300MPa (II)

[in formula, so-called first elasticity modulus is the suction with the polarization plates under 23 DEG C of temperature, relative humidity 55%RH The tensile modulus of elasticity on the orthogonal direction of axis is received, so-called second elasticity modulus is under 23 DEG C of temperature, relative humidity 55%RH Tensile modulus of elasticity on the direction parallel with the absorption axiss of the polarization plates.]

[8] according to the polarization plates monolithic body with protective film recorded in [7], wherein keep the face of the polarization plates side convex The amount of curl on the direction parallel with the absorption axiss of the polarization plates risen is 40mm or more.

[9] according to the polarization plates monolithic body with protective film recorded in [7] or [8], wherein the thickness of the polarization plates It is 70 μm or less.

[10] a kind of strip has the polarization plates of protective film, it includes the polarization plates of strip and is laminated in its one side The protective film of strip,

The protective film includes the region for meeting lower formula (III).

First the-the second elasticity modulus of elasticity modulus >=300MPa (III)

[in formula, so-called first elasticity modulus is inclined with the strip under 23 DEG C of temperature, relative humidity 55%RH Tensile modulus of elasticity on the orthogonal direction of the absorption axiss of vibration plate, so-called second elasticity modulus are 23 DEG C of temperature, relative humidity The tensile modulus of elasticity on the direction parallel with the absorption axiss of the polarization plates of the strip under 55%RH.]

[11] polarization plates of protective film are had according to the strip recorded in [10], wherein the region spreads the guarantor The entire width direction of cuticula.

According to the present invention it is possible to which the polarization plates list with protective film with biggish just crimp can be manufactured by providing one kind The method of sheet body.

According to the present invention it is possible to provide a kind of polarization plates monolithic with protective film that can have biggish just crimp Body.

According to the present invention it is possible to provide a kind of polarization plates of the strip with protective film, it is capable of providing with biggish The polarization plates monolithic body with protective film of just crimp.

Detailed description of the invention

Fig. 1 is the flow chart for indicating the manufacturing method of the polarization plates monolithic body with protective film.

Fig. 2 is the schematic sectional view of an example for indicating that the layer of polarization plates is constituted.

Fig. 3 is another schematic sectional view for indicating the layer of polarization plates and constituting.

Fig. 4 is the side view for indicating an example for the bonding process S101 for being bonded polarization plates with protective film.

Fig. 5 is the schematic sectional view of an example for indicating that the layer of the polarization plates monolithic body with protective film is constituted.

Fig. 6 is the schematic diagram for illustrating the measuring point of production method and MD amount of curl of the test sample of MD amount of curl.

Fig. 7 is the width position and elastic modulus difference for indicating the protective film 1~3 used respectively in experimental example 1~3 The chart of relationship.

Fig. 8 is to indicate to cut out the polarization with protective film from polarization plates of the strip of experimental example 1~3 with protective film The width position of plate monolithic body, the figure with the relationship of the MD amount of curl of the polarization plates monolithic body with protective film cut out Table.

Specific embodiment

The manufacturing method > of polarization plates monolithic body of the < with protective film

Referring to Fig.1, the manufacturing method of the polarization plates monolithic body with protective film of the invention includes following processes:

Protective film is fitted in into the one side of polarization plates and obtain with protective film polarization plates bonding process S101 and

Cut out the monolithic body of the polarization plates with protective film cuts out process S102.Hereinafter, being carried out specifically to each process It is bright.

" monolithic body " so-called in this specification refers to and cuts out from the film (such as film of strip (band-like)) of larger size Smaller size film.

(1) bonding process S101

(1-1) is supplied to the polarization plates of bonding process S101

The composition of (1-1-1) polarization plates

Polarization plates are the polarizers including at least polarizing film, usually also include the thermoplasticity for fitting in its one or both sides Resin film.

Thermoplastic resin film can be the protective film of protection polarizing film, other with the optical function different from polarizing film Optical film etc..The example of other optical films is phase difference film, brightness enhancement film etc..

Thermoplastic resin film can have the resin layer (such as optical layer) for being laminated in its surface.The example of resin layer is hard Coating, antiglare layer, anti-reflection layer, anti-static electricity interference layer, stain-proofing layer etc..

Thermoplastic resin film can be pressed from both sides and fit in polarizing film across adhesive layer or adhesive phase.

The thickness of polarization plates is usually 150 μm hereinafter, from the viewpoint and easily fabricated just crimp of the filming of polarization plates From the viewpoint of the sufficiently large polarization plates monolithic body with protective film, preferably 100 μm hereinafter, more preferably 80 μm hereinafter, Further preferably 70 μm or less.

The thickness of polarization plates is usually 20 μm or more or 30 μm or more.

It is illustrated referring to the example that layer of the Fig. 2 and Fig. 3 to polarization plates is constituted, however layer composition is not limited to these examples Son.

Polarization plates 2a shown in Fig. 2 has polarizing film 10；Fit in the first thermoplastic resin film of the one side of polarizing film 10 20；Fit in the second thermoplastic resin film 30 of the another side of polarizing film 10.First and second thermoplastic resin film 20,30 is for example For protective film.

A side of first and second thermoplastic resin film 20,30 can be omitted as polarization plates 2b shown in Fig. 3.? The second thermoplastic resin film 30 is omitted in polarization plates 2b.It is such that only there is the inclined of thermoplastic resin film in the one side of polarizing film 10 Vibration plate is conducive to the filming of polarization plates.

Although in Fig. 2 and Fig. 3, the illustration is omitted, can it is preferable to use bonding agent carry out polarizing film 10 and first and The fitting of second thermoplastic resin film 20,30.

The polarization plates for being supplied to bonding process S101 are preferably strip.

The length for being supplied to the polarization plates of the strip of bonding process S101 is, for example, 100~20000m, and preferably 1000 ~10000m.Additionally, it is provided the width to the polarization plates of the strip of bonding process S101 is, for example, 0.5~3m, preferably 1~ 2.5m。

(1-1-2) polarizing film

Constitute polarization plates polarizing film 10 be with absorb be parallel to its absorption axis vibration plane rectilinearly polarized light, Transmit the polarization with the absorption-type of the property of rectilinearly polarized light of (with the axis of homology parallel) vibration plane orthogonal with absorption axiss Piece.An example of polarizing film 10 is to make the polyvinyl alcohol resin film absorption dichroism pigment by being uniaxially stretched and be orientated inclined Shake piece.Such polarizing film 10 for example can use the process including being uniaxially stretched to polyvinyl alcohol resin film；Passing through will Polyvinyl alcohol resin film dichroism pigment dyes and the process of adsorbing dichroism pigment；The poly- of dichroism pigment will be adsorbed with The process of the crosslinked fluids such as vinyl alcohol resin film boric acid aqueous solution processing；And it is washed after the processing using crosslinked fluid The method of process manufacture.

As polyvinyl alcohol resin, resin obtained by being saponified polyvinyl acetate system resin can be used.As poly- Vinyl acetate resin can be with other than it can enumerate the polyvinyl acetate as the homopolymer of vinyl acetate Enumerate the copolymer etc. of vinyl acetate with the other monomers that can be copolymerized.It can be with the other monomers of vinyl acetate copolymerization Example includes unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class and (methyl) propylene with ammonium Amides etc..

" (methyl) acrylic compounds " so-called in this specification, refer in acrylic compounds and methacrylic at least One side.Also identical in " (methyl) acryloyl group ", " (methyl) acrylate " etc..

The saponification degree of polyvinyl alcohol resin is usually 85~100mol%, preferably 98mol% or more.Polyethenol series Resin can also be modified, such as the polyvinyl formal or polyvinyl acetal being modified by aldehydes also can be used Deng.The average degree of polymerization of polyvinyl alcohol resin is usually 1000~10000, and preferably 1500~5000.

The saponification degree and average degree of polymerization of polyvinyl alcohol resin can be found out according to JIS K 6726.

Film obtained by such polyvinyl alcohol resin film is used by the former material film as polarizing film 10.By polyvinyl alcohol It is that the method that resin is film-made is not particularly limited, well known method can be used.The thickness of polyvinyl alcohol resin film is without spy It does not limit, for example, 10~150 μm or so, preferably 50 μm are hereinafter, more preferably 35 μm or less.

Being uniaxially stretched for polyvinyl alcohol resin film simultaneously or can contaminated before the dyeing of dichroism pigment, with dyeing It is carried out after color.In the case where being uniaxially stretched after dyeing, this is uniaxially stretched can be before crosslinking Treatment or in crosslinking Treatment It carries out.Alternatively, it is also possible to be uniaxially stretched in these multiple stages.

When being uniaxially stretched, it can be stretched between the different roller of peripheral speed with uniaxial manner, heat also can be used Roller is stretched with uniaxial manner.It can be the dry type stretching stretched in an atmosphere in addition, being uniaxially stretched, be also possible to Make the wet tensile stretched in the state of polyvinyl alcohol resin membrane swelling using solvent, water.Stretching ratio is usually 3~ 8 times or so.

As the method for dyeing polyvinyl alcohol resin film with dichroism pigment, for example, can using by the film immersion in Method in aqueous solution containing dichroism pigment.As dichroism pigment, iodine, dichroic organic dye are used.It needs to illustrate , the first impregnation of implementation Xiang Shuizhong preferably before dyeing processing of polyvinyl alcohol resin film.

Generalling use as the crosslinking Treatment after the dyeing using dichroism pigment will be through hyperchromatic polyethenol series tree Adipose membrane is impregnated in the method in the aqueous solution containing boric acid.In the case where using iodine as dichroism pigment, this contains boric acid Aqueous solution preferably comprise potassium iodide.

The thickness of polarizing film 10 is usually 2~40 μm or so.From the viewpoint of the filming of polarization plates, polarizing film 10 Thickness be preferably 20 μm hereinafter, more preferably 15 μm hereinafter, further preferably 10 μm or less.

On the other hand, from the viewpoint of the sufficiently large polarization plates monolithic body with protective film of easily fabricated just crimp, It is preferred that the thickness of polarizing film 10 is big, specifically preferably 10 μm or more, more preferably 15 μm or more, further preferably 20 μm More than.

(1-1-3) first and second thermoplastic resin film

First and second thermoplastic resin film 20,30 is each independently by the thermoplastic resin, preferably with translucency The film being made of optically transparent thermoplastic resin.Constitute the thermoplastic resin of first and second thermoplastic resin film 20,30 It such as can be chain polyolefin-based resins (polypropylene-based resin etc.), cyclic polyolefin hydrocarbon system resin (norbornene resin etc.) Etc polyolefin-based resins；The cellulose-based resin of triacetyl cellulose, diacetyl cellulose etc；Poly terephthalic acid second The polyester based resin of diol ester, polybutylene terephthalate (PBT) etc；Polycarbonate-based resin；Methyl methacrylate system tree (methyl) acrylic resin of rouge etc；Polystyrene resin；Polyvinyl chloride resin；Acrylonitrile/butadiene/styrene It is resin；Acrylonitrile/phenylethylene resin series；Polyvinyl acetate system resin；Polyvinylidene chloride resin；Polyamide-based tree Rouge；Polyacetals system resin；Noryl system resin；Polysulfones system resin；Polyether sulfone system resin；Polyarylate system resin；Polyamide Imide series resin；Polyimides system resins etc..

Chain olefin as chain polyolefin-based resins, in addition to polyvinyl resin, acrylic resin etc can be enumerated Homopolymer other than, the copolymer formed by two or more chain olefins can also be enumerated.More specific example includes poly- third Alkene system resin (acrylic resin of the homopolymer as propylene, the copolymer based on propylene), polyethylene-based resin (as The polyvinyl resin of the homopolymer of ethylene, the copolymer based on ethylene).

Cyclic polyolefin hydrocarbon system resin is the general name for the resin being polymerize using cyclic olefin as polymerized unit.If enumerating ring-type The concrete example of polyolefin-based resins is then the open loop (co) polymer of cyclic olefin, the addition polymer of cyclic olefin, cyclic annular alkene Hydrocarbon is with the copolymer (representative situation is random copolymer) of the chain olefin of ethylene, propylene etc and by them with not Graft polymers and their hydride that saturated carboxylic acid or derivatives thereof has been modified etc..Wherein, it is preferable to use as ring-type Alkene has used the norbornene resin of the orbornene-baseds monomers such as norbornene, polycyclic orbornene-based monomer.

So-called cellulose-based resin refers to and is obtained by raw celluloses such as cotton linters, wood pulps (broad leaf tree slurry, softwood pulp) Cellulose hydroxyl hydrogen atom part or all by acetyl group, propiono and/or bytyry instead of cellulose Organic acid esters or cellulose mixed organic acid ester.For example, by the acetic acid esters of cellulose, propionic ester, butyrate and The resin of the formation such as their mixed ester.Wherein, preferably triacetyl cellulose, diacetyl cellulose, cellulose ethanoate propionic acid Ester, cellulose acetate butyrate.

Polyester based resin is the resin having other than the above-mentioned cellulose-based resin of ester bond, generally by polyacid or its spread out The resin that the condensation polymer of biology and polyalcohol is formed.2 yuan binary acid or derivatives thereof conduct polyacid can be used or it spreads out Biology, for example, terephthalic acid (TPA), M-phthalic acid, dimethyl terephthalate (DMT), naphthalene diformic acid dimethyl ester etc..It can be with Use 2 yuan of glycol as polyalcohol, for example, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexamethylene diformazan Alcohol etc..The example of suitable polyester based resin includes polyethylene terephthalate.

Polycarbonate-based resin is the engineering plastic that the polymer as obtained by being bonded monomeric unit by carbonate group is formed Material, is the resin with high impact properties, heat resistance, anti-flammability, the transparency.Polycarbonate-based resin is also possible to reduce Photoelastic coefficient and modified the resin referred to as modified polycarbonate of polymer backbone, improved the copolymerization of wavelength dependency Polycarbonate etc..

(methyl) acrylic resin is the polymer comprising the Component units from (methyl) acrylic monomer.It should Polymer is the polymer comprising methacrylate in the typical case.Preferably from the structure of methacrylate Polymer of the ratio of unit relative to entire infrastructure unit comprising 50 weight % or more.(methyl) acrylic resin can be The homopolymer of methacrylate is also possible to the copolymer comprising the Component units from other polymerizable monomers.The feelings Under condition, from other polymerizable monomers Component units ratio preferably with respect to entire infrastructure unit be 50 weight % with Under.

As the methacrylate that can constitute (methyl) acrylic resin, preferably alkyl methacrylate.Make For alkyl methacrylate, methyl methacrylate, ethyl methacrylate, n propyl methacrylate, first can be enumerated Base isopropyl acrylate, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid The carbon atom number of the alkyl of 2- ethylhexyl, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate etc is 1~8 Alkyl methacrylate.The carbon atom number of alkyl contained in alkyl methacrylate is preferably 1~4.At (methyl) In acrylic resin, one kind can be only used alone in methacrylate, also can be used together two or more.

As other the above-mentioned polymerizable monomers that can constitute (methyl) acrylic resin, can enumerate acrylate, And it is other in the molecule with the compound of polymerism carbon-to-carbon double bond.Other polymerizable monomers can only be used alone One kind also can be used together two or more.As acrylate, preferably alkyl acrylate.As alkyl acrylate, Ke Yiju Out methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, The carbon of the alkyl of tert-butyl acrylate, 2-EHA, cyclohexyl acrylate, acrylic acid 2- hydroxy methacrylate etc is former The alkyl acrylate etc. that subnumber is 1~8.The carbon atom number of alkyl contained in alkyl acrylate is preferably 1~4.In (first Base) in acrylic resin, one kind can be only used alone in acrylate, also can be used together two or more.

As other in the molecule with the compound of polymerism carbon-to-carbon double bond, ethylene, propylene, benzene second can be enumerated The vinyl cyanide compound of the vinyl compounds such as alkene, acrylonitrile etc.It is other that there is polymerism carbon-to-carbon in the molecule One kind can be only used alone in the compound of double bond, also can be used together two or more.

First and second thermoplastic resin film 20,30, which can be, is laminated the inclined for protecting of the one side for fitting in polarizing film 10 The protective film of vibration piece 10.What first or second thermoplastic resin film 20,30 was also possible to phase difference film, brightness enhancement film etc has both light Learn the protective film of function.

For example, (being stretched uniaxially or biaxially by being stretched to the thermoplastic resin film formed by above-mentioned material Deng) or formation liquid crystal layer etc. on the film, the phase difference film for having been assigned arbitrary phase difference value can be made.First and/or It is dry that second thermoplastic resin film 20,30 also can have the hard conating for being laminated in its surface, antiglare layer, anti-reflection layer, antistatic Disturb the surface-treated layer (coat) of layer, stain-proofing layer etc.

The thickness of first and second thermoplastic resin film 20,30 is usually 1~100 μm, however is seen from intensity, disposition property etc. Point consideration, preferably 5~60 μm, more preferably 5~50 μm.

From the viewpoint of the polarization plates monolithic body with protective film sufficiently large from easily fabricated just crimp, the preferably first heat Plastic resin film 20, the thickness of the second thermoplastic resin film 30 are small, specifically preferably 40 μm hereinafter, more preferably 30 μm with Under.

In the case where having thermoplastic resin film on the two sides of polarizing film 10 as polarization plates 2a shown in Fig. 2, this A little thermoplastic resin films can be made of thermoplastic resin of the same race, can also be made of thermoplastic resin not of the same race.In addition, Thickness may be the same or different.Furthermore, it is possible to phase difference characteristics having the same, it is possible to have different phase differences Characteristic.In the case where fitting in the composition of thermoplastic resin film on two sides difference, it is particularly susceptible in the polarization for having protective film Curling is generated in plate monolithic body, therefore of the invention especially advantageous in this case.

(1-1-4) bonding agent

Polarization is fitted in across adhesive layer as set forth above, it is possible to for example press from both sides the first, second thermoplastic resin film 20,30 Piece 10.As the bonding agent for forming adhesive layer, water system bonding agent, active energy ray-curable bonding agent or heat can be used Solidity bonding agent, preferably water system bonding agent, active energy ray-curable bonding agent.

As water system bonding agent, the bonding agent formed by polyvinyl alcohol resin aqueous solution, water system bi-component can be enumerated Type carbamate system emulsion adhesive etc..Wherein it is possible to suitably use the water formed by polyvinyl alcohol resin aqueous solution It is bonding agent.As polyvinyl alcohol resin, in addition to the polyvinyl acetate to the homopolymer as vinyl acetate can be used Ester carries out obtained by saponification process other than alcotex, can also use to vinyl acetate with can be copolymerized therewith its The copolymer of his monomer carries out polyvinyl alcohol based copolymer obtained by saponification process or is modified their hydroxylic moiety and obtains Modified polyvinylalcohol based polymer etc..Water system bonding agent may include aldehyde compound (glyoxal etc.), epoxide, trimerization The crosslinking agents such as cyanamide based compound, methylol compound, isocyanate compound, amine compounds, multivalent metal salt.

Using water system bonding agent, preferably by polarizing film 10 and the first, second thermoplastic resin film 20,30 After fitting, implement the drying process for removing water contained in water system bonding agent.After drying process, such as it can be set The curing step of 20~45 DEG C of temperature curing.

So-called active energy ray-curable bonding agent is containing because of ultraviolet light, visible light, electron beam, X-ray etc The irradiation of active energy beam and the bonding agent of cured curability compound, preferably ultra-violet solidified bonding agent.

Curability compound can be the curability compound of cationically polymerizable, free-radical polymerised curability chemical combination Object.As the curability compound of cationically polymerizable, for example, epoxy compound (has 1 or 2 in the molecule The compound of a above epoxy group), oxetanes based compound is (in the molecule with 1 or 2 or more oxa- ring fourth The compound of alkane ring) or their combination.As free-radical polymerised curability compound, for example, (methyl) Acrylic compounds (in the molecule with the compound of 1 or 2 or more (methyl) acryloxy) have free radical The other vinyl compounds or their combination of the double bond of polymerism.Also the solidification of cationically polymerizable can be used together Property compound and free-radical polymerised curability compound.Active energy ray-curable bonding agent is usually also comprising for drawing Send out the cationic polymerization initiators and/or radical polymerization initiator of the curing reaction of curability compound.

It, to improve cementability, can be right when polarizing film 10 to be bonded with the first, second thermoplastic resin film 20,30 The binding face of their at least any one party implements surface activation process.As surface activation process, can enumerate sided corona treatment, Corona treatment, discharge treatment (glow discharge process etc.), flame treatment, ozone treatment, UV ozone treatment, ionization activity are penetrated Line handles the dry process of (UV treatment, electron beam treatment etc.) etc；At the ultrasonic wave for having used water, acetone equal solvent The wet processed of reason, saponification process, anchor painting processing etc.These surface activation process can be carried out individually, can also combine two Kind or more.

In the case where the two sides of polarizing film 10 is bonded thermoplastic resin film, for what these thermoplastic resin films were bonded Bonding agent can be bonding agent of the same race, be also possible to bonding agent not of the same race.

(1-2) is supplied to the protective film of bonding process S101

The composition of (1-2-1) protective film

Protective film is the film for protecting the surface of polarization plates, usually in the polarization plates monolithic body fitting that will have protective film After such as image-displaying member etc., removing is peeled off together with the adhesive phase with adhesive phase.Thus, it protects Cuticula 1 can be fitted in the above-mentioned surface of polarization plates 2 with removing.

Protective film can be for example made of the adhesive phase of base material film and stacking thereon.

Base material film can be by thermoplastic resin, such as polyethylene-based resin, polypropylene-based resin, cyclic polyolefin hydrocarbon system resin Equal polyolefin-based resins；The polyester based resins such as polyethylene terephthalate, polyethylene naphthalate；It is polycarbonate-based Resin；(methyl) acrylic resin etc. is constituted.Base material film can be single layer structure, be also possible to multilayered structure.

Adhesive phase can be by (methyl) acrylic adhesive, epoxy adhesive, carbamate system adhesive, silicon Ketone system adhesive etc. is constituted.

In addition, protective film is also possible to the resin film that polypropylene-based resin and polyethylene-based resin etc. have self adhesion. In this case, protective film does not have adhesive phase.

The thickness of protective film for example can be 5~150 μm, preferably 10~100 μm, more preferably 20~75 μm, into one Preferably 25~70 μm of step (for example, 60 μm or less, further preferably 55 μm or less).Protective film thickness less than 5 μm In the case of, the case where protections of polarization plates is not enough is had, it is in addition also unfavorable in terms of disposition property.If the thickness of protective film Degree is greater than 150 μm, then unfavorable in terms of with the filming of polarization plates monolithic body of protective film, the re-workability of protective film.

The protective film for being supplied to bonding process S101 is preferably strip.

The length for being supplied to the protective film of the strip of bonding process S101 is, for example, 100~20000m, and preferably 1000 ~10000m.Additionally, it is provided the width to the protective film of the strip of bonding process S101 is, for example, 0.5~3m, preferably 1~ 2.5m。

The elasticity modulus of (1-2-2) protective film

The protective film for being supplied to bonding process S101 includes the region for meeting lower formula (I):

TD elasticity modulus-MD elasticity modulus >=300MPa (I)

In formula (I), so-called TD elasticity modulus is the stretching bullet on the direction TD under 23 DEG C of temperature, relative humidity 55%RH Property modulus (MPa), so-called MD elasticity modulus is the tensile elasticity mould on the direction MD under 23 DEG C of temperature, relative humidity 55%RH It measures (MPa).

The so-called direction MD refers to that the mechanical flow direction of film, the i.e. length direction of film, the so-called direction TD refer to and the side MD To orthogonal direction.

By will include that the protective film of above-mentioned zone fits in polarization plates, and cuts from the region in cutting out process S102 Monolithic body out, that is, the protective film for meeting formula (I) by having cut out monolithic body, available just crimp are sufficiently large Polarization plates monolithic body with protective film.

Above-mentioned so-called " cutting out monolithic body from the region ", refers to the whole of protective film possessed by cut out monolithic body Body is contained in the region.

Herein, the curling of the polarization plates monolithic body with protective film is in addition to as above-mentioned " just crimp " and " inverse curling " Other than classification, two kind can also be classified as " MD curling " and " TD curling ".So-called " MD curling " is since stress (is received Contracting power, expansive force etc.) the reason of and the curling that generates, the direction of the stress and be cut out the polarization plates monolithic with protective film The direction MD of polarization plates of the strip of body with protective film is parallel.

MD is crimped, specifically, in the record according to aftermentioned embodiment one from strip with protective film Test sample (monolithic body) is cut out in polarization plates and is above to be placed on horizontal platform with the face of concave side by the test sample When, it can be used as the angle in the direction MD of the polarization plates in two diagonal lines of test sample with strip with protective film Curling that two angles on a small diagonal line are lifted measures its size.In polarization plates of the strip with protective film partially When the absorption axis direction of vibration plate and the parallel direction MD of protective film, two diagonal lines that MD curling can be used as test sample are worked as In the curling lifted of two angles on a diagonal line small with the angle of the absorption axis direction of the polarization plates of test sample (inhale Receive the curling of axis direction) it measures.

So-called " TD curling ", be due to stress (convergent force, expansive force etc.) caused by crimp, the stress Direction is parallel with the direction TD of polarization plates of protective film with the strip for being cut out the polarization plates monolithic body with protective film.

In the present invention, it is conceived to MD curling.Can use it is produced by the present invention " just crimp it is sufficiently large with protective film The so-called just crimp of polarization plates monolithic body " refers to the just crimp for MD curling.Hereinafter, the curling is also referred to as " MD just crimp ".

Above-mentioned " protective film for being supplied to bonding process S101 includes the region for meeting formula (I) " and " monolithic body cut out Have the protective film for meeting formula (I) " in so-called " meeting formula (I) ", refer to throughout the entire protective film, that is, no matter in the guarantor Which station acquisition test sample of cuticula, according to the TD elasticity modulus and MD bullet of aftermentioned embodiment one record measurement Property modulus all meets formula (I).

The research of people according to the present invention, it is therefore apparent that if along the direction TD of the general protective film that can be obtained to formula (I) the left side measures multiple points, then according to differences such as commerical batches, there are large variation is generated in the numerical value on the left side Protective film.On the other hand also distinguish, in the direction MD along the general protective film that can be obtained, the left side measurement to formula (I) is multiple In the case where point, there is no biggish variation in the numerical value on the left side in same a roll.

Thus, the protective film of formula (I) is met throughout the entire direction TD usually it may be said that throughout the entire protective film (that is, no matter from which station acquisition test sample of the protective film) meets formula (I).

From the viewpoint of the yield rate for improving the polarization plates monolithic body with protective film, above-mentioned area possessed by protective film Domain preferably has occupied area as big as possible, and the more preferable region, which is spread, is supplied to the protective film of bonding process S101 at least The entire direction TD (width direction), further preferably spreads entire protective film.

From the viewpoint of the MD just crimp for increasing the resulting polarization plates monolithic body with protective film, the left side of formula (I) Preferably 400MPa or more, more preferably 500MPa or more.The left side of formula (I) is usually 2000MPa hereinafter, in typical situation For 1500MPa or less.

As the protective film for being supplied to bonding process S101, as long as making to the left side of acquired protective film measurement formula (I) With the protective film in the region comprising meeting formula (I).

(1-3) polarization plates are bonded with protective film

Referring to Fig. 4, a pair of rolls (doubling roller) 5,5 can be used for example to carry out in being bonded for polarization plates 2 and protective film 1.From From the viewpoint of manufacture efficiency, this method is particularly advantageous in the case where polarization plates 2 and protective film 1 are strip.

Specifically, continuously transporting the polarization plates 2 of strip, the protective film 1 of strip is simultaneously continuously transported, inclined 1 ground of a face overlapping protection film of vibration plate 2 passes through between a pair of of doubling roller 5,5 and sandwiches, and has been bonded two films it is possible thereby to manufacture Polarization plates 3 with protective film.

The direction MD (carriage direction) of polarization plates 2 is usually parallel with the direction MD (carriage direction) of protective film 1.It is so-called flat Row, the direction the MD angulation in the direction MD and protective film 1 that refer to polarization plates 2 are 0 degree ± 5 degree, preferably 0 degree ± 2 degree.

From the viewpoint of the MD just crimp for increasing the resulting polarization plates monolithic body with protective film, preferably so that polarization Two films are bonded by the absorption axiss of plate 2 mode parallel with the direction MD of protective film 1.It is so-called parallel, refer to the absorption axiss of polarization plates 2 The direction MD angulation with protective film 1 is 0 degree ± 5 degree, preferably 0 degree ± 2 degree.

Between so that the laminated body of polarization plates 2 and protective film 1 is passed through a pair of of doubling roller 5,5, thus laminated body is pushed from upper and lower, To which two films are closely sealed.

In polarization plates 2 in its outmost surface with transparent hard-coating layer (hard conating of smooth surface) and in the transparent hard painting In the case where being bonded protective film 1 on layer, it is easy to improve the closing force between polarization plates 2 and protective film 1, is thus easily obtained MD The trend of the sufficiently large polarization plates monolithic body with protective film of just crimp.Thus, polarization plates 2 preferably have in its outmost surface Transparent hard-coating layer (hard conating of smooth surface).

In the case where protective film 1 is made of the adhesive phase of base material film and stacking thereon, in the one side weight of polarization plates 2 When passing through a pair of of doubling roller 5,5 after folded protective film 1, the adhesive phase of protective film 1 is by with the above-mentioned face contact with polarization plates 2 Mode be overlapped.It can be before the stacking of protective film 1 and polarization plates 2, at least any one party of protective film 1 and polarization plates 2 Binding face carries out corona treatment, sided corona treatment, ultraviolet treatment with irradiation, flame (flame) processing, saponification process etc Surface activation process.

In the process being bonded using a pair of of doubling roller 5,5, the laminated body of protective film 1 and polarization plates 2 is assigned Pressure (clamping pressure) is, for example, 0.01~0.5MPa, or 0.05~0.3MPa.As doubling roller 5,5, table can be used Face is the metal (alloys such as including SUS.), the known doubling roller such as the roller of rubber system.

In the process for being bonded polarization plates 2 with protective film 1, the same of tension preferably is being applied to polarization plates 2 and protective film 1 Shi Jinhang fitting, the fitting forward pull of more preferable polarization plates 2 are less than the fitting forward pull of protective film 1.Such tension force is from increasing It is advantageous from the aspect of the MD just crimp of the big resulting polarization plates monolithic body with protective film.Fitting forward pull refers to two films The tension in the direction MD for being applied to film before fitting (laminated body of two films passes through a pair of of doubling roller 5,5), can be according to aftermentioned The record measurement that embodiment is one.

From the viewpoint of the MD just crimp for increasing the resulting polarization plates monolithic body with protective film, the MD of polarization plates 2 Fitting forward pull on direction is preferably 250N/m hereinafter, more preferably 200N/m or less.

From the same viewpoint, the fitting forward pull on the direction MD of protective film 1 is preferably 260N/m or more, more preferably For 300N/m or more.

(2) process S102 is cut out

This process is to meet the above-mentioned of formula (I) from the polarization plates 3 for having protective film obtained in bonding process S101 The process for being cut out in region, obtaining the polarization plates monolithic body with protective film.

It cuts out and (cuts) to can be used to cut with the known cutting means such as cutting machine and carry out.

As described above, so-called " monolithic body is cut out from region " refers to, protective film possessed by the monolithic body being cut out Entirety is contained in the region.

It the size of the polarization plates monolithic body with protective film cut out, shape and cuts out angle and is not particularly limited.

Polarization plates monolithic body with protective film is preferably square configuration, more preferably with the rectangular shape of long side and short side Shape.This is rectangular to be preferably shaped to rectangle.

In the case where having the shape of polarization plates monolithic body of protective film and being rectangular situation, the length of long side is, for example, 50mm ~300mm, preferably 70mm~150mm.The length of short side is, for example, 30mm~200mm, preferably 40mm~100mm.

In general, if the polarization plates monolithic body with protective film becomes large-sized, there will be difficult to generate MD just rolling up Bent trend.Thus, in the case where the size of the polarization plates monolithic body with protective film is big, just rolled up to assign enough MD Qu Liang, it is sometimes preferred to further increase the left side of formula (I).

It is rectangular situation in the shape of the polarization plates monolithic body with protective film although being not particularly limited Under, can according to from protective film side have protective film polarization plates monolithic body when, make polarization plates absorption axis direction (polarization The direction MD of plate) relative to its longer side and a shorter side formed 45 degree angles mode, from have protective film polarization plates 3 in cut out Polarization plates monolithic body with protective film.

Alternatively, in the case where the shape of the polarization plates monolithic body with protective film is rectangular situation, it can also be according to from guarantor Cuticula side observation have protective film polarization plates monolithic body when, make polarization plates absorption axis direction (directions MD of polarization plates) and its The parallel mode of long side, or the mode of the angle relative to 90 degree of the formation of its long side, cut from the polarization plates 3 with protective film The polarization plates monolithic body of protective film is had out.

< has the polarization plates monolithic body > of protective film

Polarization plates monolithic body with protective film of the invention includes polarization plates and the protective film for being laminated in its one side, protection Film meets lower formula (II):

First the-the second elasticity modulus of elasticity modulus >=300MPa (II)

In formula (II), so-called first elasticity modulus is the absorption with polarization plates under 23 DEG C of temperature, relative humidity 55%RH Tensile modulus of elasticity (MPa) on the orthogonal direction of axis, so-called second elasticity modulus are 23 DEG C of temperature, relative humidity 55%RH Under the direction parallel with the absorption axiss of polarization plates on tensile modulus of elasticity (MPa).

By having the protective film for meeting formula (II), the polarization plates monolithic body with protective film can have sufficiently large MD Just crimp.

According to the polarization plates monolithic body with protective film with sufficiently large MD just crimp, even if in its polarization plates side layer 1 or more other optical functional layer etc. is folded in the case where above-mentioned multilayer structure making is made, can also maintain not having The state (flat state) or the state with just crimp of inverse curling, thus in the polarization plates monolithic body that will have protective film or When multilayer structure making folder fits in image-displaying member across adhesive phase, it can inhibit to generate fitting mistake or bubble is mixed into The not good situation at the interface of adhesive phase and image-displaying member.

Polarization plates monolithic body with protective film of the invention can use the above-mentioned polarization plates monolithic with protective film The manufacturing method of body manufactures.

For the direction orthogonal with the absorption axiss of polarization plates, the above-mentioned polarization plates monolithic body with protective film is being utilized It is synonymous with the direction TD of protective film and polarization plates in the case where polarization plates monolithic body of the manufacturing method manufacture with protective film.

So-called " meeting formula (II) " refers to throughout the entire protective film, that is, no matter the protective film which station acquisition Test sample all meets formula according to the first elasticity modulus and the second elasticity modulus of aftermentioned embodiment one record measurement (II)。

Based on < with reason identical the reasons why record in manufacturing method > mono- of polarization plates monolithic body of protective film By meeting formula throughout direction entirely orthogonal with the absorption axiss of polarization plates in the polarization plates monolithic body with protective film (II) protective film is usually it may be said that throughout the entire protective film (that is, no matter measuring from which station acquisition of the protective film With sample) meet formula (II).

From the viewpoint of the MD just crimp for increasing the polarization plates monolithic body with protective film, the left side of formula (II) is preferably 400MPa or more, more preferably 500MPa or more.The left side of formula (II) is usually 2000MPa hereinafter, being in typical situation 1500MPa or less.

The size and shape of polarization plates monolithic body with protective film is not particularly limited, for specific size and shape Shape, manufacturing method > mono- record of polarization plates monolithic body of the reference < with protective film.In the polarization plates for having protective film In the case that the size of monolithic body is big, in order to assign enough MD just crimp amounts, it is sometimes preferred to further increase a left side of formula (II) Side.

Polarization plates monolithic body with protective film (utilizes the manufacturer of the polarization plates monolithic body with protective film of the invention The polarization plates monolithic body with protective film that method obtains is also identical) preferred display goes out MD just crimp, and it is above-mentioned in order to can be used as Multilayer structure making also shows that MD just crimp or shows the flat state without curling, more preferably according to aftermentioned reality The MD just crimp amount for applying example one record measurement is 40mm or more.MD just crimp amount may be 45mm or more.MD just crimp Amount is preferably 100mm or less.

It is rectangular situation in the shape of the polarization plates monolithic body with protective film although being not particularly limited Under, from protective film side have protective film polarization plates monolithic body when, can make the absorption axis direction of polarization plates relative to Its longer side and a shorter side forms 45 degree of angle.

Alternatively, being seen in the case where having the shape of polarization plates monolithic body of protective film and being rectangular situation from protective film side When examining the polarization plates monolithic body with protective film, the absorption axis direction of polarization plates can be parallel with its long side, or relative to it Long side forms 90 degree of angle.

An example that the layer of polarization plates monolithic body with protective film is constituted is shown in Fig. 5.As shown in figure 5, protecting In the case that film 1 is made of the adhesive phase 50 of base material film 40 and stacking thereon, quilt is so that adhesive possessed by protective film 1 Layer 50 is be overlapped with the mode of an above-mentioned face contact of polarization plates 2.

For the more specific description of polarization plates 2 and protective film 1, the system of polarization plates monolithic body of the < with protective film is quoted Make method > mono- record.

< strip has the polarization plates > of protective film

The polarization plates of strip of the invention with protective film include the polarization plates of strip and the length for being laminated in its one side The protective film of strip, protective film include the region for meeting lower formula (III):

First the-the second elasticity modulus of elasticity modulus >=300MPa (III)

In formula (III), so-called first elasticity modulus is inclined with strip under 23 DEG C of temperature, relative humidity 55%RH Tensile modulus of elasticity (MPa) on the orthogonal direction of the absorption axiss of vibration plate, so-called second elasticity modulus are 23 DEG C of temperature, opposite Tensile modulus of elasticity (MPa) on the direction parallel with the absorption axiss of the polarization plates of strip under humidity 55%RH.

The polarization plates that protective film is had according to the strip comprising above-mentioned zone, cut out monolithic body, thus from the region The monolithic body cut out has the protective film for meeting formula (III), thus can obtain just crimp it is sufficiently large with protective film Polarization plates monolithic body.

Above-mentioned so-called " cutting out monolithic body from the region ", refers to the whole of protective film possessed by cut out monolithic body Body is contained in the region.

The polarization plates of strip of the invention with protective film can be by implementing the above-mentioned polarization plates with protective film The bonding process S101 of the manufacturing method of monolithic body is manufactured.

For the direction orthogonal with the absorption axiss of polarization plates, by implementing the above-mentioned polarization plates monolithic with protective film The bonding process S101 of the manufacturing method of body and manufacture strip with protective film polarization plates in the case where, with protective film and partially The direction TD of vibration plate is synonymous.

So-called " meeting formula (III) " refers to throughout the entire protective film, that is, no matter adopt in which position of the protective film Collect test sample, all meets according to the first elasticity modulus and the second elasticity modulus of aftermentioned embodiment one record measurement Formula (III).

Based on < with reason identical the reasons why record in manufacturing method > mono- of polarization plates monolithic body of protective film By meeting formula throughout direction entirely orthogonal with the absorption axiss of polarization plates in polarization plates of the strip with protective film (III) protective film is usually it may be said that throughout the entire protective film (that is, no matter measuring from which station acquisition of the protective film With sample) meet formula (III).

From the viewpoint of the yield rate for improving the polarization plates monolithic body with protective film, above-mentioned area possessed by protective film Domain preferably has occupied area as big as possible, and the more preferable region, which is spread, is supplied to the protective film of bonding process S101 at least Entire width direction further preferably spreads entire protective film.

From the polarization plates monolithic body improved obtained by being cut out in the polarization plates that strip has protective film with protective film MD just crimp from the viewpoint of, the left side of formula (III) is preferably 400MPa or more, more preferably 500MPa or more.Formula (III) The left side be usually 2000MPa hereinafter, being 1500MPa or less in typical situation.

It the size of polarization plates monolithic body with protective film, shape and cuts out angle and is not particularly limited, for specific Size, shape and angle is cut out, manufacturing method > mono- record of polarization plates monolithic body of the reference < with protective film.From In the case that size of the strip with the polarization plates monolithic body with protective film obtained by cutting out in the polarization plates of protective film is big, In order to assign enough MD just crimp amounts, it is sometimes preferred to further increase the left side of formula (III).

The length of polarization plates of the strip with protective film is, for example, 100~20000m, preferably 1000~10000m.Separately Outside, the width of polarization plates of the strip with protective film is, for example, 0.5~3m, preferably 1~2.5m.

The layer of polarization plates for strip with protective film constitutes, constitutes the inclined of polarization plates of the strip with protective film The more specific description of vibration plate and protective film, the manufacturing method > and < of polarization plates monolithic body of the reference < with protective film have Polarization plates monolithic body > records of protective film.

< multilayer structure making >

It can be in the one side of the polarization plates side of the polarization plates of polarization plates or strip with protective film with protective film, also Press from both sides 1 layer or more of the optical functional layer or diaphragm (stripping film) etc. other across adhesive phase, adhesive layer stacking.

Optical functional layer can be phase separation layer etc., and optical functional layer can be pressed from both sides across adhesive phase, adhesive layer stacking One side in polarization plates side.

[embodiment]

Hereinafter, provide experimental example and the present invention is further elaborated with, however the present invention is not limited by these examples.

In following experimental examples, the thickness of polarization plates and film, the elasticity modulus of protective film are determined according to following methods The MD of fitting forward pull on the direction MD of difference, polarization plates and protective film and the polarization plates monolithic body with protective film curling Amount.

(1) thickness of polarization plates and film

The digital micrometer " MH-15M " of (strain) Nikon is used to measure.

(2) elastic modulus difference of protective film

Long side 100mm × short side 25mm length is cut out from polarization plates of the strip with protective film using super cutting machine Rectangular small pieces.So that the long side of small pieces and strip with the direction MD of polarization plates of protective film parallel, small pieces short sides and The mode that the direction TD of polarization plates of the strip with protective film is parallel is cut out.Polarization plates are removed from the small pieces, by institute Test sample of the small pieces of the protective film monomer obtained as MD elasticity modulus.

In addition, be used in the same manner super cutting machine from strip with protective film polarization plates in cut out long side 100mm × The rectangular small pieces of short side 25mm.Wherein, so that the direction TD of the polarization plates of the long side of small pieces and strip with protective film In parallel, the short side of small pieces is cut out with strip with the parallel mode in the direction MD of polarization plates of protective film.From the small pieces Middle removing polarization plates, using the small pieces of resulting protective film monomer as the test sample of TD elasticity modulus.

Then, with the folder up and down of cupping machine ((strain) Shimadzu Seisakusho Ltd. Autograph AG-Xplus testing machine) Tool, clamps the longitudinal direction both ends of said determination sample, in 23 DEG C, relative humidity in a manner of being divided into 5cm between making fixture In the environment of 55%, stretched with the tensile speed 1mm/ minutes length directions by test sample along test sample, according to institute Load-deformation curve in 3~6MPa between straight line slope, calculate 23 DEG C, the tensile elasticity under relative humidity 55% Modulus (MPa).At this point, only used as the thickness for calculating stress by biaxial stretch-formed poly terephthalic acid second two The thickness value of alcohol ester (base material film).

It is MD elasticity modulus by the tensile modulus of elasticity that the measurement of the test sample of MD elasticity modulus is calculated, by TD bullet Property modulus the tensile modulus of elasticity that is calculated of measurement of test sample be TD elasticity modulus.

In following each experimental examples, due to so that the absorption axiss (direction MD) of polarization plates are parallel with the direction MD of protective film Mode two films are bonded and manufacture the polarization plates with protective film, therefore the TD elasticity modulus of above-mentioned formula (I) and above-mentioned formula (II) and the first elasticity modulus of formula (III) is synonymous, the MD elasticity modulus of above-mentioned formula (I) and above-mentioned formula (II) and formula (III) Second elasticity modulus is synonymous.

Hereinafter, TD elasticity modulus (the first elasticity modulus) is referred to as " TD elasticity modulus ", by MD elasticity modulus (the second bullet Property modulus) referred to as " MD elasticity modulus ".

According to resulting TD elasticity modulus and MD elasticity modulus, TD elasticity modulus-MD elasticity modulus (the first elasticity is calculated The-the second elasticity modulus of modulus).

Hereinafter, TD elasticity modulus-MD elasticity modulus (first the-the second elasticity modulus of elasticity modulus) is referred to as " elasticity Modulus is poor ".

(3) the fitting forward pull on the direction MD of polarization plates and protective film

Using doubling roller and the tension-sensing roller between a pair of of niproll of doubling roller is set to, determine with In a pair of of doubling roller for being bonded polarization plates with protective film and trip side disposed thereon and near a pair of of niproll of doubling roller it Between the layer tension (N/m) of polarization plates and protective film advanced, as the fitting forward pull on the direction MD.

(4) the MD amount of curl of the polarization plates monolithic body with protective film

As shown in fig. 6, making when with from protective film side partially from polarization plates 60 of the resulting strip with protective film The mode that the absorption axiss 61 of vibration plate are 45 degree relative to longer side and a shorter side, cuts out rectangle (long side 140mm using super cutting machine × short side 70mm) small pieces (monolithic body), as the test sample 70 of MD amount of curl.It is pasted by polarization plates and protective film After conjunction soon, cutting out with sample 70 is measured in the environment of 23 DEG C, relative humidity 55%.

By test sample 70 with the face of concave side be above be placed on datum level (horizontal platform).In this state to measurement With in two diagonal lines of sample 70 test sample 70 with the angle of the absorption axis direction of polarization plates small one it is diagonal Two angles 80 on line measure the height relative to datum level respectively, and being averaged for the height as the two angles 80 finds out MD curling It measures (mm).

The concave state in protective film side is that have the state of just crimp, and the concave state in polarization plates side has inverse curling State.In following experimental examples 1~3, arbitrary test sample (the polarization plates monolithic body with protective film) all has positive volume It is bent.

1~3 > of < experimental example

(A) production of polarizing film

Continuously transport long size polyvinyl alcohol film (average degree of polymerization: about 2400, saponification degree: 99.9 moles of % with Upper, thickness: 30 μm) while, being uniaxially stretched in the way of dry type is about 4 times, then keeps tense situation constant, at 40 DEG C After being impregnated 1 minute in pure water, impregnated 60 seconds in the aqueous solution that iodine/potassium iodide/water weight ratio is 0.1/5/100 at 28 DEG C. Thereafter, it is impregnated 300 seconds in the aqueous solution that potassium iodide/boric acid/water weight ratio is 10.5/7.5/100 at 68 DEG C.Next, It is 180 seconds dry at 70 DEG C after cleaning 5 seconds with 5 DEG C of pure water, it obtains being adsorbed with iodine on the polyvinyl alcohol film by being uniaxially stretched And the polarizing film for the strip being orientated.Polarizing film with a thickness of 13 μm.

(B) production of polarization plates

The polarizing film of strip obtained in above-mentioned (A) is continuously transported, the first heat of strip is simultaneously continuously transported Plastic resin film (Nippon Paper (strain) system the trade name " COP25ST-HC " as clear hard coat film, in cyclic polyolefin hydrocarbon system Be formed with film, the thickness of transparent hard-coating layer on resin film: 29 μm) and strip the second thermoplastic resin film (Fujiphoto The trade name " ZRG20SL " as triacetyl cellulose (TAC) film of (strain) system, thickness: 20 μm), on one side to polarizing film and the Water system bonding agent is injected between one thermoplastic resin film and between polarizing film and the second thermoplastic resin film, passes through one on one side Between doubling roller, obtaining by the first thermoplastic resin film/water system adhesive layer/polarizing film/water system adhesive layer/second thermoplasticity The stacked film that resin film is constituted.

Next, transporting resulting stacked film, the heat treatment of 80 DEG C, 300 seconds is carried out across air drier, thus Keep water system adhesive layer dry, obtains the polarization plates of strip.

As above-mentioned water system bonding agent, used by pva powder (Japanese synthetic chemical industry (strain) system Trade name " GOHSEFIMER ", average degree of polymerization: 1100) it is dissolved in the poly- second of 3 weight % of concentration obtained by 95 DEG C of hot water Relative to 10 parts by weight of pva powder with ratio mixed cross-linker (Japan's synthesis chemistry of 1 parts by weight in enol aqueous solution The sodiam glyoxlate of industrial (strain) system) obtained by aqueous solution.Resulting polarization plates with a thickness of 62 μm.

(C) production of polarization plates of the strip with protective film

The polarization plates of strip obtained in above-mentioned (B) are continuously transported, the length for having removed diaphragm is simultaneously continuously transported The protective film of strip is (by being laminated with (methyl) third on biaxial stretch-formed polyethylene terephthalate (thickness: 38 μm) The trade name " AY-4212 " of rattan lumber industry (strain) system of olefin(e) acid system adhesive phase (thickness: 15 μm)), they are overlappingly passed through Between a pair of of doubling roller, thus from the upper and lower laminated body for pushing protective film and polarization plates, strip is continuously manufactured by out with protection The polarization plates of film.

Protective film is pressed from both sides to the first thermoplastic resin film (clear hard coat film) face that polarization plates are fitted in across its adhesive phase.

It should be noted that the pressure (clamping is pressed) assigned using laminated body of the doubling roller to protective film and polarization plates is 0.1MPa.At this point, the fitting forward pull on the direction MD of polarization plates is 151N/m, the fitting forward pull on the direction MD of protective film For 327N/m.

The manufacturing method of polarization plates of the strip of experimental example 1~3 with protective film is in addition to the different (quotient of protective film used Condition is same, however batch is different.) identical in addition.Hereinafter, protective film used in experimental example 1~3 is also referred to as protective film 1~3.

The polarization plates that protective film is had by resulting strip find out TD elasticity modulus and MD elasticity according to above-mentioned method Modulus and elastic modulus difference.

Protective film 1~3 is respectively provided with the width (direction TD length) of 1300mm.In the measurement of the elasticity modulus of each protective film When, in some the arbitrary direction MD position, along width direction one end relative to width direction be 100mm, 280mm, Total 7 points of the position 470mm, 650mm, 830mm, 1020mm and 1200mm cuts out test sample, to this 7 test samples TD elasticity modulus, MD elasticity modulus and elastic modulus difference are found out respectively.Their result is shown in " 1 " column of table 1.In phase 7 measurements are cut out as described above along the position that 20mm is left in the direction MD for some the above-mentioned arbitrary direction MD position With sample, TD elasticity modulus, MD elasticity modulus and elastic modulus difference are found out respectively to this 7 test samples.By their knot Fruit is shown in " 2 " column of table 1.In the position for leaving 50mm along the direction MD relative to some the above-mentioned arbitrary direction MD position It sets and cuts out 7 test samples as described above, TD elasticity modulus, MD springform are found out respectively to this 7 test samples Amount and elastic modulus difference.Their result is shown in " 3 " column of table 1.

In addition, the width position and the elastic modulus difference (bullet recorded in " 1 " column of table 1 that will indicate protective film 1~3 Property modulus) relationship graphics table it is shown in Figure 7.

About the position for cutting out test sample, such as the so-called " position for being 100mm in one end relative to width direction Cut out test sample ", refer to so that one end relative to width direction is the position of 100mm and the width side of test sample Test sample is cut out to the consistent mode in center.It is also same relative to the position of one end of width direction for others Sample.

[table 1]

As shown in table 1 and Fig. 7, it is known that the protective film 1 and 2 of strip include throughout it is whole, i.e. spread the entire direction TD (with The orthogonal direction of the absorption axiss of the polarization plates of strip) and spread the entire direction MD (the absorption axiss side of the polarization plates of strip To) meet formula (I) and the region of (III), and the region spreads the entire width direction of protective film.

It is different, although the protective film 3 of strip is comprising spreading the entire direction the TD (absorption with the polarization plates of strip The orthogonal direction of axis) and meet throughout the entire direction MD (the absorption axis directions of the polarization plates of strip) formula (I) and (III) region, however the region does not spread the entire width direction of protective film.That is, the protective film 3 of strip is relative to width The one end for spending direction, only meets formula (I) and (III) in the one end into the region of about 700mm.

It should be noted that as described above, meeting formula (I) and the protection of (III) in each the arbitrary direction MD position Film usually also meets formula (I) and (III) in other directions MD position.

(D) production of the polarization plates monolithic body with protective film

As shown in fig. 6, from polarization plates of the strip obtained in above-mentioned (C) with protective film, to be seen from protective film side Make the absorption axiss of polarization plates relative to 45 degree of longer side and a shorter side of mode when examining, it is (long to cut out rectangle using super cutting machine Side 140mm × short side 70mm) small pieces (monolithic body), obtain the polarization plates monolithic body with protective film.

To the resulting polarization plates monolithic body with protective film, MD amount of curl is determined according to above-mentioned method.

The strip of experimental example 1~3 is respectively provided with the width (direction TD length) of 1330mm with the polarization plates of protective film. In the measurement of the MD amount of curl for the polarization plates monolithic body with protective film that the polarization plates for having protective film by each strip obtain When, in some the arbitrary direction MD position, along width direction one end relative to width direction be 100mm, 280mm, Total 7 points of the position 470mm, 650mm, 830mm, 1020mm and 1200mm cuts out the polarization plates monolithic body with protective film, right This 7 monolithic bodies determine MD amount of curl respectively.That records from " 1 " column of table 1 is used to measure the elastic modulus difference of protective film Cutting out for test sample 7 monolithic bodies are cut out near position.It the results are shown in Table 2.In addition, will indicate from experiment The strip of example 1~3 with protective film polarization plates in cut out the polarization plates monolithic body with protective film width position, It is shown in Figure 7 with the graphics table of the relationship of the MD amount of curl of the polarization plates monolithic body with protective film cut out.

It is such as so-called " in one relative to width direction about the position for cutting out the polarization plates monolithic body with protective film End is that the position of 100mm cuts out the polarization plates monolithic body with protective film ", refer to and is relative to one end of width direction to be The consistent mode in width direction center of the position of 100mm and the polarization plates monolithic body with protective film is cut out with protection The polarization plates monolithic body of film.It is also the same relative to the position of one end of width direction for others.

The polarization plates monolithic with protective film cut out from polarization plates of the strip of experimental example 1~3 with protective film Body all has just crimp.Thus, the MD amount of curl measured is the amount of MD just crimp.

[table 2]

7 cut out from polarization plates of the strip for the experimental example 1 for having used protective film 1 with protective film are with protection The polarization plates monolithic body of film and from the strip for the experimental example 2 for having used protective film 2 with protective film polarization plates in cut out 7 polarization plates monolithic bodies with protective film in, the protective film for being laminated in polarization plates meets formula (II).

7 cut out from polarization plates of the strip for the experimental example 3 for having used protective film 3 with protective film are with protection In the polarization plates monolithic body of film, relative to strip with protective film polarization plates width direction one end be 100mm, The monolithic body that the position of 280mm, 470mm and 650mm are cut out meets formula (II), so for the protective film for being laminated in polarization plates And formula (II) is unsatisfactory in the monolithic body that the position of 830mm, 1020mm and 1200mm are cut out.

As shown in table 2 and Fig. 8, meet the MD that 40mm or more is shown with the polarization plates monolithic body of protective film of formula (II) Just crimp amount.On the other hand, be unsatisfactory for the MD just crimp amount of the polarization plates monolithic body with protective film of formula (II) 40mm with Under.

The explanation of symbol

1 protective film, 2,2a, 2b polarization plates, 3 have the polarization plates of protective film, 5 doubling rollers, 10 polarizing films, 20 first thermoplastics Property resin film, 30 second thermoplastic resin films, 40 base material films, 50 adhesive phases, 60 strips have protective film polarization plates, 61 The absorption axiss of polarization plates, the test sample of 70 MD amount of curl, the angle of 80 test samples.

Claims (11)

1. a kind of manufacturing method of the polarization plates monolithic body with protective film,

The manufacturing method includes:

The protective film in the region comprising meeting lower formula (I) is fitted in into the one side of polarization plates and obtains the polarization plates with protective film Process and

The process of the monolithic body of the polarization plates with protective film is cut out from the region；

TD elasticity modulus-MD elasticity modulus >=300MPa (I)

In formula, so-called TD elasticity modulus is the tensile modulus of elasticity on the direction TD under 23 DEG C of temperature, relative humidity 55%RH, So-called MD elasticity modulus is the tensile modulus of elasticity on the direction MD under 23 DEG C of temperature, relative humidity 55%RH.

2. the manufacturing method according to claim 1, wherein

The polarization plates are sandwiched between a pair of rolls with the protective film and are bonded.

3. manufacturing method according to claim 2, wherein

The polarization plates are strip, and the protective film is strip.

4. manufacturing method according to claim 3, wherein

The fitting forward pull of the polarization plates be 200N/m hereinafter,

The fitting forward pull of the protective film is 300N/m or more.

5. manufacturing method according to any one of claims 1 to 4, wherein

It is bonded in the mode for keeping the absorption axiss of the polarization plates parallel with the direction MD of the protective film.

6. manufacturing method according to any one of claims 1 to 4, wherein

The polarization plates with a thickness of 70 μm or less.

7. a kind of polarization plates monolithic body with protective film,

It includes polarization plates and the protective film for being laminated in its one side,

The protective film meets lower formula (II):

First the-the second elasticity modulus of elasticity modulus >=300MPa (II)

In formula, so-called first elasticity modulus, be under 23 DEG C of temperature, relative humidity 55%RH with the absorption axiss of the polarization plates just Tensile modulus of elasticity on the direction of friendship, so-called second elasticity modulus, be under 23 DEG C of temperature, relative humidity 55%RH with it is described Tensile modulus of elasticity on the parallel direction of the absorption axiss of polarization plates.

8. the polarization plates monolithic body according to claim 7 with protective film, wherein

Face with the polarization plates side be protrusion the direction parallel with the absorption axiss of the polarization plates on amount of curl for 40mm More than.

9. the polarization plates monolithic body according to claim 7 or 8 with protective film, wherein

The polarization plates with a thickness of 70 μm or less.

10. a kind of strip has the polarization plates of protective film,

It includes the protective film of the polarization plates of strip and the strip for being laminated in its one side,

The protective film includes the region for meeting lower formula (III):

First the-the second elasticity modulus of elasticity modulus >=300MPa (III)

In formula, so-called first elasticity modulus is the polarization plates with the strip under 23 DEG C of temperature, relative humidity 55%RH Tensile modulus of elasticity on the orthogonal direction of absorption axiss, so-called second elasticity modulus are under 23 DEG C of temperature, relative humidity 55%RH The direction parallel with the absorption axiss of the polarization plates of the strip on tensile modulus of elasticity.

11. the polarization plates that strip according to claim 10 has protective film, wherein

The region spreads the entire width direction of the protective film.