CN109932763A - Laminated body - Google Patents

Abstract

The present invention provides a kind of curling that can reduce the laminated body comprising polarization plates and stripping film and the laminated body of the tilting that is difficult to happen stripping film.Laminated body of the invention is the laminated body for being sequentially laminated with polarization plates and stripping film; the polarization plates successively include protective film, polarizing film and adhesive phase; described adhesive layer is configured at the position adjacent with stripping film; the polarizing film with a thickness of 15 μm or less; the puncture strength of the protective film is 3.0gf/ μm or more, and the creep power of described adhesive layer and the stripping film is 4.5N or more and 15N or less.

Description

Laminated body

Technical field

The present invention relates to a kind of laminated bodies.

Background technique

Liquid crystal display device, organic EL display device make full use of that power consumption is low, movement, light weight and slim etc. at low voltage Feature is used in various display equipment.Liquid crystal display device has the one of the visible side and back side that are configured at liquid crystal cells To polarization plates.Organic EL display device has the polarization plates (circularly polarizing plate) for the visible side for being configured at organic EL display element.

Polarization plates are generally by the table that can be removed as the pollution, damage that are bonded on a surface for preventing the surface Surface protective film (also referred to as protect film.) and be bonded stripping film (also referred to as seperate on another surface film.) laminated body circulate on the market.When making display device, the adhesive that exposes after stripping film will be peeled off layer by layer It is laminated on display element.Thus, stripping film needs to will not fall off before when using, closely sealed with polarization plates always.However, according to The type of adhesive phase is different, because it is long-term certainly when bonding force deteriorate, and there are the end stripping film in laminated body from The problem of polarization plates fall off, i.e., the problem of tilting there are stripping film.

In addition, laminated body be on the basis of polarizing film sometimes up and down it is asymmetric is constituted (thickness difference, material type not The different composition of same, layer number), curling is generated sometimes.Once generating curling in laminated body, then there is production display device Yield penalty the case where.In the past, the volume of laminated body is controlled using tension when surface protection film to be fitted in polarization plates It is bent.Recently, along with the slimming of display device, the component for constituting laminated body is thinning, it is easier to curling is generated, merely with tension Control be not enough to solve the problems, such as this.

In patent document 1, recorded be sequentially laminated with adhesive phase, polarizing film screening glass, polarizing film, Mght-transmitting base material, The optical laminate of shielding layer and hard conating.It, can by using the small Polyester substrate of size changing rate as Mght-transmitting base material To prevent the generation of curling caused by being changed as humidity.It is generated in the environment of high temperature and humidity in addition, recording cellulose ester membrane Stress, entire liquid crystal cells crimp.Patent document 1 is to reduce the liquid crystal display panel after polarization plates to be fitted in liquid crystal cells For the purpose of curling, the curling of optical laminate itself is not accounted for.Moreover, not accounting for the tilting of stripping film in patent document 1.

In patent document 2, recorded and be sequentially laminated with adhesive phase, transparent supporting body, iodine system PVA polarizing film and hard The polarization plates of film.Even if the hard coat film recorded in patent document 2 also can reduce consolidating by film when transparent supporting body is thinned Change the curling of hard coat film caused by hardness reduction, cure shrinkage.Patent document 2 for the purpose of the curling for reducing hard coat film monomer, The curling of laminated body entirety when not accounting for hard coat film applied to polarization plates.Moreover, not accounting for removing in patent document 2 The tilting of film.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2014-6447 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2016-64399 bulletin

Summary of the invention

Problem to be solved by the invention

The object of the present invention is to provide a kind of curlings that can reduce the laminated body comprising polarization plates and stripping film, difficulty With the laminated body of the tilting of peeling-off film.

The method for solving problem

[1] a kind of laminated body is the laminated body for being sequentially laminated with polarization plates and stripping film,

The polarization plates successively include protective film, polarizing film and adhesive phase,

Described adhesive layer is configured at the position adjacent with stripping film,

The polarizing film with a thickness of 15 μm hereinafter,

The puncture strength of the protective film is 3.0gf/ μm or more,

The creep power of described adhesive layer and the stripping film is 4.5N or more and 15N or less.

[2] according to the laminated body recorded in [1], wherein the moisture permeability of the protective film is 600g/m²R or less for 24 hours.

[3] according to the laminated body recorded in [1] or [2], wherein the protective film with stripping film side opposite side With hard conating.

[4] according to the laminated body recorded in [3], wherein the sheet resistance value of the hard conating is 1.0 × 10⁷Ω/ with It is upper and 1.0 × 10¹⁰Ω/ or less.

[5] laminated body recorded according to any one of [1]~[4], wherein the protective film includes to be selected from cellulose-based tree Rouge, polycarbonate-based resin, polyolefin-based resins, PET series resin and methyl methacrylate It is at least one of resin.

[6] laminated body recorded according to any one of [1]~[5], wherein on the basis of the polarization plates with the stripping There is surface protection film from film side opposite side.

Invention effect

According to the present invention it is possible to which the curling of the laminated body comprising polarization plates and stripping film can be reduced, be difficult to by providing one kind The laminated body of the tilting of peeling-off film.

Detailed description of the invention

Fig. 1 is the schematic sectional view of an example for indicating that the layer of laminated body is constituted.

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

Fig. 3 is (a) top view and (b) side view of the shape of test film when indicating measurement creep power.

Specific embodiment

< laminated body >

Fig. 1 is the schematic sectional view of an example for indicating that the layer of laminated body of the invention is constituted.In Fig. 1 and Fig. 2, adhesive layer It is not shown.As shown in Fig. 1 (a), the laminated body 100 of present embodiment has the layer for being laminated with polarization plates 10 and stripping film 60 It constitutes.Polarization plates 10 successively include protective film 20, polarizing film 11 and adhesive phase 30.Adhesive phase 30 is configured at and removes The adjacent position of film 60, in other words, adhesive phase 30 is formed at the layer of the outmost surface of polarization plates 10.

Laminated body of the invention can be also comprising other layers.As shown in Fig. 1 (b), the laminated body 101 of present embodiment with There is surface protection film 50 with 60 side opposite side of stripping film on the basis of polarization plates 10.

Can be as shown in Fig. 1 (a), laminated body only has protective film 20 in the one side of polarizing film 11, can also be such as Fig. 1 (b) Shown, laminated body is respectively provided with protective film 20,21 on the two sides of polarizing film 11.

As shown in Fig. 1 (b), the polarization plates 10 of the laminated body 101 of present embodiment have hard conating 40.Hard conating 40 is preferred It is formed on protective film 20, that is, protective film 20 preferably has hard conating 40 with 60 side opposite side of stripping film.Hard conating 40 can To be configured at the position adjacent with surface protection film 50, hard conating 40 is also possible to be formed in the outmost surface of polarization plates 10 Layer.

Hereinafter, being illustrated to each component for constituting laminated body of the invention.

(polarizing film 11)

Polarizing film 11 used in the present invention generally goes through the process being uniaxially stretched to polyvinyl alcohol resin film, logical It crosses and polyvinyl alcohol resin film dichroism pigment is dyed and is allowed to adsorb the process of dichroism pigment, dichroism will be adsorbed with The process and carried out after the processing using boric acid aqueous solution that the polyvinyl alcohol resin film of pigment is handled with boric acid aqueous solution The process of washing and 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.As can be with other lists of vinyl acetate copolymerization Body, for example, unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class and the propylene with ammonium Amides etc..

The saponification degree of polyvinyl alcohol resin is usually 85mol%~100mol% or so, preferably 98mol% or more. The polyvinyl alcohol resin can also be modified, such as the polyvinyl formal being modified by aldehydes, poly- second also can be used Enol acetal etc..In addition, the degree of polymerization of polyvinyl alcohol resin is usually 1000~10000 or so, preferably 1500~ 5000 or so.

Film obtained by polyvinyl alcohol resin is film-made is used by the former material film as polarizing film 11.For by polyvinyl alcohol It is the method for resin film, can use well known method film.For the film thickness of former material film, if it is considered that by resulting inclined The thickness of vibration piece 11 is set as 15 μm hereinafter, being then preferably 5~35 μm or so, more preferably 5~20 μm.If the film thickness of former material film It is 35 μm or more, then needs to improve stretching ratio when production polarizing film, in addition the dimensional contraction of resulting polarizing film 11 has change Big trend.On the other hand, if the film thickness of former material film be 5 μm hereinafter, if implement stretch when operability reduce, have and manufacturing In be prone to cutting etc. not good situations trend.

Polyvinyl alcohol resin film be uniaxially stretched can before the dyeing of dichroism pigment, with dyeing simultaneously or It is carried out after dyeing.In the case where being uniaxially stretched after dyeing, this is uniaxially stretched can or boric acid processing preceding in boric acid processing Middle progress.Alternatively, it is also possible to be uniaxially stretched in these multiple stages.

When being uniaxially stretched, polyvinyl alcohol resin film can be carried out the different roller of peripheral speed with uniaxial manner It stretches, hot-rolling also can be used and stretched with uniaxial manner.In addition, be uniaxially stretched can be stretched in an atmosphere it is dry Formula stretches, and is also possible to the wet tensile stretched in the state of making polyvinyl alcohol resin membrane swelling using solvent.It draws Stretching multiplying power is usually 3~8 times or so.

As the method for dyeing polyvinyl alcohol resin film with dichroism pigment, such as can use polyethenol series Resin film is impregnated in the method in the aqueous solution containing dichroism pigment.As dichroism pigment, specifically, using iodine, two Color organic dyestuff.It should be noted that polyvinyl alcohol resin film preferably first implements the dipping of Xiang Shuizhong before dyeing processing Processing.

In the case where using iodine as dichroism pigment, generally use polyvinyl alcohol resin film immersion in containing iodine And the method dyed in the aqueous solution of potassium iodide.The content of iodine in the aqueous solution is usually in every 100 parts by weight water 0.01~1 parts by weight or so.In addition, the content of potassium iodide is 0.5~20 parts by weight or so usually in every 100 parts by weight water. The temperature of aqueous solution used in dyeing is usually 20~40 DEG C or so.In addition, dip time in the aqueous solution is (when dyeing Between) it is usually 20~1800 seconds or so.

On the other hand, it in the case where using dichroic dye as dichroism pigment, generallys use polyethenol series Resin film is impregnated in the aqueous solution containing water-soluble dichroic dye and the method for dyeing.Dichroic dye in the aqueous solution Content usually in every 100 parts by weight water be 1 × 10^-4~10 parts by weight or so, preferably 1 × 10^-3~1 parts by weight or so. The aqueous solution can contain the inorganic salts such as sodium sulphate as dyeing assistant.The temperature of dichroic dye aqueous solution used in dyeing Usually 20~80 DEG C or so.In addition, dip time (dyeing time) in the aqueous solution is usually 10~1800 seconds or so.

It usually can be by will be through hyperchromatic polyethenol series tree using the boric acid processing after the dyeing of dichroism pigment Adipose membrane is impregnated in the aqueous solution of boronic acid containing to carry out.

The amount of boric acid in the aqueous solution of boronic acid containing is 2~15 parts by weight or so usually in every 100 parts by weight water, preferably For 5~12 parts by weight.In the case where using iodine as dichroism pigment, the aqueous solution of the boronic acid containing preferably comprises potassium iodide. The amount of potassium iodide in the aqueous solution of boronic acid containing is 0.1~15 parts by weight or so usually in every 100 parts by weight water, preferably 5 ~12 parts by weight or so.Dip time in the aqueous solution of boronic acid containing is usually 60~1200 seconds or so, preferably 150~ 600 seconds or so, more preferably 200~400 seconds or so.The temperature of the aqueous solution of boronic acid containing is usually 50 DEG C or more, preferably 50 ~85 DEG C, more preferably 60~80 DEG C.

Boric acid treated polyvinyl alcohol resin film is usually by carry out washing process.Washing process can for example pass through by Through perboric acid handle polyvinyl alcohol resin film immersion Yu Shuizhong and carry out.The temperature of water in washing process is usually 5~ 40 DEG C or so.In addition, dip time is usually 1~120 second or so.

Implement to be dried after washing, obtains polarizing film 11.Air drier can be used in drying process, far infrared adds Hot device carries out.The temperature of drying process is usually 30~100 DEG C or so, and preferably 50~80 DEG C.The time of drying process is logical It is often 60~600 seconds or so, preferably 120~600 seconds.

In addition, polyvinyl alcohol resin film in the manufacturing process of polarizing film 11 selected from stretch, dyeing, boric acid processing, At least one process in washing step and drying process for example can be according to recording in Japanese Unexamined Patent Publication 2012-159778 Method carry out.In the method that the document is recorded, using coating of the polyvinyl alcohol resin on base material film, it is formed into partially The polyvinyl alcohol resin layer of vibration piece 11.

In the present invention, constitute the polarizing film 11 of polarization plates with a thickness of 15 μm or less.By the way that the thickness of polarizing film 11 is set For 15 μm hereinafter, the convergent force of polarizing film itself also can reduce, therefore falling off under hot environment can also be prevented.The present invention Middle polarizing film 11 is preferably 13 μm or less, or 10 μm or less.It is examined from being easy to assign desired optical characteristics this point Consider, the thickness of polarizing film 11 is usually 2 μm or more.According to the present invention, thin to 15 μm hereinafter, can also even if the thickness of polarizing film 11 With the curling of inhibition layer stack.

(protective film 20,21)

Protective film 20 be configured on the basis of polarizing film 11 with 30 side opposite side of adhesive phase, be configured at visible side Protective film.Protective film 21 is the protective film that can be configured between polarizing film 11 and adhesive phase 30.

The puncture strength of protective film 20 is 3.0gf/ μm or more, preferably 3.5gf/ μm or more, more preferably 4.0gf/ μm More than.Upper limit value is not particularly limited, however usually 15.0gf/ μm or less, or 10.0gf/ μm or less.Passing through will The puncture strength of protective film 20 is set as above range, and makes the aftermentioned model of creep power of adhesive phase 30 Yu stripping film 60 It encloses, can reduce the curling of laminated body.

The puncture strength of protective film can measure as shown below.In puncture test, using being equipped with tip diameter 1mm The testing machine of the needle of φ, 0.5R.Two fixtures for offering circular hole used in center clamp protective film, and protective film is fixed on In testing machine.Make needle relative to protective film across the hole of the fixture vertical decline, intensity when measurement protective film ruptures.Examination The condition of testing be set as 23 ± 3 DEG C of temperature in the environment of, puncture speed 0.33cm/ seconds.Puncture test is carried out to 12 test films, by it Average value divided by protective film thickness, it is possible thereby to find out the puncture strength of the per unit film thickness of protective film.Have in protective film In the case where hard conating, puncture strength is measured in the state of foring hard conating.

The moisture permeability of protective film 20 is preferably 600g/m²R is hereinafter, more preferably 550g/m for 24 hours²R or less for 24 hours.Lower limit Value is not particularly limited, however usually 0g/m²R or more for 24 hours is 10g/m in more typical situation²R or more for 24 hours, can also Think 100g/m²R or more for 24 hours.By the way that the moisture permeability of protective film 20 is set as above range, the moisture of polarization plates can reduce The amplitude that the environment of rate and surrounding accordingly changes.As a result, it is possible to reduce the expansion or shrinkage of polarization plates, reduce laminated body Curling.The moisture permeability of protective film can use agar diffusion method specified in JIS Z 0208 (カ ッ プ method), in 40 DEG C of temperature, relatively It is measured under conditions of humidity 90%.In the case where protective film has hard conating, surveyed in the state of foring hard conating Determine moisture permeability.

Protective film 20,21 is for example made of resin film, can be further made of transparent resin film.Particularly preferably by saturating The excellent material such as bright property, mechanical strength, thermal stability, water preventing ability is constituted.It, can also in the case where laminated body has hard conating To use protective film 20 as the substrate for forming hard conating.It is so-called transparent to refer to transmissivity in visible light region in this specification It is 80% or more.In addition, the solidification of actinic energy ray curable resion composition also can be used as protective film 20,21 Layer, brightness enhancement film, phase difference film.

In the case where protective film 20,21 are laminated in the two sides of polarizing film respectively, mutually the same film is can be used in protective film, Also film different from each other can be used.

As the resin for forming protective film 20,21, it is not particularly limited, for example, by methyl methacrylate system It is resin, polyolefin-based resins (chain polyolefin-based resins, cyclic polyolefin hydrocarbon system resin), polyvinyl chloride resin, cellulose-based Resin, phenylethylene resin series, acrylonitrile/butadiene/styrene system resin, acrylonitrile/phenylethylene resin series, polyvinyl acetate It is resin, polyvinylidene chloride resin, polyamide resin, polyacetals system resin, polycarbonate-based resin, Noryl It is resin, polybutylene terephthalate (PBT) system resin, PET series resin, polysulfones system resin, polyethers The film of the formation such as sulfone system resin, polyarylate system resin, polyamidoimide system resin and polyimides system resins.

These resins can be used alone, or be applied in combination two or more.In addition, these resins can also carry out arbitrarily Appropriate polymer modification after use, as the polymer modification, for example, include copolymerization, crosslinking, molecular end Modified, stereoregularity control and mixing the case where along with reaction between not similar polymers etc. are modified.

In them, as the material of protective film 20,21, preferably comprise selected from cellulose-based resin, polycarbonate-based tree At least one in rouge, polyolefin-based resins, PET series resin and methyl methacrylate system resin Kind.Polyolefin-based resins described herein include chain polyolefin-based resins and cyclic polyolefin hydrocarbon system resin.

So-called methyl methacrylate system resin is the polymerization of the methyl methacrylate units comprising 50 weight % or more Object.The content of methyl methacrylate units is preferably 70 weight % or more, or 100 weight %.Methyl methacrylate Ester units are that the polymer of 100 weight % is methyl methacrylate homopolymerization obtained by polymerizeing methyl methacrylate individually Object.

The methyl methacrylate system resin can usually make with the monofunctional monomer of methyl methacrylate principal component It polymerize in the presence of radical polymerization initiator and obtains.In polymerization, polyfunctional monomer, chain can also as needed turned Agent is moved to coexist.

As can be not particularly limited, with the monofunctional monomer of methyl methacrylate copolymer for example, first Base ethyl acrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, first Methacrylic acid other than the methyl methacrylates such as base 2-EHA and 2-hydroxyethyl methacrylate Esters；Methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, propylene The esters of acrylic acid such as sour 2- ethylhexyl and acrylic acid 2- hydroxy methacrylate；2- (hydroxymethyl) methyl acrylate, 3- The hydroxyls such as (hydroxyethyl) methyl acrylate, 2- (hydroxymethyl) ethyl acrylate and 2- (hydroxymethyl) butyl acrylate Base alkylacrylate；The unsaturation acids such as methacrylic acid and acrylic acid；The halogeno-benzenes second such as chlorostyrene and bromstyrol Alkenes；The substituted phenylethylenes class such as vinyltoluene and α-methylstyrene；The unsaturated nitriles such as acrylonitrile and methacrylonitrile； The unsaturated acids anhydride such as maleic anhydride and citraconic anhydride；And the unsaturations such as phenyl maleimide and N-cyclohexylmaleimide Acid imide etc..Such monomer can use individually, and can also be applied in combination two or more.

As can be not particularly limited, with the polyfunctional monomer of methyl methacrylate copolymer for example, second Glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tetrem two Alcohol two (methyl) acrylate, nine ethylene glycol, two (methyl) acrylate and ten tetraethylene glycol two (methyl) acrylate etc. Monomer obtained by two terminal hydroxyls of ethylene glycol or its oligomer are esterified with acrylic or methacrylic acid；By propylene glycol or Monomer obtained by two terminal hydroxyls of its oligomer are esterified with acrylic or methacrylic acid；Neopentyl glycol two (methyl) propylene Acid esters, (methyl) acrylate of hexylene glycol two and butanediol two (methyl) acrylate etc. are by the hydroxyl propylene of dihydric alcohol Monomer obtained by acid or methacrylated；By bisphenol-A, the alkylene oxide adducts or their halogen substituents of bisphenol-A Two terminal hydroxyls be esterified with acrylic or methacrylic acid obtained by monomer；Trimethylolpropane and pentaerythrite etc. is more Monomer obtained by first alcohol is esterified with acrylic or methacrylic acid and the open loop addition third on the terminal hydroxyl of these polyalcohols Monomer obtained by the epoxy group of olefin(e) acid ethylene oxidic ester or glycidyl methacrylate；In succinic acid, adipic acid, to benzene two Formic acid, phthalic acid, their the upper open loop addition of the binary acid and their alkylene oxide adducts etc. such as halogen substituents Monomer obtained by the epoxy group of glycidyl acrylate or glycidyl methacrylate；(methyl) allyl acrylate； And divinyl aromatic compounds such as divinylbenzene etc..Wherein, it is preferable to use ethylene glycol dimethacrylate, tetrem Diol dimethacrylate and neopentylglycol dimethacrylate.

Reacting between the functional group that further progress has been copolymerized with resin also can be used in methyl methacrylate system resin And the resin being modified.As the reaction, for example, the carbomethoxy of methyl acrylate and 2- (hydroxymethyl) propylene The carboxyl of separating methanol condensation reaction or acrylic acid and 2- (hydroxymethyl) acrylic acid first in the macromolecular chain of the hydroxyl of sour methyl esters Dehydration condensation etc. in the macromolecular chain of the hydroxyl of ester.

So-called PET series resin refers to the 80mol% or more of repetitive unit by terephthalic acid (TPA) The resin that glycol ester is constituted, also may include other dicarboxylic acid components and diol component.As other dicarboxylic acid components, Be not particularly limited, for example, M-phthalic acid, 4,4 '-dicarboxyl diphenyl, 4,4 '-benzophenonedicarboxylic acids, Bis- (4- carboxyl phenyl) ethane, adipic acid, decanedioic acid and Isosorbide-5-Nitrae-dicarboxyl butylcyclohexane etc..

It as other diol components, is not particularly limited, propylene glycol, butanediol, neopentyl glycol, diethyl two can be enumerated Alcohol, cyclohexanediol, the ethylene oxide adduct of bisphenol-A, polyethylene glycol, polypropylene glycol and poly- 1,4-butanediol etc..

These dicarboxylic acid components, diol component can be applied in combination two or more as needed.Alternatively, it is also possible to and with pair Hydroxybenzoic acid, to hydroxycarboxylic acids such as beta-hydroxy ethoxybenzoic acids.In addition, also can be used as other copolymer compositions A small amount of dicarboxylic acid component containing amido bond, urethane bond, ehter bond or carbonic acid ester bond etc. or diol component.

As the manufacturing method of PET series resin, can use makes terephthalic acid (TPA) and ethylene glycol The method of (and other dicarboxylic acids used as needed or other glycol) direct polycondensation, the dialkyl ester for making terephthalic acid (TPA) Ester exchange reaction retraction is carried out with ethylene glycol (and dialkyl ester or other glycol of other dicarboxylic acids used as needed) Poly- method and make the glycol ester of terephthalic acid (TPA) (and other dicarboxylic acids used as needed) (and according to need Other diol esters to be used) polycondensation in the presence of a catalyst method etc..In addition it is also possible to which it is poly- to carry out solid-state as needed It closes, improves molecular weight, or reduce low molecular weight compositions.

Cyclic polyolefin hydrocarbon system resin is by the cyclic olefin list of such as norbornene and other cyclopentadiene derivants etc Resin obtained by body polymerize in the presence of a catalyst.Using such cyclic polyolefin hydrocarbon system resin be easily obtained with it is aftermentioned to The protective film of fixed length of delay, therefore preferably.

As cyclic polyolefin hydrocarbon system resin, for example: by cyclopentadiene and olefines or (methyl) acrylic acid Or its esters by norbornene obtained by diels Alder reaction or derivatives thereof as monomer carry out ring-opening metathesis polymerization, Followed by resin obtained by hydrogenation；To pass through Di Er by dicyclopentadiene and olefines or (methyl) acrylic acid or its esters Tetracyclododecen obtained by this Alder reaction or derivatives thereof carries out ring-opening metathesis polymerization as monomer, followed by hydrogenation Obtained by resin；Make in norbornene, tetracyclododecen, their derivative and other cyclic olefin monomers extremely Few two kinds of monomers are carried out similarly ring-opening metathesis copolymerization, followed by resin obtained by hydrogenation；In norbornene, Fourth Ring 12 Addition copolymerization chain olefin and/or the aromatic compound with vinyl on the cyclic olefin of alkene or their derivative etc Resin obtained by object etc..

The typical case of chain polyolefin-based resins is polyethylene-based resin and polypropylene-based resin.Wherein it is possible to suitably Use the homopolymer of propylene；Or the ratio copolymerization using propylene as main body and with 1~20 weight %, preferably 3~10 weight % Copolymer obtained by co-monomer that can be copolymerized therewith, such as ethylene.

Polypropylene-based resin can contain alicyclic saturated hydrocarbon resin.By containing alicyclic saturated hydrocarbon resin, it is easy to control Length of delay processed.The content of alicyclic saturated hydrocarbon resin is set as 0.1~30 weight % relative to polypropylene-based resin to be advantageous Way, preferred content are 3~20 weight %.If the content of alicyclic saturated hydrocarbon resin, can not less than 0.1 weight % The effect of control length of delay is fully obtained, on the other hand, if its content is greater than 30 weight %, it is likely that over time The exudation of alicyclic saturated hydrocarbon resin is generated from protective film.

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, wrap cellulose-containing acetic acid esters, propionic ester, butyrate, with And the resin of their mixed ester etc..Wherein, preferably tri acetyl cellulose membrane, diacetyl cellulose film, cellulose ethanoate third Acid esters film and cellulose acetate butyrate film etc..

For being made for by methyl methacrylate system resin, PET series resin, polyolefin It is the method for the protective film that resin and cellulose-based resin etc. are adhered to polarizing film, as long as properly selecting and each resin Corresponding method, is not particularly limited.For example, to made of metal band or can be roused using the resin that will be dissolved in solvent Solvent seasoning removing is obtained the solvent cast method of film by upper curtain coating；And by the way that resin is heated to its melting temperature or more And the extrusion by melting of film is obtained from die head extrusion, cooling after being kneaded.In the extrusion by melting, squeezing for monofilm can be Out, in addition it is also possible to extrusion while multilayer film.It can also be by the way that the film formed with the material be stretched and/or is shunk Processing etc., and assign phase difference value.

Protective film 20,21 can also contain additive as needed.As additive, for example, lubricant, anti- Adhesion agent, heat stabilizer, antioxidant, photostabilizer, impact resistance modifying agent etc..Protective film 20,21 preferably with polarizing film Before fitting, implement saponification process, sided corona treatment or corona treatment etc..

The film used as protective film 20,21 can easily buy commercially available product, if it is methyl methacrylate system tree Adipose membrane then indicates that Sumipex (Sumitomo Chemical Co's system), Acrylite (registrar can be enumerated respectively with trade name Mark), Acryprene (registered trademark) (the above are Mitsubishi Rayon Co. Ltd.'s systems), Delaglas (registered trademark) (Asahi Chemical Industry Co. Ltd. system), Paraglas (registered trademark), Comoglas (registered trademark) (the above are Co., Ltd.'s Kuraray systems), with And Acryviewa (registered trademark) (Nippon Shokubai Co., Ltd's system) etc..If it is polyolefin-based resins film, then respectively with commodity Name indicates, can enumerate Zeonor (registered trademark) (Japanese Zeon Co., Ltd.), Arton (registered trademark) (JSR plants of formula meetings Society) etc..It if it is PET series resin film, is then indicated respectively with trade name, Novaclear can be enumerated (registered trademark) (Mitsubishi chemical Co., Ltd's system) and Supreme Being people A-PET piece (Teijin Chemicals, Ltd.'s system) etc..If it is poly- third Alkene resin film, then indicated respectively with trade name, can enumerate FILMAXCPP film (FILMAX corporation), Suntox (registrar Mark) (SUN TOX Co. Ltd. system), Tohcello (registered trademark) (Tohcello Co. Ltd. system), Toyobo Pylen Film (registered trademark) (Toyo Boseki K.K's system), Torayfan (registered trademark) (Toray film process Co. Ltd. system), Nippon Polyace (Japanese Polyace Co. Ltd. system) and too pavilion (registered trademark) FC (Futamura Chemical Co. Ltd. system) etc..In addition, then indicating respectively with trade name if it is cellulose-based resin film, Fujitac (note can be enumerated Volume trade mark) TD (Fuji Photo Film Co., Ltd.'s system) and KC2UA and Konica Minolta TAC Film KC (KonicaMinolta Co. Ltd. system) etc..

In the case where forming protective film 20,21 using above-mentioned resin film, resin film (does not include the thickness of hard conating etc. Degree.) thickness be usually 1~50 μm or so, preferably 10~40 μm, or 10~30 μm.

The cured layer of actinic energy ray curable resion composition can be used as protective film 20,21.As activity The cured layer of energy ray-curable resin combination can be enumerated by shining to actinic energy ray curable resion composition Penetrate active energy beam and cured layer.As actinic energy ray curable resion composition, can enumerate comprising polymerism The composition of compound and Photoepolymerizationinitiater initiater, the composition comprising light reactive resin include binder resin and light reaction The composition etc. of property crosslinking agent.As polymerizable compound, photo-curable epoxy monomer, light-curable acrylic can be enumerated It is the photopolymerization monomer of monomer, photo-curable carbamate system monomer, photo-curable liquid-crystal compounds etc, from light The oligomer of polymerizable monomer.As Photoepolymerizationinitiater initiater, can enumerate comprising the active energy beam because of ultraviolet light etc It irradiates and generates free radicals, the initiator of the substance of the reactive species of cation or anion etc.As including polymerism chemical combination It is preferable to use include photo-curable epoxy for the actinic energy ray curable resion composition of object and Photoepolymerizationinitiater initiater The composition of monomer and light cationic polymerization initiator.

The cured layer of actinic energy ray curable resion composition can be obtained by carrying out following process, that is, Active energy ray-curable is coated on polarizing film, on protective film or in the alignment films that are formed on polarizing film or protective film Property resin combination after, process is dried as needed, then carry out by irradiate active energy beam make active-energy The cured curing process of ray-curable resin combination.The active energy beam irradiated can be solid according to active energy beam Change property resin type from ultraviolet light, electron beam, near ultraviolet ray, visible light, near infrared ray, infrared ray, X-ray etc. suitably Selection.As active energy beam, preferably ultraviolet light or electron beam, from operation especially simplicity and high-energy can be readily available This point consideration, preferably ultraviolet light.

Above-mentioned composition can contain additive.As additive, ion trap agent, antioxidant, chain can be enumerated and turned Move agent, sensitizer, tackifier, thermoplastic resin, filler, flow modifier, plasticizer, defoaming agent etc..

For protective layer of the cured layer of actinic energy ray curable resion composition as the surface of protection polarizing film It is useful.Since the cured layer of actinic energy ray curable resion composition can be made thinner than common protective film, It is effective for the slimming of polarization plates.By using photo-curable liquid-crystal compounds, active-energy can be penetrated as described later The cured layer of line hardening resin composition assigns desired phase difference.

The thickness of the cured layer of actinic energy ray curable resion composition is preferably 0.01~20 μm, more preferably 0.01~10 μm, further preferably 0.01~5 μm.

Phase difference can be assigned to protective film 20,21.In the case where protective film 20,21 has phase difference, protective film 20, 21 can be the plate of λ/4, the plate of λ/2, positive c plate etc..Phase difference value Re (550) in face when the plate of λ/4 is its wavelength 550 [nm] meets The layer of 100nm≤Re (550)≤200nm relationship.The plate of λ/4, which can be shown, meets Re (450) < Re (550) < Re (650) Inverse wave length dispersibility.The plate of λ/2 is that Re (550) meets 210nm≤Re (550)≤300nm layer.Positive c plate meets Nz > Nx= Phase difference value Rth (λ) satisfaction -300nm≤Rth (550) of thickness direction when the relationship of Ny, preferably its wavelength X [nm]≤- The relationship of 20nm.

In the case where protective film 20,21 has phase difference, protective film 20,21 can be formed by a kind of phase separation layer, It can be formed by a variety of phase separation layers.In the case where phase separation layer is formed by a variety of phase separation layers, preferred 1/4 wavelength plate and 1/ The combination of 2 wavelength plates, the combination of 1/4 wavelength plate and positive c plate.

As the material for having dephased protective film 20,21 is formed, the resin film being illustrated above, liquid crystal can be enumerated Layer obtained by compound is cured etc..In the case where forming phase difference film by resin film, wherein being used as the preferably poly- carbon of material Acid esters system resin, annular ethylene series resin, phenylethylene resin series, cellulose-based resin.By to the film formed by the material into Row stretches and/or contraction is processed etc., can assign phase difference value.

For the type of liquid-crystal compounds, it is not particularly limited, however according to its shape, rodlike type (stick can be classified as Shape liquid-crystal compounds) and discoid type (disc-like liquid crystal compound, disc liquid-crystal compounds).In addition, there is low molecule type respectively And polymer electrolyte.It should be noted that so-called macromolecule, generally refers to the compound that the degree of polymerization is 100 or more.To given base Coating forms film comprising having the composition of the liquid-crystal compounds of polymerizable group and being orientated liquid-crystal compounds on material.It is logical It crosses and curing process (ultraviolet irradiation (photo-irradiation treatment) or heat treatment) is implemented to resulting film, phase difference can be manufactured Layer.By selecting thickness according to material, desired phase difference can be assigned.Manufactured phase separation layer can be transferred to Such as on polarizing film or on other films.

Brightness enhancement film can be used as protective film 20.The thickness of brightness enhancement film be preferably 35 μm hereinafter, more preferably 30 μm with Under.

As brightness enhancement film, can be used with the emergent light from light source (backlight) is separated into transmission-polarizing light and anti- Penetrate the polarization light conversion element of the function of polarised light or scattering polarization light.The brightness enhancement film can use from polarization by reflection light or dissipate The return light for penetrating the backlight of polarised light improves the outgoing efficiency of rectilinearly polarized light.

As brightness enhancement film, for example, anisotropic emission polarizing film.It, can be with as anisotropic emission polarizing film Rectilinearly polarized light, the anisotropy for the rectilinearly polarized light for reflecting another direction of vibration for enumerating one direction of vibration of transmission are multiple Film.As the multiple film of anisotropy, for example, the trade name " APF " of 3M corporation.In addition, as anisotropy Reflecting polarizer can enumerate the complex of cholesteric liquid crystal layers Yu the plate of λ/4.As the complex, day east electrician can be enumerated The trade name " PCF " of Co. Ltd. system.In addition, reflecting grating polarizing film can be enumerated as anisotropic emission polarizing film.Make For reflecting grating polarizing film, it can enumerate and is implemented by microfabrication and can also project polarization by reflection light in visible light region for metal Metal lattice reflecting polarizer.The brightness enhancement film wherein preferably formed by the multiple film of anisotropy.

(hard conating 40)

Protective film 20 preferably has hard conating 40 with 60 side opposite side of stripping film.It, can be with by forming hard conating 40 Reduce the moisture permeability of protective film 20, increase puncture strength.

The sheet resistance value for being formed with the protective film 20 of hard conating 40 is preferably 1.0 × 10⁷Ω/ or more and 1.0 × 10¹⁰ Ω/ is hereinafter, more preferably 1.0 × 10⁸Ω/ or more and 1.0 × 10¹⁰Ω/ or less.By being set as such sheet resistance Value, furthermore adhesive phase 30 has the function of anti-static electricity interference, multiple acquisition, product can not be caused poorly to effectively manufacture aobvious Showing device.Sheet resistance value can use the method recorded in aftermentioned embodiment and be measured.In order to be assigned to hard conating 40 Above-mentioned sheet resistance characteristic, as long as such as making to contain anti-static electricity interference agent in hard conating 40.As anti-static electricity interference agent, by In the puncture strength for being easy to improve protective film 20, therefore it is preferable to use electroconductive particles.It, can not by using electroconductive particle Increase puncture strength with increasing the film thickness of hard conating.

As anti-static electricity interference agent, quaternary ammonium salt can be enumerated, pyridiniujm, there are the cationic groups such as primary~tertiary amino Various cationic compounds；With anionic properties bases such as sulfonate group, sulfuric ester alkali, phosphate alkali, phosphonic acids alkali The anionic property compound of group；The amphoteric compounds such as amino acid system, amidosulphuric acid ester system；Amino alcohol system, glycerol system, polyethylene glycol The nonionics compounds such as system；The organo-metallic compound of the alkoxide of tin and titanium etc；The gold of their acetylacetonate etc Belong to complex compound etc..

Alternatively, it is also possible to use with tertiary amino, quaternary ammonium group or metallo-chelate portion and photopolymerization monomer or oligomeric The photopolymerizable compounds such as the organo-metallic compound of object or coupling agent with optical polymerism functional group etc are quiet as preventing Electrical interference agent.These anti-static electricity interference agent are also possible to ionic liquid.

As anti-static electricity interference agent, electric conductive polymer can also be enumerated.It is not particularly limited as electric conductive polymer, For example, poly- (to the penylene) of aromatic series conjugated system, the polypyrrole of hetero ring type conjugated system, polythiophene, aliphatic conjugated system Polyacetylene, the polyaniline of the conjugated system containing hetero atom, mixed type conjugated system poly- (phenylacetylene), multiple as having in the molecule The multichain type conjugated system of the conjugated system of conjugated chain is total to as by conjugated polymer chain above-mentioned with macromolecular grafted or block is saturated Poly- high molecular conductive composite body etc..

As anti-static electricity interference agent, electroconductive particle can also be enumerated.As the concrete example of electroconductive particle, can enumerate Particle comprising metal oxide.As such metal oxide, for example, antimony doped tin oxide (referred to as: ATO), p-doped Tin oxide (referred to as: PTO), tin-doped indium oxide (referred to as: ITO), Al-Doped ZnO (referred to as: AZO), gallium-doped zinc oxide (referred to as: GZO)、ZnO、CeO₂、Sb₂O₅、SnO₂、In₂O₃And Al₂O₃。

Hard conating 40 can be lived by the way that actinic energy ray curable resion composition is coated on resin film rear, irradiation Property energy-ray and make curing of coating to be formed.Use light-cured resin etc. as active energy ray-curable resin In the case of, Photoepolymerizationinitiater initiater is usually contained in coating fluid.As Photoepolymerizationinitiater initiater, can enumerate comprising because ultraviolet light it The irradiation of the active energy beam of class and generate free radicals, the initiator of the substance of the reactive species of cation or anion etc. Anti-static electricity interference agent is preferably 2~40 relative to the content of all solids ingredient of actinic energy ray curable resion composition Quality %, more preferably 20~35 mass %.Composition may include organic solvent equal solvent, levelling agent, dispersing agent, anti-fouling agent Deng other additives.

The coating method of composition can be gravure coating process, micro gravure coating method, rolling method, stick coating method, scrape cutter painting The known methods such as cloth method, air knife coating method, kiss coating, die coating method.

The active energy beam irradiated can be according to the type of active energy ray-curable resin from ultraviolet light, electronics It is properly selected in beam, near ultraviolet ray, visible light, near infrared ray, infrared ray, X-ray etc..As active energy beam, preferably Ultraviolet light or electron beam from operation especially simplicity and can be readily available the consideration of high-energy this point, preferably ultraviolet light.

The thickness of hard conating 40 is for example preferably 0.01~20 μm, more preferably 1~10 μm, further preferably 3~7 μ m.If the thickness of hard conating is big, has and be easy to the case where generating curling because of cure shrinkage.

Hard conating 40 can also be endowed anti-glare, light diffusing, antireflection other than being for example endowed hard painting propert Etc. functions.Hard conating 40 can be formed by single layer, can also be formed by multiple layers.The case where hard conating 40 is formed by multiple layers Under, it can also include antiglare layer, light diffusion layer, anti-reflection layer, low-index layer, high refractive index layer etc..

Antiglare layer is the reflected glare (Ying り Write body for preventing ambient light), given concave-convex is imparted to surface The optical functional layer of shape.Antiglare layer can use following method etc. for example to be formed, that is, (a) method: on transparent resin film After being coated with the coating fluid containing particle and resin, make coating layer solidification (forming the concave-convex surface as caused by particle) as needed； (b) method: coating fluid (can also containing organic filler and/or inorganic particulate) of the coating containing resin and particle on resin film Afterwards, solidify coating layer as needed while pushing the mold with given surface unevenness profile to coating layer, to painting Layer of cloth assigns concave-convex surface.

As the resin for constituting antiglare layer, as long as the resin with translucency, is just not particularly limited.For example, in addition to Other than the solidfied material that can be active energy ray-curable resin as described above, the solidification of thermosetting resin can also be Object；Thermoplastic resin；Metal alkoxide based polymer etc..Wherein, it is suitably for the solidfied material of active energy ray-curable resin.? Use uv curing resin etc. as in the case where active energy ray-curable resin, it is same as described above, in coating fluid In contain Photoepolymerizationinitiater initiater (radical polymerization initiator), and irradiate active energy beam, thus solidify coating layer.

As thermosetting resin, the thermosetting property amino first comprising the pure and mild isocyanate prepolymer of acrylic acid multielement can be enumerated Acid ester resin, phenolic resin, urea-melamine resin, epoxy resin, unsaturated polyester resin, polyorganosiloxane resin etc..As thermoplastic Property resin, may be exemplified out the material of above-mentioned protective film.

As metal alkoxide based polymer, the silicon oxide series matrix using the material of silicon alkoxide system as raw material can be used Deng.Specifically, metal alkoxide based polymer can be the water of the alkoxy silanes such as tetramethoxy-silicane, tetraethoxysilane Solve inorganic system or organic and inorganic compound collaboration matrix obtained by object dehydrating condensation.

Use thermosetting resin solidfied material, metal alkoxide based polymer as translucent resin in the case where, applying After cloth coating fluid, it is sometimes desirable to heat.

One or more kinds of particles can be used in particle.In order to obtain desired anti-glare, other optical characteristics, Type, partial size, refractive index, the content etc. of particle can be suitably adjusted.

Light diffusion layer is for the purpose of expanding visual angle of liquid crystal display device etc., for making the backlight by liquid crystal cells The optical functional layer of light diffusion.Light diffusion layer for example can use on transparent resin film coating containing particle (light diffusing agent) and After the coating fluid of translucent resin, as needed form the cured method of coating layer.It, can as particle and translucent resin With the identical material of the material for using with being described to antiglare layer.

In order to obtain desired light diffusing, the type of transparent resin film, translucent resin can be suitably adjusted Type, the type of particle, partial size, refractive index, content, thickness of light diffusion layer etc..

Anti-reflection layer is the optical functional layer for reducing or preventing the reflection of ambient light, such as can be and have low refraction The layer of rate layer.Alternatively, it is also possible to being to be also equipped with high refractive index layer and/or middle refraction between transparent resin film and low-index layer The multilayered structure of rate layer.

Low-index layer can use coating containing above-mentioned actinic energy ray curable resion composition solidfied material, After the coating fluid of the translucent resins such as metal alkoxide based polymer and inorganic particulate, make the cured method of coating layer as needed It is formed.As inorganic particulate, for example, LiF (refractive index 1.4), MgF (refractive index 1.4), 3NaFAlF (refractive index 1.4), AlF (refractive index 1.4), Na₃AlF₆The low refracting particles such as (refractive index 1.33), hollow silica particle etc..

High refractive index layer can use solidfied material, the metal alcohol that coating contains above-mentioned active energy ray-curable resin After the coating fluid of the translucent resins such as salt based polymer and inorganic particulate and/or organic filler, as needed solidify coating layer Method formed.

(adhesive phase 30)

Adhesive phase 30 is the layer for polarization plates to be fitted in the display elements such as liquid crystal cells, organic EL display element. The creep power of adhesive phase 30 and aftermentioned stripping film 60 is 4.5N or more and 15N or less.By by adhesive phase 30 and removing The creep power of film 60 is set as 4.5N or more and the puncture strength of protective film 20 is set as range above-mentioned, can reduce stacking The curling of body.You can think of it because when laminated body is intended to bend backward, by subtracting between polarization plates 10 and stripping film 60 Small offsetting can reduce the curling of laminated body.Consider that adhesive phase 30 and the creep power of stripping film 60 are preferably from such viewpoint 5.0N or more, more preferably 6.0N or more.On the other hand, by the way that the creep power of adhesive phase 30 and stripping film 60 is set as 15N Hereinafter, the tilting of the stripping film 60 as caused by the deterioration of bonding force can be inhibited.Consider from such viewpoint, adhesive phase 30 and stripping Creep power from film 60 is preferably 14N or less.

Referring to Fig. 3, the measuring method of the creep power of stripping film and adhesive phase is illustrated.By made laminated body It is cut into the size of 110mm (length of double-head arrow 82) × 15mm (length of double-head arrow 81).So that polarization plates are mutual with stripping film The length (length of the length and double-head arrow 84 of double-head arrow 83 and) of the part of overlapping is the mode of 15mm in the long side direction, From the position of midpoint (part shown in dotted line 80) 7.5mm apart from longitudinal direction respectively cut off remove end side stripping film and partially Vibration plate.The test film of shape as shown in Figure 3 is made as described.Test film is installed on cupping machine and measures creep Power.Specifically, by make the longitudinal direction of test film perpendicular to ground in a manner of, utilize upside chuck hold test film long side One end in direction, holds another end using downside chuck.So that distance was broadened between chuck with 1mm/ minutes speed Mode, move downside chuck downwards, until moving distance reaches 5mm during it is on the move needed for maximum masterpiece It is measured for creep power.

Such as adhesive phase 30 and stripping film 60 can be controlled by adjusting the additive amount of the crosslinking agent of adhesive phase Creep power.In addition, since creep power is also influenced by aftermentioned stripping film 60, the side of the demoulding processing of adjustment stripping film 60 Method is also effective method.

By making adhesive phase 30 have the function of anti-static electricity interference, and hard conating has given sheet resistance value, can Not cause multiple acquisition, product poorly to effectively manufacture liquid crystal display device.In order to assign antistatic to adhesive phase 30 Interference function, as long as such as making to contain anti-static electricity interference agent in adhesive phase 30.That is, containing antistatic in adhesive phase 30 In the case where agent interfering, it may be said that adhesive phase 30 has the function of anti-static electricity interference.As anti-static electricity interference agent, can be used The anti-static electricity interference agent stated.Anti-static electricity interference agent possessed by anti-static electricity interference agent possessed by adhesive phase and hard conating can be with Using identical substance, different substances also can be used.

The thickness of adhesive phase 30 is preferably 5~40 μm, more preferably 10~30 μm, further preferably 15~25 μm.

As the adhesive of formation adhesive phase 30, such as use can be properly selected with acrylic acid series polymeric compounds, silicon Ketone based polymer, polyester, polyurethane, polyamide, polyvingl ether, vinyl acetate/vinyl chloride copolymer, improved polyalkene, Adhesive of the polymer such as the rubber series such as epoxy, fluorine system, natural rubber, synthetic rubber as basic polymer.As bonding Agent, particularly preferred optical transparence is excellent, the adhesion characteristic that shows appropriate wetability, coherency and cementability, weatherability, The excellent adhesive such as heat resistance.

In the case where using base polymer of the acrylic acid series polymeric compounds as adhesive, the weight of acrylic acid series polymeric compounds Average molecular weight Mw is preferably 500,000~2,500,000, more preferably 1,000,000~2,000,000.If weight average molecular weight is 500,000 or more, The durability of the adhesive phase in the environment of high temperature and humidity can be improved.If weight average molecular weight be 2,500,000 hereinafter, if be coated with and contain There is the operability when coating fluid of adhesive to become good.With the weight average molecular weight Mw and number-average molecular weight of acrylic acid series polymeric compounds The molecular weight distribution (Mw/Mn) that the ratio of Mn indicates is preferably 2~10.Weight average molecular weight Mw and number-average molecular weight Mn is to utilize gel The polystyrene scaled value of permeation chromatography (GPC) method measurement.

Adhesive preferably also contains crosslinking agent.As crosslinking agent, may be exemplified out the metal ion more than as divalent and The crosslinking agent of carboxylic metallic salt is formed between carboxyl at it；Amide is formed between carboxyl as polyamine compounds and at it The crosslinking agent of key；The crosslinking agent of ester bond is formed between carboxyl as polyepoxides or polyalcohol and at it；As polyisocyanate Cyanate esters and the crosslinking agent for forming amido bond between carboxyl at it.Wherein, preferred polyisocyanate compound.It hands over Joining agent relative to the additive amount of 100 mass parts of base polymer is preferably 0.15~1 mass parts.Crosslinking agent can only add one Kind, it also can be used together and add two or morely.

Adhesive preferably comprises silane coupling agent.By containing silane coupling agent, adhesive phase and adherend can be improved Adaptation.Silane coupling agent is preferably 0.01~10 mass parts relative to the additive amount of 100 mass parts of base polymer, more excellent It is selected as 0.05~2 mass parts, further preferably 0.1~1 mass parts.Silane coupling agent can only add one kind, can also be simultaneously With adding two or morely.

Adhesive may include for assign light scattering particle, pearl (resin bead, bead etc.), glass fibre, Resin, tackifier, filler (metal powder or other inorganic powders etc.), antioxidant, ultraviolet light other than base polymer are inhaled Receive the additives such as agent, dyestuff, pigment, colorant, defoaming agent, corrosion-resistant agent, Photoepolymerizationinitiater initiater.

(surface protection film 50)

Surface protection film 50 may include the adhesive phase 52 of base material film 51 and stacking thereon.Surface protection film 50 is to use Film in the surface of protection polarization plates 10, the quilt usually after polarization plates 10 to be fitted in such as display element or other optical components Removing is peeled off together with its adhesive phase 52.

Surface protection film 50 has more stiffness generally compared with the protective films such as brightness enhancement film 20,21, for stripping film 60 It is important for the raising of fissility.The thickness of surface protection film 50 is the bonding of the thickness and stacking of base material film 51 thereon The aggregate value of the thickness of oxidant layer 52, preferably 30 μm or more, more preferably 50 μm or more.On the other hand, if surface protection film 50 thickness is excessive, then when removing stripping film 60, is easy to generate removing between surface protection film 50 and polarization plates 10, because The thickness of this surface protection film 50 is preferably 100 μm hereinafter, more preferably 70 μm or less.

Base material film 51 is preferably thermoplastic resin film.The thermoplastic resin of thermoplastic resin film is constituted for example, poly- The polyolefin-based resins of vinylite, polypropylene-based resin etc；Cyclic polyolefin hydrocarbon system resin；Polyethylene terephthalate The polyester based resin of ester, polyethylene naphthalate etc；Polycarbonate-based resin；(methyl) acrylic resin etc..Base Material film can be single layer structure, be also possible to multilayered structure.

The thickness of base material film 51 can be 20~150 μm (for example, 30~80 μm, preferably 30~60 μm).For bonding The composition of oxidant layer 52 substantially quotes the description of the adhesive phase 30 possessed by polarization plates 10 above-mentioned.

Especially the storage modulus of adhesive phase 52 at 80 DEG C preferably 0.15MPa hereinafter, more preferably 0.14MPa with Under, further preferably 0.10MPa or less.In general, storage modulus at 80 DEG C of adhesive phase 52 is 0.01MPa or more.It is viscous The determination of viscoelasticity of commercially available determination of viscoelasticity device, such as REOMETRIC corporation can be used in the storage modulus of mixture layer Device " DYNAMIC ANALYZER RDA II " is measured.

Surface protection film 50 may include anti-static electricity interference agent.Such as anti-static electricity interference can be contained in adhesive phase 52 Agent.It can also be substituted in adhesive phase 52 containing anti-static electricity interference agent, or therewith, in the viscous with stacking of base material film 51 The anti-static electricity interference layer containing anti-static electricity interference agent is arranged in the face of the face opposite side of mixture layer 52.As anti-static electricity interference agent, The anti-static electricity interference agent that can be added in hard conating can be enumerated.

(stripping film)

Stripping film 60 be in order to by adhesive phase 30 fit in display element (such as liquid crystal cells, organic EL element) or The film protecting its surface before other optical components and temporarily attaching.Stripping film 60 can also be by implementing by silicon its one side The demoulding of the release agents such as ketone system, fluorine system etc. is handled to adjust the creep power with adhesive phase 30.Stripping film 60 is by passing through demoulding The thermoplastic resin film of reason is constituted, and can be demoulded process face at it and is bonded adhesive phase 30.

The thermoplastic resin for constituting stripping film 60 for example can be the polyethylene-based resin of polyethylene etc, polypropylene Polypropylene-based resin, polyethylene terephthalate or polyethylene naphthalate etc polyester based resin etc..Stripping Thickness from film 60 is, for example, 10~50 μm.

Peeling force between adhesive phase 30 and stripping film 60 be preferably 10mN/25mm or more and 200mN/25mm hereinafter, More preferably 40mN/25mm or more and 100mN/25mm or less.By being set as the peeling force of such range, stripping film can be inhibited Tilting, improve the fissility of stripping film.Peeling force, which is used, to be set as 300mm/ minutes for peeling rate, is set as peel angle Value at 180 °.

(manufacturing method of laminated body)

It is bonded each other by for example pressing from both sides above-mentioned illustrated component across adhesive layer or adhesive phase stacking and, it can be with Make laminated body.Each component can be cut to be laminated after given shape, can also by each component in a manner of roll-to-roll layer Poststack cuts to give shape.The shape of laminated body is not particularly limited, such as can be made and the length of long side is set as 4.0~ 18.0cm, the rectangular shape that the length of short side is set as to 3.0~9.0cm.Aperture processing can be carried out to laminated body, or by corner It is processed as R shape.

Adhesive layer is for the layer that such as polarizing film 11 is Nian Jie with protective film 20,21, as formation adhesive layer Bonding agent can enumerate active energy ray-curable bonding agent and water system bonding agent.Alternatively, it is also possible to use above-mentioned activity Energy ray-curable resin combination.

Using water system bonding agent, preferably after being bonded polarizing film 11 with protective film 20,21, in order to remove Water contained in water system bonding agent and implement to be allowed to dry process.After drying process, it can be set for example on 20~45 DEG C of left sides The curing step that right temperature is cured.

Using active energy ray-curable bonding agent, polarizing film 11 is being bonded with protective film 20,21 Afterwards, process is dried as needed, then carries out keeping active energy ray-curable viscous by irradiating active energy beam Connect the cured curing process of agent.The light source of active energy beam is not particularly limited, however it is preferred that has below wavelength 400nm Shine the ultraviolet light being distributed, specifically, Cooper-Hewitt lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, super-pressure mercury can be used Lamp, chemical lamp, black light lamp, microwave-excitation mercury vapor lamp, metal halide lamp etc..

When polarizing film 11 to be bonded with protective film 20,21, the binding face of their at least any one party can be implemented Saponification process, sided corona treatment, corona treatment etc..

It can be used for the thickness of the adhesive phase by polarizing film 11 and protective film 20,21 (especially brightness enhancement film) stacking for example It can be set to 3~15 μm.The material for forming adhesive phase can choose the material for carrying out illustrating in above-mentioned adhesive phase 30.

Adhesive phase 30 usually by by the solution coating of adhesive on the release sheet of stripping film 60 etc and doing It is dry and formed.The release sheet for being equipped with adhesive phase can be pressed from both sides and be laminated in polarization plates 10 across adhesive phase 30.Utilizing removing Film 60 can obtain laminated body without re-pasting 60 ground of stripping film as in the case where release sheet.Using stripping film 60 with In the case that outer material is as release sheet, release sheet can be first removed, then stripping film 60 is laminated on adhesive phase 30.

Surface protection film 50 can be laminated on protective film 20 in advance in the manufacturing process of polarization plates 10, can also made It is laminated on protective film 20 after making polarization plates 10.Tension when by adjusting coating surface protective film 50, also can control stacking The curling of body, however the control direction of tension is limited to a direction.On the other hand, according to the present invention, due to the control in curling Adhesive phase 30 and protective film 20 are utilized in system, therefore anisotropy is small in controlling elements, a direction can be not limited to Ground control curling.

(manufacturing method of display device)

Fig. 2 is the schematic sectional view of an example that the layer for the display device for indicating to be utilized laminated body is constituted.In Fig. 2, omit Backlight, polarization plates of back side etc..Display device shown in Fig. 2 (a) is pressed from both sides in a face of display element 70 across bonding Oxidant layer 30 is laminated with the successively polarization plates comprising protective film 20, polarizing film 11 and adhesive phase 30.Dress is shown shown in Fig. 2 (b) Set display element 70 a face folder across adhesive phase 30 be laminated with successively comprising be formed with hard conating 40 protective film 20, The polarization plates of polarizing film 11, protective film 21 and adhesive phase 30.

By removing stripping film 60 from laminated body, the adhesive phase 30 exposed is laminated in display element 70, and can be with Polarization plates are laminated in display element 70.In polarization plates in the case where having surface protection film 50 on protective film, it can incite somebody to action After polarization plates are laminated in display element 70, surface protection film 50 is removed.

As display element 70, liquid crystal cells, organic EL element etc. can be enumerated.In image display device, this is utilized A little image-displaying members, can control image.Coplanar conversion (IPS) mode, perpendicular alignmnet can be used for example in liquid crystal cells (VA) mode, multi-domain vertical alignment (MVA) mode, continuous fireworks shape arrange (CPA) mode, mixing arranges nematic (HAN) mode, The liquid crystal list of the arbitrary patterns such as twisted-nematic (TN) mode, super twisted nematic (STN) mode, light compensated birefringence (OCB) mode Member.

Organic EL element successively has transparent electrode layer, luminescent layer and an electrode layer, and luminescent layer can be because by from transparent electrode Layer and electrode layer apply voltage and generate light.As the example for the material for constituting organic luminous layer, p-phenylene vinylene can be enumerated The material of system, polyfluorene system and polyvinyl carbazole system.In addition, luminescent layer can have the layer of the different layer of multiple illuminant colours Stack or in the layer of some pigment doped with the mixed layer of different pigments.In addition, organic EL element can have hole note Enter the functional layers such as layer, hole transmission layer, electron injecting layer, electron transfer layer, equipotential plane forming layer, charge generating layer.

[embodiment]

Hereinafter, using embodiment, the present invention is described in more detail, however the present invention is not limited by these examples.Example In, the % for indicating content or usage amount and part are exactly quality criteria as long as no particularly pointing out.It should be noted that embodiment Used in evaluation method is as follows shown.

(1) thickness:

It is measured using the digital micrometer MH-15M of Co., Ltd. Nikon.

(2) the creep power of stripping film and adhesive phase:

Referring to Fig. 3, the measuring method of the creep power of stripping film and adhesive phase is illustrated.By made laminated body It is cut into the size of 110mm (length of double-head arrow 82) × 15mm (length of double-head arrow 81).So that polarization plates are mutual with stripping film The length (length of the length and double-head arrow 84 of double-head arrow 83 and) of the part of overlapping is the mode of 15mm in the long side direction, From the position of midpoint (part shown in dotted line 80) 7.5mm apart from longitudinal direction respectively cut off remove end side stripping film and partially Vibration plate.Resulting test film is shape as shown in Figure 3.Test film is installed on cupping machine (Autograph (registrar Mark) AG-1S MO (console mode) type, Shimadzu Scisakusho Ltd's system) in and determine creep power.Specifically, so that examination Mode of two edge directions perpendicular to ground for testing piece holds an end of the longitudinal direction of test film with upside chuck, under Side chuck holds another end.Distance keeps downside chuck downward in a manner of speed broadening in 1mm/ minutes between making chuck Fang Yidong.Required maximum power is measured as creep power on the move during until reaching 5mm using moving distance.

(3) puncture strength:

The puncture test of protective film is carried out.In puncture test, the needle for being equipped with tip diameter 1mm φ, 0.5R has been used Kato Tech Co. Ltd. system Portable compressed tester " KES-G5 syringe needle penetrating force measure specification ".It is opened used in center Two fixtures equipped with circular hole clamp protective film, and protective film is fixed on testing machine.Make needle with passing through the hole of the fixture Perpendicular to protective film decline, intensity when measurement protective film ruptures.In the environment of 23 ± 3 DEG C of temperature, puncturing speed It is carried out under 0.33cm/ seconds determination conditions.The puncture strength measured in puncture test is to carry out puncture examination to 12 test films It tests, using its average value.Using the method recorded in above-mentioned (1), the thickness of protective film is measured, the per unit film of protective film is found out Thick puncture strength.

(4) moisture permeability:

Protection is determined under conditions of 40 DEG C of temperature, relative humidity 90% using agar diffusion method specified in JIS Z 0208 The moisture permeability of film.

(5) peeling force:

Use Shimadzu Scisakusho Ltd as the Autograph (registered trademark) of desk type accurate universal testing machine AGS-X, the peeling force for determining stripping film between adhesive phase that polarization plates have.Peeling rate is set as 300mm/ points Peel angle is set as 180 ° by clock.

(6) sheet resistance value:

Using Mitsubishi, Co., Ltd. chemistry ANALYTECH MCP-HT450 determine protective film sheet resistance value (Ω/ □).In the case where protective film has hard conating, in the state of being formed with hard conating, sheet resistance value is determined.

(7) the tilting evaluation of stripping film:

Made laminated body is placed under ambient temperature and moisture environment, evaluate whether based on the following benchmarks stripping film with Tilting (the phenomenon that stripping film falls off from the adhesive phase of polarization plates) is produced between polarization plates.

Zero: after manufacture laminated body, at the time point by 9 months, without generating tilting in stripping film；

×: after manufacture laminated body, at the time point by 9 months, tilting is produced in stripping film.

(8) evaluation crimped:

Made laminated body is cut into 7 inches of diagonal line of size (155mm × 87.2mm), in 25 DEG C of temperature, humidity Damping 3 hours or more in the environment of 60%RH.Laminated body is placed on flat platform, puts counterweight in the center of laminated body, surveyed Make the maximum value of the tilting height of end.The evaluation is carried out to longitudinal direction and short side direction, the value after being averaged is as volume Qu Liang.The evaluation of curling is determined based on following benchmark.

Zero: absolute value is less than 5.0mm

×: absolute value 5.0mm

(Production Example 1: the production of polarizing film)

Thick 30 μm of polyvinyl alcohol film (99.9 moles of average degree of polymerization about 2400, saponification degree % or more) is drawn using dry type Stretch that be uniaxially stretched be about 5 times, then after keeping tense situation unchangeably to impregnate 1 minute in 60 DEG C of pure water, at 28 DEG C in iodine/iodine Change and is impregnated 60 seconds in the aqueous solution that potassium/water weight ratio is 0.05/5/100.Thereafter, at 72 DEG C in potassium iodide/boric acid/water weight It is impregnated 300 seconds in the aqueous solution that amount ratio is 8.5/8.5/100.Next after cleaning 20 seconds with 26 DEG C of pure water, in 65 DEG C of dryings, Obtain 12 μm of thickness of the polarizing film for being adsorbed with iodine on polyvinyl alcohol film and being orientated.

(Production Example 2: the production of water system bonding agent)

The carboxy-modified polyvinyl alcohol for dissolving 3 parts by weight relative to 100 parts by weight of water (is obtained from Co., Ltd. Kuraray Trade name " KL-318 "), the daiamid epoxy as water-soluble epoxy resin of 1.5 parts by weight is added into the aqueous solution Be additive (from Taoka Chemical Industries Co. Ltd. obtain trade name " Sumirez Resin (registered trademark) 650 (30) ", The aqueous solution of 30 weight % of solid component concentration), prepare water system bonding agent.

(the polymerization example of acrylic resin 1,2)

Into the reaction vessel for having cooling tube, nitrogen ingress pipe, thermometer and blender, with use level shown in table 1 Put into acrylic monomer.Acetic acid is added in a manner of being 150 parts relative to 100 parts of total weight of acrylic monomer thereto Ethyl ester prepares 40% solution of acrylic monomer.Be set as with the air in nitrogen replaceable equipment it is oxygen-free simultaneously Interior temperature is increased to 55 DEG C, 0.14 part of azodiisobutyronitrile (polymerization initiator) is dissolved in 10 parts of ethyl acetate and obtains by addition Solution whole amount.With temperature holding 1 hour after adding polymerization initiator, interior temperature is then being remained 54~56 DEG C While ethyl acetate is added continuously into reaction vessel with 17.3 parts/hr of adding speed, in the concentration of acrylic resin Stop the addition of ethyl acetate at the time of reaching 35%, then with the temperature to from the addition for starting ethyl acetate by 12 Until hour.It is eventually adding ethyl acetate and the concentration of acrylic resin is adjusted to 20%, prepare acrylic resin Ethyl acetate solution 1 and 2.The Weight-average molecular that the polystyrene found out using the GPC of resulting acrylic resin is converted Amount Mw and Mw/Mn is recorded in table 1.

[table 1]

[table 1]

BA: butyl acrylate

MA: methyl acrylate

HEA: acrylic acid 2- hydroxy methacrylate

AA: acrylic acid

PEA: acrylic acid 2- phenoxy ethyl

MEA: acrylic acid 2- methoxy acrylate

BMAA:2- butoxy methyl acrylamide

(preparation of adhesive phase)

Adhesive phase below is prepared.

Adhesive phase A: relative to 100 parts of solid component of acrylic resin solution 2, cooperate as crosslinking agent 1.2 parts of CORONATE L (TOSOH Co. Ltd. system), KBM-403 (SHIN-ETSU HANTOTAI's chemical industry strain formula meeting as silane coupling agent Society's system) 0.5 part, then methyl ethyl ketone is added in a manner of making solid component concentration 14%, use blender (YAMATO science strain formula " the Three-One Motor " of commercial firm), it is stirred 30 minutes with 300rpm, prepares adhesive composition A.It will bonding Agent composition A is coated in such a way that the adhesive layer after making to dry is with a thickness of 20 μm using sizing applicator implemented demoulding processing Polyethylene terephthalate film (trade name " SP-PLR382190 " of LINTEC Co., Ltd. is referred to as stripping film) takes off Mould process face is dried 1 minute at 100 DEG C and produces adhesive phase A.

Adhesive phase B: relative to 100 parts of solid component of acrylic resin solution 1, cooperate as crosslinking agent 0.6 part of CORONATE HXR (TOSOH Co. Ltd. system), KBM-403 (SHIN-ETSU HANTOTAI's chemical industry strain formula as silane coupling agent Commercial firm's system) 0.5 part, then methyl ethyl ketone is added in a manner of making solid component concentration 14%, use blender (YAMATO science strain " the Three-One Motor " of formula commercial firm), it is stirred 30 minutes with 300rpm, prepares adhesive composition A.It will glue Mixture composite A is coated in such a way that the adhesive layer after making to dry is with a thickness of 20 μm using sizing applicator implemented demoulding processing Polyethylene terephthalate film (trade name " SP-PLR382190 " of LINTEC Co., Ltd., be referred to as stripping film) Process face is demoulded, dried 1 minute at 100 DEG C and produces adhesive phase B.

Adhesive phase C: other than the additive amount of CORONATE L is changed to 0.4 part, using identical as adhesive phase A Preparation method produce adhesive phase C.

Adhesive phase D: other than the additive amount of CORONATE L is changed to 0.3 part, using identical as adhesive phase A Method produce adhesive phase D.

Adhesive phase E: other than the additive amount of CORONATE L is changed to 0.2 part, using identical as adhesive phase B Method produce adhesive phase E.

Adhesive phase F: other than the additive amount of CORONATE L is changed to 0.1 part, using identical as adhesive phase B Method produce adhesive phase F.

Adhesive phase G: other than the additive amount of CORONATE L is changed to 0.05 part, using with adhesive phase B phase Same method produces adhesive phase G.

(preparation of protective film)

Protective film below is prepared.

Protective film A: be formed on cellulose-based resin film (KC2UA) hard conating film (Toppan Printing Co., Ltd's system, It is 32 μm thick).Hard conating contains the anti-static electricity interference agent formed by electroconductive particle.

Protective film B: be formed on cellulose-based resin film (KC2UA) hard conating film (Toppan Printing Co., Ltd's system, It is 32 μm thick).Hard conating does not contain anti-static electricity interference agent.

Protective film C: cellulose-based resin film (Konica Minolta Co. Ltd. system, KC2UA, 25 μm of thickness).

Protective film D: annular ethylene series resin film (Japanese Zeon Co. Ltd. system, ZF14-013,13 μm of thickness).

(embodiment 1)

Protective film A is bonded across water system bonding agent in the one side folder of resulting polarizing film.In the another side of polarizing film, folder every Identical bonding agent be bonded protective film D.After fitting, it is allowed to dry and produces polarization plates.When being bonded to protective film A, make Become the binding face with polarizing film with the face for the face opposite side for being formed with hard conating.When being bonded protective film D, to protective film D Binding face implement sided corona treatment.

The coating adhesive B on protective film D and form adhesive phase B.On adhesive phase B, it is laminated by polyester based resin Form, implemented the stripping film (38 μm thick) of demoulding processing.It will be provided with polyester based resin film (38 μm thick) and adhesive phase (20 μ M) surface protection film presss from both sides on the hard conating that the adhesive phase is fitted in that protective film A has.It produces as described The laminated body constituted with surface protection film/protective film A/ polarizing film/protective film D/ adhesive phase B/ stripping film layer.

The sheet resistance value of protective film A is 1.0 × 10¹⁰Ω/, the peeling force between stripping film and adhesive phase B are 70mN/25mm.It will be shown in result set in table 2.

(embodiment 2~6, comparative example 1~3)

Other than protective film A and adhesive phase B are changed to content shown in table 1, produce same as Example 1ly Laminated body.Peeling force between adhesive phase and stripping film is 50mN/25mm in embodiment 2~6 and comparative example 2, is being compared It is 150mN/25mm in example 1, is 30mN/25mm in comparative example 3.In addition, in embodiment 2~5 and comparative example 1,3, protection The sheet resistance value of film is 1.0 × 10¹⁰Ω/□.Embodiment 6 and the sheet resistance value of comparative example 2 are greater than 1.0 × 10¹³Ω/, It can not thus measure.

It will be shown in table 2 in above result set.

[table 2]

[table 2]

Industrial availability

According to the present invention it is possible to provide a kind of curling that can reduce the laminated body comprising polarization plates and stripping film and It is difficult to happen the laminated body of the tilting of stripping film, therefore useful.

The explanation of symbol

10 polarization plates, 11 polarizing films, 20,21 protective films, 30 adhesive phases, 40 hard conatings, 50 surface protection films, 51 substrates Film, 52 adhesive phases, 60 stripping films, 70 display elements, 80 dotted lines, 81,82,83,84 double-head arrows, 100,101 laminated bodies, 200, 201 display devices.

Claims (6)

1. a kind of laminated body is the laminated body for being sequentially laminated with polarization plates and stripping film,

The polarization plates successively include protective film, polarizing film and adhesive phase,

Described adhesive layer is configured at the position adjacent with stripping film,

The polarizing film with a thickness of 15 μm hereinafter,

The puncture strength of the protective film is 3.0gf/ μm or more,

The creep power of described adhesive layer and the stripping film is 4.5N or more and 15N or less.

2. layered product according to the claim 1, wherein

The moisture permeability of the protective film is 600g/m²R or less for 24 hours.

3. laminated body according to claim 1 or 2, wherein

The protective film has hard conating with stripping film side opposite side.

4. laminated body according to claim 3, wherein

The sheet resistance value of the hard conating is 1.0 × 10⁷Ω/ or more and 1.0 × 10¹⁰Ω/ or less.

5. laminated body according to any one of claims 1 to 4, wherein

The protective film includes to be selected from cellulose-based resin, polycarbonate-based resin, polyolefin-based resins, poly terephthalic acid second At least one of diol ester system resin and methyl methacrylate system resin.

6. laminated body according to any one of claims 1 to 5, wherein

There is surface protection film with stripping film side opposite side on the basis of the polarization plates.