CN101713838A - Polarizing plate and liquid crystal display - Google Patents

Abstract

The present invention provides a polarizing plate and a liquid crystal display. The polarizing plate is provided with a polarizing film formed by polyvinyl alcohol series resin, and stretched polyethylene glycol terephthalate films stacked on one surface of the polarizing plate by a first adhesive layer, wherein the first adhesive layer is composed of a condensate layer of a solvent-free active energy line solidification composition containing epoxy compounds.

Description

Polaroid and liquid crystal indicator

Technical field

The present invention relates to polaroid and the liquid-crystal apparatus that uses it.

Background technology

In recent years, power consumption low, with low voltage operating, light-duty and slim LCDs as mobile phone, personal digital assistant device, computing machine with the information of monitor and televisor etc. with display device and popularize rapidly.And then, be accompanied by the development of liquid crystal technology, the LCDs of various patterns has been proposed, the problem of LCDs such as the response speed of Cun Zaiing, contrast and visual angle solved just gradually in the past.

On the other hand, be subjected to the market strong request with the further slim lightness of liquid crystal indicator, the slimming of liquid crystal panel, diffuser plate, backlight unit and the drive IC etc. of formation liquid crystal indicator, miniaturization are also in continuous progress.Under this situation, also require the slimming of 10 μ m units as the polaroid of the parts that constitute liquid crystal panel.Therefore, because as the diaphragm of polaroid and normally used tri acetyl cellulose membrane was 80 μ m～120 μ m in the past, thereby require to carry out to the more replacement of film.

But; with the tri acetyl cellulose membrane is the polaroid of diaphragm; be wanting in through the humidity resistance of being everlasting, cold-resistant thermal shock; particularly as mentioned above by the film formed polaroid of the protection of filming; under high temperature environment how wet, high low temperature repeatedly, cause the deterioration of polarizing properties sometimes, or light polarizing film sustains damage.

, can enumerate through the reason that the humidity resistance of being everlasting etc. is wanting in as polaroid: as moisture permeability, the water-intake rate height of the tri acetyl cellulose membrane of its inscape; And for gluing hydrophilic light polarizing film and diaphragm, the general water system tackifier that uses in its tackifier.Therefore, for example, in the Japanese kokai publication hei 7-77608 communique (patent documentation 1), the method for using moisture permeability, annular ethylene series resin film that water-intake rate is lower to replace tri acetyl cellulose membrane is disclosed.In addition, for example, in TOHKEMY 2007-102179 communique (patent documentation 2), the moisture permeability that makes tri acetyl cellulose membrane, the method that absorptivity reduces are disclosed.And then, for example, in TOHKEMY 2005-208456 communique (patent documentation 3), the method with the tackifier improvement is disclosed also.

But because annular ethylene series resin is expensive usually, thereby present situation is to be used for the higher phase retardation film of added value, only also do not carry out as the use of diaphragm.In addition,, need be provided with the surface-treated layer that is defined in this method, lack widely-used property sometimes for the low humidifying of tri acetyl cellulose membrane itself, low suctionization.And then the method for improvement tackifier also still is being short of aspect its moisture-proof thermal effect sometimes.

In addition, replace tri acetyl cellulose membrane and will also carrying out as the research of diaphragm than the polyethylene terephthalate film of low-moisture permeability and low water absorbable.But the polyethylene terephthalate film is compared with tri acetyl cellulose membrane, sometimes in existing problems aspect the adaptation of light polarizing film.In addition,, and tri acetyl cellulose membrane is compared as the polaroid of diaphragm, sometimes existing problems aspect the permanance under harsh and unforgiving environments the polaroid of polyethylene terephthalate film as diaphragm.

And then, being accompanied by popularizing of liquid crystal indicator, the market strong request reduces cost.Be subjected to this demand, and the functions of components that will constitute liquid crystal indicator integrates to reduce number of components, ready-made reduction of fructufy, throughput rate raising.For example, in TOHKEMY 2002-277623 communique (patent documentation 4), the blooming that diffuser plate, light collecting plate and prismatic lens etc. can be integrated is disclosed.But in polaroid, the restriction of the raw material that its cost, throughput rate are used is difficult to reduce cost sometimes.

On the other hand; the motion of using the tackifier of no-solvent type in the applying of light polarizing film and diaphragm is also arranged; for example in TOHKEMY 2004-245925 communique (patent documentation 5); the tackifier that is situated between and is formed by the composition that with the epoxy resin that does not contain aromatic rings is principal ingredient is disclosed, the technology of applying diaphragm on the light polarizing film that polyvinyl alcohol resin forms.

Summary of the invention

Therefore, the object of the present invention is to provide a kind of polaroid, is being in the polaroid of diaphragm with the polyethylene terephthalate film, the adaptation excellence of light polarizing film and polyethylene terephthalate film, and throughput rate is also excellent.In addition, another object of the present invention is to provide environment resistant, the liquid crystal indicator of humidity resistance excellence particularly that uses above-mentioned polaroid.

According to the present invention, a kind of polaroid is provided, it possesses the light polarizing film that is formed by polyvinyl alcohol resin and the stacked stretching polyethylene terephthalate film that is situated between by first adhesive layer on the single face of this light polarizing film, described first adhesive layer is made of the solidfied material layer of the solvent-free active energy ray-curable composition that contains epoxy compound.

When this epoxy compound is the alicyclic epoxy compound, even the also excellent polaroid of permanance under harsh and unforgiving environments can be provided, thereby preferred.

Preferred described active energy ray-curable composition further contains oxetane compound.

Polaroid of the present invention can be on described light polarizing film and the face face opposition side that is laminated with stretching polyethylene terephthalate film, possess Jie by second adhesive layer stacked diaphragm or optical compensation films.Described second adhesive layer preferably is made of the solidfied material layer of the composition identical with above-mentioned stretching polyethylene terephthalate film being glued to active-energy solidification compound on the light polarizing film.

As mentioned above, when stacked diaphragm or optical compensation films, be provided with adhesive phase in polaroid of the present invention, this adhesive phase is layered on this diaphragm or optical compensation films and the face face opposition side that is laminated with described light polarizing film.

In addition, according to the present invention, provide a kind of liquid crystal indicator, it possesses liquid crystal panel, and described liquid crystal panel is that the polaroid that is provided with above-mentioned adhesive phase is situated between by its adhesive phase and liquid crystal cells applying.

Polaroid of the present invention contains epoxy compound by use solvent-free active energy ray-curable composition is as tackifier and make its layer (adhesive layer) that is solidified to form, thereby improves the adaptation of stretching polyethylene terephthalate film and light polarizing film significantly.In addition, because tackifier is solvent-free, thereby does not need the drying process of necessary in the past tackifier, its throughput rate significantly improves.

Embodiment

＜polaroid 〉

Polaroid of the present invention possesses the light polarizing film that is formed by polyvinyl alcohol resin and the stacked stretching polyethylene terephthalate film that is situated between by first adhesive layer on the single face of this light polarizing film.In addition, polaroid of the present invention can be on light polarizing film and the face face opposition side that is laminated with stretching polyethylene terephthalate film, possess Jie by second adhesive layer stacked diaphragm or optical compensation films.Below, polaroid of the present invention is specifically described.

(light polarizing film)

The light polarizing film of Shi Yonging is made through following operation: the operation of the polyvinyl alcohol resin film being carried out uniaxial tension with known method usually in the present invention; By usefulness dichromatism pigment the polyvinyl alcohol resin film is dyeed, and the operation that the dichromatism pigment is adsorbed; The operation that the polyvinyl alcohol resin film that is adsorbed with the dichromatism pigment is handled with boric acid aqueous solution; And the operation of after adopting boric acid aqueous solution to handle, washing.

As polyvinyl alcohol resin, can use polyvinyl acetate is resin saponification and the polyvinyl alcohol resin that obtains.As polyvinyl acetate is resin, except the polyvinyl acetate as leifa, can also enumerate vinyl acetate and can be with the multipolymer of other monomers of its copolymerization etc.As can with other monomers of vinyl acetate copolymerization, for example can enumerate unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class and have acrylic amide of ammonium etc.

The saponification degree of polyvinyl alcohol resin is normally about 85～100 moles of %, preferred 98 moles more than the %.This polyvinyl alcohol resin can be modified, for example also can use through the aldehydes modification and polyvinyl formal, polyvinyl acetal etc.In addition, the degree of polymerization of polyvinyl alcohol resin normally about 1000～10000, preferred about 1500～5000.

The film that this polyvinyl alcohol resin system film is obtained can be used as the original membrane (former anti-Off イ Le system) of light polarizing film and uses.Method with polyvinyl alcohol resin system film is not particularly limited, can be with known method system film.Thickness by the polyethenol series original membrane is not particularly limited, and for example is about 10～150 μ m.

The uniaxial tension of polyvinyl alcohol resin film can carry out before the dyeing of dichromatism pigment, also can carry out simultaneously with dyeing, can also carry out after dyeing.When carrying out uniaxial tension after dyeing, this uniaxial tension can carry out before boric acid is handled, and also can carry out in the boric acid processing procedure.In addition, also can carry out uniaxial tension in these a plurality of stages.

When uniaxial tension, can between the different roller of peripheral speed, carry out uniaxial tension, can also use hot-rolling to carry out uniaxial tension.In addition, uniaxial tension can be the dry type stretching that stretches in atmosphere, can also be the wet type that stretches under the state of polyvinyl alcohol resin film swelling is stretched.Stretching ratio is normally about 3～8 times.

As the method that the polyvinyl alcohol resin film is dyeed with the dichromatism pigment, for example, can adopt the method for polyvinyl alcohol resin film immersion in the aqueous solution that contains the dichromatism pigment.As the dichromatism pigment, particularly can use iodine, dichroic dye etc.In addition, the polyvinyl alcohol resin film was preferably implemented the dip treating in water in advance before dyeing is handled.

When using iodine, adopt the method that dipping polyvinyl alcohol resin film dyes in the aqueous solution that contains iodine and potassium iodide usually as the dichromatism pigment.About the content of iodine in this aqueous solution, be 0.01～1 weight portion with respect to water 100 weight portions usually.In addition, about the content of potassium iodide, be 0.5～20 weight portion with respect to water 100 weight portions usually.The temperature of the aqueous solution of using during dyeing is normally about 20～40 ℃.In addition, the dip time in this aqueous solution (dyeing time) is normally about 20～1800 seconds.

On the other hand, when using dichroic dye, adopt the method that dipping polyvinyl alcohol resin film dyes in containing the aqueous solution of water-soluble dichroic dye usually as the dichromatism pigment.About the content of the dichroic dye in this aqueous solution, be 1 * 10 with respect to water 100 weight portions usually ^-4About～10 weight portions, preferred 1 * 10 ^-3About～1 weight portion.This aqueous solution can also contain inorganic salts such as sodium sulphate as dyeing assistant.The temperature of the dichroic dye aqueous solution that is used to dye is normally about 20～80 ℃.In addition, the dip time in this aqueous solution (dyeing time) is normally about 10～1800 seconds.

Utilize the boric acid behind the dichromatism pigment dyeing to handle, can in the aqueous solution that contains boric acid, carry out by the polyvinyl alcohol resin film immersion that will be colored usually.

About the amount of the boric acid in containing the aqueous solution of boric acid, be about 2～15 weight portions with respect to water 100 weight portions usually, preferred 5～12 weight portions.When using iodine as the dichromatism pigment, this aqueous solution that contains boric acid preferably contains potassium iodide.About the amount of the potassium iodide in containing the aqueous solution of boric acid, be about 0.1～15 weight portion with respect to water 100 weight portions usually, about preferred 5～12 weight portions.Dip time in containing the aqueous solution of boric acid is normally about 60～1200 seconds, and preferred about 150～600 seconds, more preferably about 200～400 seconds.The temperature of aqueous solution that contains boric acid is normally more than 50 ℃, and preferred 50～85 ℃, more preferably 60～80 ℃.

Polyvinyl alcohol resin film after boric acid is handled is implemented washing usually and handles.Washing is handled for example can be by carrying out in water through the polyvinyl alcohol resin film immersion that boric acid is handled.The temperature of water was normally about 5～40 ℃ when washing was handled.In addition, dip time is normally about 1～120 second.

Dried is implemented in the washing back, obtains light polarizing film.Dried can use air drier, far infra-red heater to carry out.Baking temperature is normally about 30～100 ℃, preferred 50～80 ℃.The time of dried is normally about 60～600 seconds, preferred 120～600 seconds.

Drying is handled, and the moisture rate of light polarizing film is reduced to practical level.Its moisture rate is generally 5～20 weight %, preferred 8～15 weight %.If moisture rate is lower than 5 weight %, the then flexible disappearance of light polarizing film, light polarizing film is damage sometimes or fracture after its drying.In addition, if moisture rate surpasses 20 weight %, then the thermal stability of light polarizing film is wanting in sometimes.

The thickness of the light polarizing film that obtains so usually can be about 5～40 μ m.

(stretching polyethylene terephthalate film)

The what is called stretching polyethylene terephthalate film that uses among the present invention, be by the PET series resin with more than one melt extrude make film after, carry out the above monadic stretching membrane of one deck that cross directional stretch forms, or and then carry out longitudinal stretching behind the system film, carry out the above biaxially-stretched film of one deck that cross directional stretch forms then.

So-called PET series resin is meant that 80 moles by repetitive are the resin that ethylene glycol terephthalate constitutes more than the %.The dicarboxylic acid composition and the diol component that can contain other.As other dicarboxylic acid composition, be not particularly limited, for example can enumerate m-phthalic acid,, 4 '-dicarboxyl hexichol, 4 beta-hydroxy ethoxybenzoic acid, 4,4 '-benzophenonedicarboxylic acid, two (4-carboxyl phenyl) ethane, hexane diacid, decanedioic acid and 1,4-dicarboxyl cyclohexane etc.

Diol component as other is not particularly limited, and can enumerate ethylene oxide adduct, polyglycol, polypropylene glycol and the polytetramethylene glycol etc. of propylene glycol, butylene glycol, neopentyl glycol, diethylene glycol, cyclohexane diol, bisphenol-A.

These other dicarboxylic acid composition, other diol component can be used in combination more than 2 kinds as required.In addition, also can and with the hydroxycarboxylic acid of P-hydroxybenzoic acid etc.In addition, as other copolymer composition, also can use dicarboxylic acid composition or the diol component that contains a spot of amido link, urethane bond, ehter bond and carbonic acid ester bond etc.

As the manufacture method of PET series resin, can adopt the method etc. that makes terephthalic acid (TPA) and ethylene glycol (and other dicarboxylic acid as required or other the glycol) method of direct polycondensation, the dialkyl that makes terephthalic acid (TPA) and ethylene glycol (and the dialkyl group of other dicarboxylic acid as required or other glycol) take place to carry out the method for polycondensation after the ester exchange reaction and make glycol ester (and other diol ester as required) polycondensation of terephthalic acid (TPA) (and other dicarboxylic acid as required).

In each polyreaction, can use the polymerization catalyst that comprises antimony system, titanium system, germanium system or aluminium based compound, perhaps comprise the polymerization catalyst of above-mentioned complex chemical compound.

The monomer that this polymeric reaction condition can be used in combination, catalyzer, reaction unit and suitably select as the rerum natura of target resin, be not particularly limited, for example, temperature of reaction is generally about 150 ℃～about 300 ℃, preferred about 200 ℃～about 300 ℃, more preferably from about 260 ℃～about 300 ℃.In addition, its pressure is generally atmospheric pressure～about 2.7Pa, and wherein, preferably the second half in reaction is a depressurised side.

Polyreaction is undertaken by following: stir under above-mentioned high temperature, high reduced pressure, thereby elimination reaction things such as glycol, alkylate or water are sloughed volatilization.

In addition, polyplant can be to finish in a reactive tank, perhaps also a plurality of reactive tanks can be linked.At this moment, according to the degree of polymerization limit reactant is transferred the limit between reactive tank usually and carry out polymerization.In addition, can also adopt and have horizontal type reaction unit in polymerization the second half, the method for volatilization is sloughed on limit heating, mixing limit.

Resin after polymerization finishes is after taking out from reactive tank, horizontal type reaction unit under molten condition, after coolings such as drum cooler, salband, pulverizing, obtain with the state of sheet, perhaps import to extruder, be extruded into severing behind the ribbon, obtain with granular state.

And then, can also carry out solid phase as required, and make the molecular weight raising or low molecular weight compositions is reduced.As the low molecular weight compositions that can in the PET series resin, contain, can enumerate the cyclic trimer composition, but the content of this cyclic trimer composition in resin is preferably below the 5000ppm, more preferably below the 3000ppm.If ring-type 3 aggressiveness compositions surpass 5000ppm, then sometimes the optics rerum natura of film is produced harmful effect.

The molecular weight of PET series resin, when representing with the limiting viscosities that resin dissolves is measured under 30 ℃ in the mixed solvent of phenol/tetrachloroethane=50/50 (weight ratio), be generally 0.45～1.0dL/g, preferred 0.50～1.0dL/g, the more preferably scope of 0.52～0.80dL/g.If limiting viscosity is less than 0.45dL/g, the throughput rate when then film is made sometimes reduces or the physical strength of film reduces.In addition, if limiting viscosity surpasses 1.0dL/g, then sometimes in the film manufacturing polymkeric substance melt extrude poor stability.

In addition, the PET series resin can contain adjuvant as required.As adjuvant, for example, can enumerate lubricant, anti blocking agent, thermal stabilizer, antioxidant, antistatic agent, photostabilizer and resistance to impact modifying agent etc.Its addition does not preferably bring dysgenic scope to the optics rerum natura.

The PET series resin is in order to cooperate these adjuvants and in order to carry out film moulding described later, to use with the graininess shape of the granulation with extruder usually.Size, the shape of particle are not particularly limited, and are generally high, diameter and are following cylindric, spherical or flat spherical of 5mm.

The PET series resin forming that obtains like this is membranaceous, carries out stretch processing, thereby can make the high polyethylene terephthalate film of physical strength transparent, homogeneous.As its manufacture method, be not particularly limited, for example can adopt method as described below.

At first, to melt extrusion apparatus, it is above and carry out fusion to be heated to fusing point with the pellet supply that is formed by pet resin of drying.Then, the resin of fusion is extruded from the mouth mould, on the rotation drum cooler, carried out quench cooled and solidify, obtain the unstretching film of non-crystal state in fact in the mode that becomes the temperature below the glass transition temperature.This melt temperature is according to the fusing point of the PET series resin that uses, extruder and definite, is not particularly limited, and is generally 250～350 ℃.

In addition,, preferably improve the adaptation of film and rotation drum cooler, preferred static driving fit method or the liquid coating driving fit method of applying that adopt in order to improve the planarity of film.What is called applies static driving fit method, normally the upper face side at film is provided with wire electrode on the direction vertical with the flow direction of film, by this electrode is applied the DC voltage of about 5～10kV and gives film with static charge, thereby make the method for rotation drum cooler and the adaptation raising of film.In addition, so-called liquid coating driving fit method is the part (for example only with the part of film two end in contact) on whole surface by liquid being coated equably the rotation drum cooler or surface, thereby improves the method for the adaptation of rotation drum cooler and film.

The PET series resin that uses can mix resin structure, the different resin of composition more than 2 kinds as required.For example, can enumerate and to have cooperated the particle and the situation of not having the particle mixing use that cooperates of particulate filler, ultraviolet light absorber or antistatic agent etc. as anti blocking agent.

In addition, the stacked number of extruded film can be more than 2 layers as required.For example, can enumerate and prepare to have cooperated as the particle of the particulate filler of anti blocking agent and do not have the particle that cooperates, supply to identical mouth mould, extrude by the situation of the film of 2 kinds of 3 layers of formations of " cooperating filler/nothing cooperation/cooperation filler " etc. by different extruders.

Above-mentioned unstretching film, the temperature more than glass transition temperature is usually at first to extruding the direction longitudinal stretching.Draft temperature is generally 70～150 ℃, and preferred 80～130 ℃, more preferably 90～120 ℃.In addition, stretching ratio is generally 1.1～6 times, preferred 2～5.5 times.The physical strength of polyethylene terephthalate film has not enough tendency if this stretching ratio less than 1.1 times, then stretches.In addition, if surpass 6 times, there is not enough situation sometimes in then horizontal intensity when practicality.This stretching can once finish, and also can carry out as required and several times.Usually, when repeatedly stretching, the also preferred stretching ratio that adds up to is above-mentioned scope.

The longitudinal stretching film that so obtains can be heat-treated subsequently.Then, can also carry out relaxation processes as required.This heat treatment temperature is generally 150～250 ℃, and preferred 180～245 ℃, more preferably 200～230 ℃.In addition, heat treatment time is generally 1～600 second, and preferred 1～300 second, more preferably 1～60 second.

The temperature of relaxation processes is generally 90～200 ℃, preferred 120～180 ℃.In addition, slack is generally 0.1～20%, and preferred 2～5%.About the temperature and the slack of this relaxation processes, be mode below 2% temperature when setting slack and relaxation processes at 150 ℃ percent thermal shrinkage preferably with the polyethylene terephthalate film after the relaxation processes.

When obtaining uniaxial tension and biaxially-stretched film, handle the back or, carry out cross directional stretch at longitudinal stretching usually with stenter as required after thermal treatment or relaxation processes.This draft temperature is generally 70～150 ℃, and preferred 80～130 ℃, more preferably 90～120 ℃.In addition, stretching ratio is generally 1.1～6 times, preferred 2～5.5 times.If the stretching ratio of cross directional stretch less than 1.1, then exists because the film strength due to the orientation improves not enough situation sometimes.In addition, if surpass 6 times stretching ratio, then on manufacturing technology, can't realize.

Then, can heat-treat and relaxation processes as required.Heat treatment temperature is generally 150～250 ℃, and preferred 180～245 ℃, more preferably 200～230 ℃.Heat treatment time is generally 1～600 second, and preferred 1～300 second, more preferably 1～60 second.

The temperature of relaxation processes is generally 100～230 ℃, and preferred 110～210 ℃, more preferably 120～180 ℃.In addition, slack is generally 0.1～20%, and is preferred 1～10%, and more preferably 2～5%.About the temperature and the slack of this relaxation processes, be mode below 2% temperature when coming this setting slack and relaxation processes at 150 ℃ percent thermal shrinkage preferably with the polyethylene terephthalate film after the relaxation processes.

In uniaxial tension and biaxial stretch-formed processing, if its stretch processing temperature all surpasses 250 ℃, the situation that exists optical property to reduce sometimes then because resin occurs that hot deterioration or crystallization are excessively carried out.In addition, if draft temperature is subjected to excessive pressure in less than 70 ℃, then exist stretching sometimes, or film solidifies and situation that stretching itself can not be carried out.

In addition, in uniaxial tension and biaxial stretch-formed processing, behind the cross directional stretch,, can heat-treat or carry out stretch processing once more in order to make to be the crooked mitigation of the orientation main shaft of representative through skew of weft (ボ one イ Application グ).By through the orientation main shaft due to the skew of weft with respect to the crooked maximal value of draw direction usually in 45 °, it is relaxed in 30 °, more preferably be in 15 °.If the crooked maximal value of orientation main shaft surpasses 45 °, then in follow-up operation, constitute polaroid and during singualtion, occur the inhomogeneous of optical characteristics between this monolithic sometimes.

At this, so-called draw direction, the big direction of stretching ratio when being meant longitudinal stretching or cross directional stretch.In polyethylene terephthalate film biaxial stretch-formed, the cross directional stretch multiplying power is bigger slightly than longitudinal stretching multiplying power usually, and therefore, this moment, so-called draw direction was meant the direction vertical with the long side direction of described film.In addition, in uniaxial tension, carry out the stretching of horizontal direction as described above usually, therefore, this moment, so-called draw direction was meant the direction vertical with long side direction equally.

In addition, at this, so-called orientation main shaft is meant the molecular orientation direction of the arbitrfary point on stretching polyethylene terephthalate film.In addition, so-called orientation main shaft is crooked with respect to draw direction, is meant the differential seat angle of orientation main shaft and draw direction.And then its maximal value is meant the maximal value of the value on the direction vertical with long side direction.

Above-mentioned orientation main shaft for example can use phase retardation film/optical material testing fixture RETS (big tomb Electronics Co., Ltd system) or molecular orientation meter MOA (prince's instrumentation machine Co., Ltd. system) to measure.

When the stretching polyethylene terephthalate film of Shi Yonging in the present invention, this film are used for the visual side of polaroid, preferably give anti-dazzle property (mist degree).The method of giving anti-dazzle property is not particularly limited, and for example can adopt following method: mix inorganic particles or organic fine particles and the method for membranization in above-mentioned material resin; According to the method for making of above-mentioned multilayer film, by the method for the membranization that stretches at one-sided unstretching film with the layer that has mixed inorganic particles or organic fine particles; Perhaps one-sided at stretching polyethylene terephthalate film is coated on and mixes the coating fluid that inorganic particles or organic fine particles form in the curable resin glue, resin glue solidified and the method etc. of antiglare layer is set.

As the inorganic particulate that is used to give anti-dazzle property, be not particularly limited, for example can enumerate monox, cataloid, aluminium oxide, alumina sol, aluminosilicate, aluminium oxide-silicon oxide composite oxides, porcelain earth, talcum, mica, lime carbonate and calcium phosphate etc.In addition, as organic fine particles, be not particularly limited, for example can enumerate crosslinked polypropylene acid particles, methyl methacrylate/styrene copolymer resin particle, crosslinked polystyrene particle, crosslinked polymethylmethacrylaparticles particle, silicone resin particle and polyimide particle etc.

The haze value of the stretching polyethylene terephthalate film of having given anti-dazzle property that so obtains is preferably in 6～45% scope.If the haze value of stretching polyethylene terephthalate film of having given anti-dazzle property then can not manifest sufficient antiglare effect sometimes less than 6%.In addition, if surpass 45%, the situation of then using the picture of the liquid crystal indicator that this film forms to exist sometimes to cause gonorrhoea, image quality to reduce.

On the above-mentioned stretching polyethylene terephthalate film of having given anti-dazzle property, so can stacked conductive layer, the functional layer of hard conating and low reflection layer etc.In addition, as the resin combination that forms above-mentioned antiglare layer, can also select to have concurrently the resin combination of above-mentioned arbitrary function.

On the other hand, when stretching polyethylene terephthalate film is used for the source backlight of polaroid, can not give anti-dazzle property.At this moment, its haze value is usually less than 6%.But, even do not give anti-dazzle property, also can stacked above-mentioned functional layer.

This haze value is meant according to JIS K 7136, for example uses mist degree/transmissivity meter HM-150 (Murakami K. K.'s dye technology institute system) and the value of mensuration.When the mensuration haze value, in order to prevent the warpage of film, transparent adhesives is given face with anti-dazzle property on for example preferred employing use optics becomes the working sample of surperficial mode with face and glass substrate applying.

On the stretching polyethylene terephthalate film that the present invention uses, only otherwise overslaugh effect of the present invention, just can be in the stacked above-mentioned functional layers in addition such as antiglare layer of single face or two sides.For stacked functional layer, for example can enumerate conductive layer, hard conating, smoothing layer, easy slipization layer, antiblocking layers and easy adhesive layer etc.Wherein, this stretching polyethylene terephthalate film is because Jie is stacked by adhesive layer and light polarizing film, so preferred stacked easy adhesive layer.

The composition that forms easy adhesive layer is not particularly limited, for example can enumerate on skeleton, have the lower lower glass transition temperatures of polar group and molecular weight, polyester based resin, polyurethane series resin or acrylic resin etc.In addition, as required, can contain crosslinking chemical, organic or inorganic filler, surfactant and lubricant etc.

The method that forms the above-mentioned functions layer on stretching polyethylene terephthalate film is not particularly limited, and for example can adopt following method: the method that forms on the film after all stretching process finish; In the operation that PET series is resin stretched, the method that between longitudinal stretching and cross directional stretch operation, forms for example; With face with light polarizing film gluing before or gluing after the method that forms etc.Wherein, from the viewpoint of throughput rate, the preferred method that forms, carries out then cross directional stretch after with PET series resin longitudinal stretching that adopts.

The stretching polyethylene terephthalate film that so obtains can easily obtain commercially available product, for example, represent with trade name respectively, can enumerate " Diafoil ", " Hostaphan ", " Fusion " (more than, Mitsubishi Plastics Inc's system), " Teijin Tetoron Film ", " Melinex ", " Mylar ", " TEFLEX " (more than, Teijin Dupont Films corporate system), " TOYOBO ESTERFILM ", " TOYOBO ESPET FILM ", " COSMOSHINE ", " CRISPER " (more than, Toyo Boseki K. K's system), " Lumirror " (eastern beautiful film is processed Co., Ltd.'s system), " EMBLON ", " EMBLET " (Unitika Corp's system), " ス カ イ ロ one Le " (SKC corporate system), " コ one Off イ Le " (Co., Ltd.'s high system of closing), " Easthome's polyester film " (STC Corp.'s system) and " too pavilion polyester film " (FUTAMURA CHEMICAL corporate system) etc.Wherein, from the viewpoint of throughput rate, cheapness, the present invention preferably uses biaxial stretch-formed goods.

(first adhesive layer)

First adhesive layer that polaroid of the present invention possesses is to undertake the layer that light polarizing film and stretching polyethylene terephthalate film is gluing, is that the solidfied material layer by the solvent-free active energy ray-curable composition that contains epoxy compound constitutes.Contain the solvent-free active energy ray-curable composition of epoxy compound by use, can improve the adaptation of light polarizing film and stretching polyethylene terephthalate film, and not need to make the operation of tackifier drying, thereby can boost productivity.

As the epoxy compound that contains in the active energy ray-curable composition, be not particularly limited, for example, can enumerate the glycidyl ether thing of aromatics with hydroxyl and chain compound, the epoxide etc. that has the diglycidyl amides of amino compound and have the chain compound of the two keys of C-C.By using these epoxy compounds, the adaptation of light polarizing film and stretching polyethylene terephthalate film is improved.

What is called has the aromatics of hydroxyl and the glycidyl ether thing of chain compound, obtains by making compound addition polycondensations under alkali condition such as hydroxyl epichlorokydrin.For example can enumerate bisphenol-type epoxy resin, multi-aromatic ring type epoxy resin and alkylene glycol type epoxy resin etc.

As bisphenol-type epoxy resin, for example, can enumerate glycidyl ether thing and oligomer and 3 of the glycidyl ether thing of bisphenol-A and oligomer thereof, Bisphenol F, 3 ', 5,5 '-methyl-4, the glycidyl ether thing of 4 '-xenol and oligomer thereof etc.

In addition, as multi-aromatic ring type epoxy resin, for example, can enumerate the glycidyl ether thing of phenol phenolics, glycidyl ether thing, phenol aralkyl resin glycidyl ether thing, naphthols aralkyl resin glycidyl ether thing and the phenol bicyclopentadiene resin glycidyl ether thing etc. of cresol novolac resin.And then, can enumerate the glycidyl ether thing of the glycidyl ether thing of trihydroxy benzene methylmethane and oligomer and trisphenol PA and oligomer thereof etc.

As alkylene glycol type epoxy resin, for example, can enumerate the glycidyl ether thing of ethylene glycol, the glycidyl ether thing, 1 of diethylene glycol, the glycidyl ether thing and 1 of 4-butylene glycol, the glycidyl ether thing of 6-hexanediol etc.

What is called has the diglycidyl amides of amino compound, obtains by making compound addition polycondensations under alkali condition such as amino epichlorokydrin.Have amino compound and can have hydroxyl simultaneously.For example, can enumerate 1, the diglycidyl amides of 3-phenylenediamine and oligomer, 1 thereof, the diglycidyl amides of the diglycidyl amides of the diglycidyl amides of 4-phenylenediamine and oligomer thereof, 3-amino-phenol and glycidyl ether thing and oligomer thereof and 4-amino-phenol and glycidyl ether thing and oligomer thereof etc.

What is called has the epoxide of the chain compound of the two keys of C-C, is by the use superoxide C-C double bond epoxidation of the chain compound with the two keys of C-C to be obtained.

Chain compound as the two keys of C-C are arranged is not particularly limited, and for example can enumerate butadiene, isoprene, pentadiene and hexadiene etc.In addition, also can use terpenes with two keys.For example, as non-ring type monoterpene, can enumerate linalool etc.As superoxide, for example can enumerate hydrogen peroxide, peracetic acid and tert-butyl hydroperoxide etc.

Also can use compound with epoxide Jie structure of dimerization of the above-mentioned chain compound that obtains with the two keys of C-C by suitable functional group.Be not particularly limited as the bond structure that comprises this functional group, for example, can enumerate ester bond, ehter bond and utilize key of alkyl etc.In addition, in the dimerization structure of above-mentioned epoxide, also can have a plurality of these keys.

In addition, these epoxy compounds and oligomer thereof etc. can be distinguished use separately, also can mix more than 2 kinds and use.

Such epoxy compound and oligomer thereof etc., can easily obtain commercially available product, for example, represent with trade name respectively, can enumerate " EPIKOTE " (japan epoxy resin Co., Ltd. system), " Epiclon " (Dainippon Ink Chemicals's system), " EPOTOHTO " (Toto Kasei KK's system), " ADEKA RESIN " (ADEKA corporate system), " EPOLEAD ", " EPOFRIEND ", " EHPE " (more than, DAICEL CHEMICALINDUSTRIES corporate system) and " TEPIC " (Nissan Chemical Ind Ltd's system) etc.

In addition, the epoxy compound that uses as above-mentioned active energy ray-curable compound, preferred alicyclic epoxy compound.Contain the solvent-free active energy ray-curable composition of alicyclic epoxy compound by use, can improve the permanance of polaroid under harsh and unforgiving environments.

At this, so-called alicyclic epoxy compound is meant directly have compound that epoxy radicals forms on the ring of saturated cyclic compound, and directly having the compound that glycidyl ether or glycidyl form on the ring of saturated cyclic compound.In structure, can also have other epoxy radicals.

So-called directly have the alicyclic epoxy compound that epoxy radicals forms on the ring of saturated cyclic compound, be by using superoxide to obtain at the C-C double bond epoxidation that makes the ring compound that has the two keys of C-C on ring under the alkali condition.

Ring compound as have the two keys of C-C on ring is not particularly limited, and can enumerate the compound with cyclopentene ring, the compound with cyclohexene ring and their polycyclic compound etc.The ring compound that has the two keys of C-C on ring can have C-C pair of keys in that ring is outer, as such compound, for example can enumerate 1-vinyl-3-cyclohexene and as the citrene of monocyclic monoterpene etc.

In addition, directly having the alicyclic epoxy compound that epoxy radicals forms on the ring of saturated cyclic compound, can be the compound with the above-mentioned epoxide Jie structure of dimerization by suitable functional group that obtains.Bond structure as comprising this functional group is not particularly limited, and for example, can enumerate ester bond, ehter bond and utilize key of alkyl etc.In addition, the dimerization structure of above-mentioned epoxide also can have a plurality of these keys.

The above-mentioned manufacture method that on the ring of saturated cyclic compound, directly has the alicyclic epoxy compound that epoxy radicals forms, can change according to each compound, be not particularly limited, for example can adopt following method: synthesize after having the ring compound of the two keys of C-C on the ring, carry out process for epoxidation; The two keys of C-C are further made functional group reactions as described above by epoxidised compound, the method for synthetic object construction etc.From the viewpoint of the subsidiary reaction that suppresses epoxy radicals etc., preferred usually the employing synthesized after having the ring compound of the two keys of C-C on the ring, carries out process for epoxidation.

Ring compound synthetic that on ring, has the two keys of C-C, can change according to the skeleton of target epoxide, be not particularly limited, as the synthesis example of the ring compound of dimerization, for example can enumerate following method: use suitable catalyzer to obtain method by Ti Senke reaction (Tishchenko Reaction) as the 3-cyclohexenyl group methyl 3-cyclohexene carboxylate ester of ester compounds by 3-cyclohexene-1-formaldehyde.

And then, use catalyzer as required, make above-mentioned ester compounds and dicarboxylic acid compound or its ester, diol compound or its ester, ployalkylene glycol or its ester or hydroxy carboxylic acid compound or its ester etc. that ester exchange reaction take place, obtain having the compound of cyclohexenyl group thus at two ends.

As dicarboxylic acid compound and its ester, for example can enumerate oxalic acid, hexane diacid and decanedioic acid and their dimethyl ester etc.In addition,, for example can enumerate ethylene glycol, diethylene glycol, 1,2-propylene glycol and polyglycol, 1,4-cyclohexanediol, 1,4 cyclohexane dimethanol and their dimethyl esters etc. as diol compound and ester thereof.In addition, as hydroxy carboxylic acid compound and ester thereof, for example can enumerate lactic acid, 3-hydroxybutyric acid and citric acid and their dimethyl ester/acetic acid esters etc., reach lactide, third lactones, butyrolactone and caprolactone etc.

The ring compound epoxidation that has the two keys of C-C on ring by using superoxide so to obtain can obtain directly having the alicyclic epoxy compound that epoxy radicals forms on the ring of saturated cyclic compound.Superoxide can wait and select according to each ring compound, permissible reaction conditions, is not particularly limited, and for example can enumerate hydrogen peroxide, peracetic acid and tert-butyl hydroperoxide etc.

In the present invention, if enumerate the concrete example that on the ring of saturated cyclic compound, directly has the alicyclic epoxy compound that epoxy radicals forms of preferred use, then for example can enumerate 3,4-epoxycyclohexyl methyl 3, the 4-epoxycyclohexane carboxylate, 1,2-epoxy-4-vinyl cyclohexane, 1,2-epoxy-1-methyl-4-(1-methyl epoxy ethyl) cyclohexane, 3,4-epoxycyclohexyl methyl acrylate, 2, the 4-(1, the 2-epoxy ethyl)-1 of two (the hydroxymethyl)-1-butanols of 2-, 2-7-oxa-bicyclo[4.1.0 addition product, ethylenebis (3, the 4-epoxycyclohexane carboxylate), oxygen di ethylene bis (3, the 4-epoxycyclohexane carboxylate), 1,4-cyclohexane dimethyl two (3, the 4-epoxycyclohexane carboxylate) and 3-(3,4-epoxycyclohexyl methoxycarbonyl) propyl group 3,4-epoxycyclohexane carboxylate etc.

So-called directly have an alicyclic epoxy compound that glycidyl ether or glycidyl form on the ring of saturated cyclic compound, be following compound: the compound that obtains, the glycidyl ether thing of saturated cyclic compound with hydroxyl and the epoxide with saturated cyclic compound of vinyl under the condition that catalyzer exists, adding that the aromatic rings of depressing optionally the glycidyl ether thing of the aromatics with hydroxyl described later carries out hydrogenation.

Glycidyl ether thing as the aromatics with hydroxyl for the treatment of hydrogenation is not particularly limited, and for example, can enumerate the glycidyl ether thing of the glycidyl ether thing of bisphenol-A and oligomer and Bisphenol F and oligomer thereof etc.

Glycidyl ether thing as the saturated cyclic compound with hydroxyl is not particularly limited, and for example, can enumerate 1,4 cyclohexane dimethanol diglycidyl ether etc.

Epoxide as the saturated cyclic compound with vinyl is not particularly limited, and for example, can enumerate 1, two (epoxy ethyl) hexanes, 1,2 of 3-, 4-three (epoxy ethyl) hexane and 2, two (the epoxy ethyl)-1-vinyl cyclohexanes of 4-etc.

In above-mentioned alicyclic epoxy compound, from show good solidfied material characteristic in the permanance that improves polaroid or have appropriateness curable, can obtain more at an easy rate simultaneously aspect, preferred 3,4-epoxycyclohexyl methyl 3, the hydride of the glycidyl ether thing of 4-epoxycyclohexane carboxylate and bisphenol-A, more preferably 3,4-epoxycyclohexyl methyl 3,4-epoxycyclohexane carboxylate.

In addition, these alicyclic epoxy compounds can be distinguished use separately, perhaps also can be mixed with two or more.

These alicyclic epoxy compounds can easily obtain commercially available product, for example, represent with trade name respectively, can enumerate, " CELLOXIDE ", " CYCLMER " (more than, DAICELCHEMICAL INDUSTRIES corporate system) and " Cyracure " (DOW CHEMICAL corporate system) etc.

The epoxide equivalent of the epoxy compound that the present invention uses is 30～2000g/eq normally, preferred 50～1500g/eq, more preferably 70～1000g/eq.During less than 30g/eq, there are the flexible reduction of first adhesive layer or the situation that adhesive strength reduces at epoxide equivalent sometimes.On the other hand, when epoxide equivalent surpasses 2000g/eq, there are curing rate reduction or the necessary rigidity of adhesive layer of solidifying, the situation of undercapacity sometimes.This epoxide equivalent is the value of measuring according to JIS K 7236 (ISO 3001).

The active energy ray-curable composition that forms first adhesive layer preferably further contains oxetane compound.By adding oxetane compound, can improve the curing rate of active energy ray-curable composition.As oxetane compound, be not particularly limited.In addition, its manufacture method also is not particularly limited, and for example can adopt following method: with 1, the method for cyclization is then carried out in the one-sided hydroxyl halogenation or the tosylation of 3-diol, derivatives compound by elimination reaction under alkali condition; By 1, the reaction of 3-diol, derivatives compound and alkyl carbonate obtains the carbonic ester of ring-type, carries out the method for cyclization then by its decarboxylic reaction; The method of cyclization is carried out in the compound by having carbonyl and the photodimerization reaction of vinyl compound; And, use inner salt (ylide) compound in epoxide ring, to insert the method for methylene.Wherein, the preferred carbonic ester that obtains ring-type by the reaction of trimethylolpropane or derivatives thereof and alkyl carbonate that adopts carries out the method for cyclization then by its decarboxylic reaction.In addition, also preferably make 2 under alkali condition, two (chloromethyl) propane of 2--1-alcohol carries out the method for dehydration.

The oxetane compound that so obtains, for example, 3-ethyl-3-hydroxymethyl the oxetanes that obtains by trimethylolpropane and alkyl carbonate and by 2, the two 3-ethyl-3-chloromethyl oxetanes that (chloromethyl) propane-1-alcohol obtains of 2-can be further used as and are used to modulate the precursor of its derivative compound and use.

If enumerate the concrete example of the oxetane compound that can use in the present invention, for example, can enumerate 1, two { [(the 3-ethyl oxetanes-3-yl) methoxyl] methyl } benzene of 4-, 3-ethyl-3-(2-ethyl hexyl oxy methyl) oxetanes, two (3-ethyl-3-oxetanes ylmethyl) ether, 3-ethyl-3-(phenoxymethyl) oxetanes, 3-ethyl-3-(cyclohexyloxy methyl) oxetanes, phenol phenolic aldehyde oxetanes and 1, two [(3-ethyl oxetanes-3-yl) methoxyl] benzene of 3-etc.

Such oxetane compound can be distinguished separately and use when cooperating with epoxy compound, also can mix more than 2 kinds and use.

Such oxetane compound can easily obtain commercially available product, for example, represents with trade name respectively, can enumerate " ARON OXETANE " (Toagosei Co., Ltd's system) and " ETERNACOLL " (emerging Industry Co., Ltd of space portion system) etc.

The oxetanes equivalent of the oxetane compound of Shi Yonging is generally 30～2000g/eq in the present invention, preferred 50～1500g/eq, more preferably 70～1000g/eq.During less than 30g/eq, there are the flexible reduction of first adhesive layer or the situation that adhesive strength reduces at the oxetanes equivalent sometimes.On the other hand, when surpassing 2000g/eq, there are curing rate reduction or the necessary rigidity of adhesive layer of solidifying, the situation of undercapacity sometimes.This oxetanes equivalent is the value that obtains according to molecular structure theory of computation value.

The match ratio of epoxy compound of Shi Yonging and oxetane compound in the present invention, with respect to epoxy compound 100 weight portions, preferred oxetane compound is 0～900 weight portion.More preferably 25～400 weight portions, further preferred 40～250 weight portions in addition.If cooperate more than oxetanes 25 weight portions, then obtain the effect that solidification effect improves easily with respect to epoxy compound 100 weight portions.On the other hand, if cooperate more than oxetanes 900 weight portions with respect to epoxy compound 100 weight portions, the situation that then exists the adhesive layer that solidifies to be wanting in sometimes in intensity, thermotolerance.

Above-mentioned epoxy compound and oxetane compound can use with epoxy compound behind the organic solvent diluting and oxetane compound.In addition, for the minor constituent of formation described later as the Photoepolymerizationinitiater initiater of the active energy ray-curable composition of adhesive compound and sensitizer etc., compare with the composition in being dissolved in organic solvent, preferred use with organic solvent remove, dry independent powder or the liquid of this compound.

Active energy ray-curable composition before solidifying is 25 ℃ viscosity, so long as can coat viscosity on the film with proper method, just is not particularly limited the scope of preferred 10～30000mPas, the more preferably scope of 50～6000mPas.If the viscosity of active energy ray-curable composition is less than 10mPas, then the device that can be coated with is limited, promptly enables to be coated with the situation that can not obtain agonic uniform coating that also exists sometimes.In addition, if surpass 30000mPas, then owing to be difficult to flow, the device that can be coated with is limited equally, has the situation that can not obtain agonic uniform coating sometimes.The viscosity of active energy ray-curable composition is to use Brookfield viscometer, with after the said composition temperature adjustment to 25 ℃, and the value of measuring with 60rpm.

Use among the present invention contain epoxy compound or contain epoxy compound and the active energy ray-curable composition of oxetane compound in whole chlorine doses of containing be preferably the scope of 0.1ppm～15000ppm, the more preferably scope of 0.5ppm～2000ppm, the more preferably scope of 1.0～1000ppm.If the whole chlorine doses that contain in the active energy ray-curable composition are less than 0.1ppm, then the curing rate of said composition becomes extremely slow sometimes.In addition, if surpass 15000ppm,, there is the situation of the metal parts corrosion of apparatus for coating burn into or liquid crystal panel sometimes then owing to the influence of chlorine.These whole chlorine doses are values of measuring according to JIS K7243-3 (ISO 21627-3).

That uses in the present invention contains epoxy compound or contains epoxy compound and the tone of the active energy ray-curable composition of oxetane compound, Gardner's colourity in the active energy ray-curable composition before solidifying, be preferably below 5, more preferably below 3, further preferred below 1.If tone surpasses 5, the influence to the tone of polaroid then appears sometimes owing to the painted of adhesive layer.

That uses in the present invention contains epoxy compound or contains epoxy compound and the active energy ray-curable composition of oxetane compound, (sclerosis) solidified in irradiation by active energy beam, is the solidification compound that the film of this solidfied material layer of clamping is given each other adhesive power.

As the active energy beam that uses, for example, can enumerate the X ray of wavelength 1pm～10nm, the ultraviolet ray of 10～400nm and the luminous ray of 400～800nm etc.Wherein, from the adjustment easiness of the easiness utilized, active energy ray-curable composition and stability thereof, with and the aspect of curing performance, preferably use ultraviolet ray.

The light source that uses is not particularly limited, and for example, can enumerate the low pressure mercury lamp that has luminescence distribution below wavelength 400nm, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp, black lamp, microwave-excitation mercury lamp, metal halide lamp etc.

Exposure intensity decides according to active energy ray-curable composition, irradiation time, is not particularly limited, and for example, preferably the exposure intensity to the effective wavelength coverage of activation of initiating agent is 0.1～1000mW/cm ²To the rayed intensity of active energy ray-curable composition less than 0.1mW/cm ²The time, the curing reaction time is elongated, that is, just can not solidify if do not apply long irradiation time, has rough sledding aspect throughput rate sometimes.In addition, if surpass 1000mW/cm ², because the heat release during from the heat of lamp radiation and the polymerization of active energy ray-curable composition exists the xanthochromia that produces the active energy ray-curable composition, the situation of light polarizing film deterioration sometimes.

Irradiation time decides according to active energy ray-curable composition, exposure intensity, is not particularly limited, and for example, preferably setting with the represented accumulative total light quantity of the product of exposure intensity and irradiation time is 10～5000mJ/cm ²To the accumulative total light quantity of active energy ray-curable composition irradiation less than 10mJ/cm ²The time, insufficient from the generation of the spike of initiating agent, there is the inadequate situation of curing of the adhesive layer that obtains sometimes.On the other hand, if surpass 5000mJ/cm ², it is very long that irradiation time becomes, and becomes unfavorable sometimes on throughput rate improves.

That uses in the present invention contains epoxy compound or contains epoxy compound and the active energy ray-curable composition of oxetane compound, is cured in order to utilize active energy beam, preferably cooperates cationic polymerization initiators.Cationic polymerization initiators produces kation kind or lewis acid by the irradiation of luminous ray, ultraviolet ray, X ray and electron beam isoreactivity energy-ray, and the polyreaction of epoxy radicals is begun.

This cationic polymerization initiators preferably is endowed potentiality.By giving potentiality, the up time of the active energy ray-curable composition that uses among the present invention is elongated, and operability also improves.

Produce kation kind, lewis acidic compound as irradiation, be not particularly limited, for example, can enumerate the such salt of aromatic series diazo salt, aromatic series salt compounded of iodine, aromatic series sulfonium salt and fragrant luxuriant iron complex compound etc. by active energy beam.

As the aromatic series diazo salt, can enumerate for example benzene diazonium hexafluoro antimonate, benzene diazonium hexafluorophosphate and benzene diazonium hexafluoro borate etc.

As the aromatic series salt compounded of iodine, can enumerate for example diphenyl iodonium four (pentafluorophenyl group) borate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoro antimonate and two (4-nonyl phenyl) iodine hexafluorophosphate etc.

As the aromatic series sulfonium salt, can enumerate for example triphenylsulfonium hexafluorophosphate, the triphenylsulfonium hexafluoro antimonate, triphenylsulfonium four (pentafluorophenyl group) borate, diphenyl [4-(thiophenyl) phenyl] sulfonium hexafluoro antimonate, 4, the two hexafluorophosphates of 4 '-two [diphenyl sulfonium] diphenyl sulfide, 4, the two hexafluoro antimonates of 4 '-two [two (beta-hydroxy ethoxy) phenyl sulfonium] diphenyl sulfide, the two hexafluorophosphates of 4,4 '-two [two (beta-hydroxy ethoxy) phenyl sulfonium] diphenyl sulfide, 7-[two (p-methylphenyl) sulfonium]-2-isopropyl thioxanthone hexafluoro antimonate, 7-[two (p-methylphenyl) sulfonium]-2-isopropyl thioxanthone four (pentafluorophenyl group) borate, 4-phenylcarbonyl group-4 '-diphenyl sulfonium-diphenyl sulfide hexafluorophosphate, 4-(to the tert-butyl-phenyl carbonyl)-4 '-diphenyl sulfonium-diphenyl sulfide hexafluoro antimonate and 4-(to the tert-butyl-phenyl carbonyl)-4 '-two (p-methylphenyl) sulfonium-diphenyl sulfide four (pentafluorophenyl group) borate etc.

As the luxuriant iron complex compound of virtue, can enumerate for example dimethylbenzene-cyclopentadienyl group iron (II) hexafluoro antimonate, isopropyl benzene-cyclopentadienyl group iron (II) hexafluorophosphate and dimethylbenzene-cyclopentadienyl group iron (II)-three (trifluoromethyl sulphonyl) methanides etc.

These cationic polymerization initiators can be distinguished use separately, also can mix more than 2 kinds and use.Wherein, aromatic series sulfonium salt especially, even if the wavelength coverage more than 300nm also has the UVA characteristic, the therefore solidfied material layer that the curable excellence can be provided, have good mechanical strength and adhesive strength, therefore preferred the use.

The use level of cationic polymerization initiators is with respect to total 100 weight portions of epoxy compound or epoxy compound and oxetane compound, 0.5～20 weight portion normally, preferred 1～15 weight portion.Use level is during less than 0.5 weight portion, solidifies to become insufficient, and physical strength, the adhesive strength of solidfied material layer reduce sometimes.And use level is when surpassing 20 weight portions, and the ionic substance in the solidfied material layer increases, so the hydroscopicity of solidfied material layer improves, and the endurance quality of the polaroid of gained reduces sometimes.

These cationic polymerization initiators can easily obtain commercially available product, represent with trade name respectively, for example, can enumerate " Kayarad (Nippon Kayaku K. K's system), " Cyracure " (associating carbonide (Union Carbide) corporate system), Photoacid generator " CPI " (San-apro corporate system), Photoacid generator " TAZ ", " BBI ", " DTS " (more than; Co., Ltd.'s system is learned in greening), " Adeka Optomer (more than, ADEKA corporate system), " RHODORSIL " (Luo Diya (Rhodia) corporate system) etc.

That uses among the present invention contains epoxy compound or contains epoxy compound and the active energy ray-curable composition of oxetane compound, can and use photosensitizer as required.By using photosensitizer, the reactive raising can make the physical strength of solidfied material layer, adhesive strength improve.

As photosensitizer, be not particularly limited, for example can enumerate carbonyls, organosulfur compound, persulfide, redox based compound, azo and diazo-compounds, halogenide and photo-reduction pigment etc.

As carbonyls, for example can enumerate benzoin methylether, benzoin iso-propylether and α, the alpha, alpha-dimethyl oxygen base-α-such benzoin derivatives of phenyl acetophenone; 9, the anthracene compound that 10-dibutoxy anthracene is such; Benzophenone, 2,4-dichloro benzophenone, o-benzoyl yl benzoic acid methyl esters, 4,4 '-two (dimethylamino) benzophenone and 4, the 4 '-such benzophenone derivates of two (lignocaine) benzophenone; The anthraquinone derivative that 2-chloroanthraquinone and 2-methylanthraquinone are such; N-methylacridine ketone and the such acridone derivatives of N-butyl acridone; α, the acetophenone derivs that α-diethoxy acetophenone is such; The xanthone derivant; And fluorenone derivatives etc.

As organosulfur compound, for example can enumerate 2-clopenthixal ketone and the such thioxanthone derivates of 2-isopropyl thioxanthone.Other also can enumerate benzil compound and uranyl compound etc.

These photosensitizers can be used alone, but also also mix together respectively.When the active energy ray-curable composition was counted 100 weight portions, preferably the scope with 0.1～20 weight portion contained photosensitizer.

In the active energy ray-curable composition that the present invention uses, only otherwise damage effect of the present invention, can cooperate various adjuvants.As various adjuvants, for example, can enumerate ion-trapping agent, antioxidant, chain-transferring agent, sensitizer, tackifier, thermoplastic resin, filling agent, flow modifier, plastifier and defoamer etc.

As ion-trapping agent, for example can enumerate the mineral compound of pulverous bismuth system, antimony system, magnesium system, aluminium system, calcium system, titanium system and their mixed stocker etc.As antioxidant, for example, can enumerate hindered phenol is antioxidant etc.

The method of the layer that formation is formed by the active energy ray-curable composition shown in above on light polarizing film or stretching polyethylene terephthalate film (adhesive layer before solidifying), be not particularly limited, for example can adopt following method: the method for coating said composition on light polarizing film or stretching polyethylene terephthalate film, blow the method for attached said composition, or will be shaped to method that membranaceous said composition fits etc. in advance.Wherein, the method for coating composition or method that membranaceous composition is fitted be because the homogenieity of filming is higher, thereby preferred, and the method for coating composition because throughput rate is higher more preferably.

Be not particularly limited as coating process, for example can utilizing, scraper, coiling rod, mould are coated with various coating methods such as machine, comma coating machine and intaglio plate coating machine.

The thickness of the adhesive layer before the curing of coating is generally 0.1～20 μ m, preferred 0.2～10 μ m, more preferably 0.5～5 μ m.If thickness is less than 0.1 μ m, then sometimes by the light polarizing film of the adhesive layer generation of solidifying and the closing force deficiency between the stretching polyethylene terephthalate film.In addition, if thickness surpasses 20 μ m, then the curing of adhesive layer sometimes can not fully be carried out, even perhaps solidify, might cause the bendability variation of film owing to its thickness, or can not get the effect of slimming.

(diaphragm, optical compensation films)

Polaroid of the present invention can be on light polarizing film and the face face opposition side that is laminated with stretching polyethylene terephthalate film, possess Jie by second adhesive layer stacked diaphragm or optical compensation films.

Diaphragm or optical compensation films can suitably use the film that has as the optical characteristics of blooming according to purpose; be not particularly limited; as diaphragm, for example can enumerate the hyaline membranes such as cellulose-based resin molding, ethylene series resin molding, acrylic resin film, polycarbonate resin film and polyester based resin film that form by triacetyl cellulose (TAC) etc.

In addition, as optical compensation films, can enumerate and the above-mentioned film enumerated as diaphragm is stretched and make it have the anisotropic film of refractive index, cooperated the film that to give optically anisotropic adjuvant and the film that has formed optical anisotropic layer on the surface.

In addition, in these diaphragms or optical compensation films, as described later, all right stacked optical functional film, or coating optical functional layer.

So-called cellulose-based resin molding is the film that is formed by cellulosic partial esterification thing or full carboxylate, for example can enumerate the film that is formed by cellulosic acetic acid esters, propionic ester, butyric ester and these mixed ester etc.Wherein, preferably use tri acetyl cellulose membrane, diacetyl cellulose film, cellulose-acetate propionate film and cellulose acetate-butyrate film etc.

Cellulose-based resin molding like this can easily obtain commercially available product, for example, represent with trade name respectively, can enumerate " FUJITAC TD " (Fuji Photo Film Co., Ltd.'s system) and " KonicaMinolta TAC Film KC " (Konica Minolta Opto corporate system) etc.

So-called ethylene series resin molding is the film that is formed by following resin: the resin that uses catalyst for polymerization that for example cyclic olefin monomers polymerization such as chain such as ethene and propylene olefinic monomer and norborene and other cyclopentadiene derivant is got.

As the ethylene series resin that comprises the chain olefinic monomer, can enumerate tygon or polypropylene-based resin.Wherein, the polypropylene-based resin that preferably constitutes by the homopolymer of propylene.In addition, also preferably based on propylene, can with the comonomer of its copolymerization with the ratio of common 1～20 weight %, the polypropylene-based resin that preferably obtains with the ratio copolymerization of 3～10 weight %.

When using the polypropylene-based resin that constitutes by propylene copolymer, as can with the comonomer of copolymerization of propylene, optimal ethylene, 1-butylene and 1-hexene.Wherein, consider from the transparency, the more excellent angle in stretch process aspect, preferably make ethylene copolymer with the ratio of 3～10 weight % and resin.Be made as more than the 1 weight % by copolymerization ratio, demonstrate the effect of the transparency, stretch process raising ethene.On the other hand, if this ratio surpasses 20 weight %, then the fusing point of resin descends, and diaphragm, the desired thermotolerance of optical compensation films are impaired sometimes.

Such polypropylene-based resin can easily obtain commercially available product, for example, represent with trade name respectively, can enumerate " Prime Polypro " (Prime Polymer corporate system), " NOVATEC ", " WINTEC " (more than, Japan Polypropylene corporate system), " SUMITOMO NOBRENE " (Sumitomo Chemical Co's system) and " Sunallomer " (Sunallomer corporate system) etc.

The ethylene series resin that cyclic olefin is polymerized is commonly referred to ring-type (gathering) ethylene series resin, ester ring type (gathering) ethylene series resin or norbornene resin.Be called annular ethylene series resin at this.

As annular ethylene series resin, for example can enumerate, the norborene or derivatives thereof that will be obtained by diels-Alder reaction by cyclopentadiene and olefines carries out ring-opening metathesis (metathesis) polymerization as monomer, then carries out hydrogenation and the resin that obtains; The tetracyclododecen or derivatives thereof that will be obtained by diels-Alder reaction by bicyclopentadiene and olefines or methyl acrylic ester carries out ring-opening metathesis polymerization as monomer, then carries out hydrogenation and the resin that obtains; Norborene, tetracyclododecen, their derivant class or other cyclic olefin monomers are similarly carried out ring-opening metathesis polymerization, then carry out hydrogenation and the resin that obtains; And above-mentioned norborene, tetracyclododecen, their derivant and aromatics etc. with vinyl made it resin that copolymerization obtains etc. by addition polymerization.

Such annular ethylene series resin can easily obtain commercially available product, for example, represent with trade name respectively, can enumerate " Topas " (Topas Advanced Polymers GmbH system), " ARTON " (JSR Corp.'s system), " ZEONOR ", " ZEONEX " (more than, Japanese Zeon corporate system) and " APEL " (Mitsui Chemicals, Inc's system) etc.

As the concrete example of preferred acrylic resin, can enumerate by methyl methacrylate is the film that resin forms.So-called methyl methacrylate is a resin, is the polymkeric substance that contains the above methyl methacrylate units of 50 weight %.The content of methyl methacrylate units is preferably more than the 70 weight %, can be 100 weight %.Methyl methacrylate units is that the polymkeric substance of 100 weight % is the imperplex that the independent polymerization of methyl methacrylate is obtained.

This methyl methacrylate is a resin, can followingly obtain usually: will be the monofunctional monomer of principal ingredient and the polyfunctional monomer that uses as required with the methyl methacrylate carries out polymerization under the coexistence of radical polymerization initiator and the chain-transferring agent that uses as required.

As can with the monofunctional monomer of methyl methacrylate copolymer, be not particularly limited, for example can enumerate methyl methacrylates such as Jia Jibingxisuanyizhi, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid 2-Octyl Nitrite and 2-hydroxyethyl methacrylate methyl acrylic ester in addition; Esters of acrylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-EHA and acrylic acid 2-hydroxy methacrylate; Hydroxy acrylate classes such as 2-(methylol) methyl acrylate, 3-(hydroxyethyl) methyl acrylate, 2-(methylol) ethyl acrylate and 2-(methylol) butyl acrylate; Unsaturated acids such as methacrylic acid and acrylic acid; Halogenated styrenes such as chlorostyrene and bromstyrol class; Substituted phenylethylene such as vinyltoluene and α-Jia Jibenyixi class; Unsaturated nitrile such as vinyl cyanide and methacrylonitrile; Unsaturated acid anhydride such as maleic anhydride and citraconic anhydride class; And unsaturated acid imides such as phenyl maleimide and cyclohexyl maleimide etc.Such monomer can be distinguished use separately, also can be used in combination more than 2 kinds.

As can with the polyfunctional monomer of methyl methacrylate copolymer, be not particularly limited, for example, can enumerate two (methyl) acrylic acid glycol ester, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, nine ethylene glycol bisthioglycolates (methyl) acrylate and ten TEGs (methyl) acrylate etc. with two terminal hydroxyls of ethylene glycol or its oligomer with the acrylic or methacrylic acid estersization and polyfunctional monomer; With two terminal hydroxyls of propylene glycol or its oligomer with the acrylic or methacrylic acid estersization and polyfunctional monomer; With the hydroxyl of dibasic alcohol such as two (methyl) acrylic acid DOPCP, two (methyl) acrylic acid hexanediol ester and two (methyl) acrylic acid butanediol ester with the acrylic or methacrylic acid estersization and polyfunctional monomer; With two terminal hydroxyls of the alkylene oxide addition product of bisphenol-A, bisphenol-A or their halogen substituent with the acrylic or methacrylic acid estersization and polyfunctional monomer; The polyfunctional monomer that polyvalent alcohols such as trimethylolpropane and pentaerythrite usefulness acrylic or methacrylic acid estersization is got; And on their terminal hydroxyl with the epoxy ring-opening addition of glycidyl acrylate or glycidyl methacrylate and polyfunctional monomer; On succinic acid, hexane diacid, terephthalic acid (TPA), phthalic acid, their dibasic acid such as halogen substituent and their alkylene oxide addition product etc., make glycidyl acrylate or glycidyl methacrylate the epoxy ring-opening addition and polyfunctional monomer; (methyl) acrylic acid aryl ester; And the biaryl compound of divinylbenzene etc. etc.Wherein, preferably use Ethylene glycol dimethacrylate, TEG dimethylacrylate and neopentylglycol dimethacrylate.

The methyl methacrylate of Shi Yonging is that resin can be by carrying out the reaction between functional group that this resin has and the modified methacrylic acid methyl esters of modification is a resin in the present invention.As this reaction, for example, can enumerate dehydration condensation in the macromolecular chain of hydroxyl of separating methanol condensation reaction in the macromolecular chain of hydroxyl of the carbomethoxy of methyl acrylate and 2-(hydroxymethyl) methyl acrylate and acrylic acid carboxyl and 2-(hydroxymethyl) methyl acrylate etc.

Methyl methacrylate is that resin can easily obtain commercially available product, for example, represent with trade name respectively, can enumerate " SUMIPEX " (Sumitomo Chemical Co), " ACRYPET " (Mitsubishi Rayon corporate system), " Delpet " (Asahi Kasei Corporation's system), " Parapet " (Kuraray corporate system) and " ACRYVIEWA " (Nippon Shokubai Co., Ltd's system) etc.

The polycarbonate-based resin that constitutes the polycarbonate resin film normally makes carbonate precursor reactions such as dihydric phenol and phosgene or diphenyl carbonate class obtain with interface polycondensation or melt transesterification process, generally be to use the aromatic polycarbonate resin of bisphenol-A as dihydric phenol.Other also can be enumerated by the solid phase ester-interchange method and make the polycarbonate-based resin that the polymerization of carbonic ester prepolymer gets or make polycarbonate-based resin that the cyclic carbonate compound ring-opening polymerization gets etc.

As dihydric phenol, as long as it is harmless as the performance of optics with transparent resin, just be not particularly limited, for example, can enumerate bisphenol-A (2, two (4-hydroxy phenyl) propane of 2-), also has p-dihydroxy-benzene in addition, resorcinol, 4,4 '-dihydroxybiphenyl, two (4-hydroxy phenyl) methane, two { (4-hydroxyls-3, the 5-dimethyl) phenyl } methane, 1, two (4-hydroxy phenyl) ethane of 1-, 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-, 1, the 1-bis(4-hydroxyphenyl)cyclohexane, 1, two (4-the hydroxy phenyl)-4-isopropyl cyclohexanes of 1-, 2, two { (4-hydroxy-3-methyl) phenyl } propane of 2-, 2, two { (the 4-hydroxyls-3 of 2-, the 5-dimethyl) phenyl } propane, 2, two { (the 4-hydroxyls-3 of 2-, the 5-dibromo) phenyl } propane, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-the hydroxy phenyl)-3-methylbutanes of 2-, 2, two (4-the hydroxy phenyl)-2-methylbutanes of 2-, 2, two (4-hydroxy phenyl) pentanes of 2-, 2, two (4-the hydroxy phenyl)-4-methylpentanes of 2-, 9, two (4-hydroxy phenyl) fluorenes of 9-, 9, two { (4-hydroxy-3-methyl) phenyl } fluorenes of 9-, 9,9-is { (4-hydroxyl-3,5-dimethyl) phenyl } fluorenes in pairs, 9, two { (the 4-hydroxyls-3 of 9-, the 5-dibromo) phenyl } fluorenes, α, the adjacent diisopropyl benzene of α '-two (4-hydroxy phenyl), α, diisopropyl benzene between α '-two (4-hydroxy phenyl), α, α '-two (4-hydroxy phenyl) is to diisopropyl benzene, 4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-dihydroxy diphenylketone and 4,4 '-dihydroxydiphenyl ether etc., they can use separately or mix more than 2 kinds and use.

In addition, for molecular weight being adjusted to suitable scope, or, also can and use the monohydric phenol compound with the C-terminal end-blocking of macromolecular chain.As this monohydric phenol,, for example, can enumerate phenol, 4-tert-butyl phenol and 1-phenyl-1-(4-hydroxy phenyl) propane etc. so long as the compound that can work as end-capping reagent just is not particularly limited.

As required, can also use 2-(the 2-hydroxyl-3-tert-butyl group-5-(2-carboxy ethyl)) phenyl benzotriazole etc. to have the absorbefacient compound of UV as end-capping reagent.

Polycarbonate-based resin can easily obtain commercially available product, for example, represent with trade name respectively, can enumerate " Lexan " (SABIC Innovative Plastics corporate system), " MAKROLON ", " Apec " (more than, Bayer Material Science corporate system), " Iupilon ", " ノ バ Star Network ス " (above Mitsubishi engineering Plastics Co., Ltd system), " Panlite " (Teijin Chemicals, Ltd.), " CALIBRE " (Dow Chemical corporate system), " SDPOLYCA " (Sumitomo Dow corporate system) and " TARFLON " (Idemitsu Kosen Co., Ltd.) etc.

As ethylene series resin, annular ethylene series resin, the methyl methacrylate that will so obtain is the method that resin and polycarbonate-based resin etc. are shaped to diaphragm, can select proper method according to this resin, is not particularly limited.For example can adopt following method: the resin that will be dissolved in solvent is to metallicity band or drum curtain coating, solvent seasoning is removed and obtains the solvent cast method of film; And carry out mixing back more than the melt temperature and extrude from the mouth mould by resin being heated to it, cool off and obtain the extrusion by melting of film.Wherein, from the viewpoint of throughput rate, preferably adopt extrusion by melting.

In addition; the film that is formed by above-mentioned resin that can be used as diaphragm can easily obtain commercially available product; for example; if polypropylene-based resin; then represent with trade name respectively, can enumerate " FILMAXCPP FILM " (FILM AX corporate system); " Suntox " (Suntox corporate system); " Tohcello " (Tohcello corporate system); " TOYOBO PYLEN FILM " (Toyo Boseki K. K's system); " Torayfan " (eastern beautiful film is processed Co., Ltd.'s system); " Japan Polyace " (JapanPolyace corporate system) and " too pavilion FC " (FUTAMURA CHEMICAL corporate system) etc.

In addition, for example, if the annular ethylene series resin film then represent with trade name respectively, can enumerate " ZEONOR FILM " (Optronics corporate system) and " ARTON " (JSR Corp.'s system) etc.

In addition, for example, if methyl methacrylate resin film, then represent with trade name respectively, can enumerate " SUMIPEX " (Sumitomo Chemical Co's system), " ACRYLITE ", " ACRYPLEN " (more than, Mitsubishi Rayon corporate system), " DELAGLAS " (Asahi Kasei Corporation's system), " Paraglass ", " Comoglass " (more than, Kuraray corporate system) and " ACRYVIEWA " (Nippon Shokubai Co., Ltd's system) etc.

In addition, for example, if carbonic ester resin film, then represent with trade name respectively, can enumerate " Lexan OQ Film " (SABIC Innovative Plastics corporate system), " MAKROFOL ", " BAYFOL " (more than, Bayer MaterialScience corporate system), " Iupilon Sheet " (Mitsubishi engineering Plastics Co., Ltd's system) and " PANLITE SHEET " (Teijin Chemicals, Ltd.'s system) etc.

In addition; as light polarizing film with the opposition side that is laminated with stretching polyethylene terephthalate film side on; the polyester based resin film as diaphragm that Jie is provided with by second adhesive layer can use and the resin that constitutes polyester based resin (PET series resin) identical type of this stretching polyethylene terephthalate film.At this moment, the polyester based resin film can use the film that is not stretched, and for example the film that obtains with above-mentioned melt extruding directly can be used.

The not stretched polyester resin film that can be used as diaphragm can easily obtain commercially available product; for example; represent with trade name respectively, can enumerate " NOVACLEAR " (Mitsubishi chemical Co., Ltd's system) and " Teijin A-PET Sheet " (Teijin Chemicals, Ltd.'s system) etc.

In addition, as by the film formed optical compensation films of cellulose-based resin, as long as have the refractive index characteristic that meets purpose, just be not particularly limited, for example, can enumerate the above-mentioned cellulose-based resin molding of enumerating is carried out single shaft or biaxial stretch-formed and film that obtain, or in cellulose-based resin molding, contain and have the film that phase differential is adjusted the compound of function, coating has the film that phase differential is adjusted the compound of function on cellulose-based surface resin film, and with further uniaxial tension of these films or the biaxial stretch-formed and film that obtains etc.

The optical compensation films that is formed by cellulose-based resin can easily obtain commercially available product, for example, represent with trade name respectively, can enumerate " FUJITAC WV " (Fuji Photo Film Co., Ltd.'s system) and " Konica Minolta TAC Film KC 8UCR " (Konica Minolta Opto corporate system) etc.

In addition,, usually unstretching film is stretched, make film have the refractive index anisotropy will be as above-mentioned diaphragm and illustrative ethylene series resin molding, acrylic resin film, polycarbonate resin film and polyester based resin film etc. during as optical compensation films.Drawing process can be selected according to the anisotropy of needed refractive index, is not particularly limited, and adopts vertical uniaxial tension, horizontal uniaxial tension and vertical, horizontal biaxial stretch-formed one by one usually.

Usually, vertically the film of uniaxial tension has n _x＞n _y=n _zThe refractive index anisotropy.At this, n _xBe the refractive index of film draw direction, n _yBe the refractive index of film wide cut direction, n _zIt is the refractive index of the normal direction of film.

Usually, had by the film of horizontal uniaxial tension The refractive index anisotropy.In addition, had n by biaxial stretch-formed one by one film usually _x＞n _y＞n _zThe refractive index anisotropy.

In order to give desired refractive index characteristic, can also carry out following operation: heat-shrinkable film and target film is bonding, substitute stretch process or when carrying out stretch process, film is shunk.Usually, this operation is to be n in order to obtain the refractive index anisotropy _x＞n _z＞n _yOr n _z＞n _x〉=n _yOptical compensation films carry out.

Optical compensation films can easily obtain commercially available product, for example, as the optical compensation films that becomes by cyclic polyolefin hydrocarbon system resin-shaped, represent with trade name respectively, can enumerate " " ZEONORFILM " (Optronics corporate system) and " ARTON FILM " (JSR Corp.'s system), " エ ス シ one Na phase retardation film " (Sekisui Chemical Co., Ltd's system) and " Pure-ace ER " (Teijin Chemicals, Ltd.'s system) etc.In addition, as the optical compensation films that forms by polycarbonate-based resin, for example, can enumerate " Pure-ace WR " (Teijin Chemicals, Ltd.'s system) etc.

And then on the diaphragm or optical compensation films that are laminated on the light polarizing film, stacked optical functional film or coating optical functional layer by second adhesive layer can also be situated between.As this optical functional film and optical functional layer, for example, can enumerate antiglare layer, conductive layer, hard conating and low reflection layer etc.

(second adhesive layer)

Second adhesive layer is to undertake light polarizing film and above-mentioned diaphragm or the gluing layer of optical compensation films.Second adhesive layer is the same with first adhesive layer, can be made of the solidfied material layer of the solvent-free active energy ray-curable composition that contains epoxy compound.In addition; as the active energy ray-curable composition that forms second adhesive layer; if use and the identical composition of active energy ray-curable composition that forms first adhesive layer; then because tackifier is a kind of thereby operation becomes easy; in addition; owing to do not need the drying of tackifier; thereby do not need the drying equipment after diaphragm or the optical compensation films applying; and then; because the active energy beam by online (inline) when making polaroid shines; thereby stretching polyethylene terephthalate film that disposes on the two sides of light polarizing film and diaphragm or optical compensation films can be simultaneously bonding, thereby the advantage that has throughput rate to improve.

In addition, as the tackifier that forms second adhesive layer, for example can use with light polarizing film and the water system tackifier that uses when bonding by the film formed diaphragm of TAC.As the adhesive component that can form this water system tackifier, for example, can enumerate water-soluble cross-linked property epoxy is resin and polyurethane series resin etc.

As water-soluble cross-linked property epoxy is resin, for example can enumerate the daiamid epoxy resin resin that makes the reaction of chloropropylene oxide and polyamide polyamine and obtain, described polyamide polyamine is by the such dicarboxylic acids reaction of the such polyalkylenepolyamines of diethylene triamine, trien and hexane diacid and obtain.

Such daiamid epoxy resin can easily obtain commercially available product, for example, represents with trade name, can enumerate " SUMIREZ RESIN 650 " " SUMIREZ RESIN 675 " (more than, by Sumitomo chemtex company sell).

When using water-soluble cross-linked epoxy resin as adhesive component, in order further to improve coating and cohesive, preferred mixing pva is other water soluble resins such as resin.Polyvinyl alcohol resin can be partly-hydrolysed polyvinyl alcohol (PVA), fully saponified polyvinyl alcohol (PVA), can be carboxy-modified polyvinyl alcohol (PVA), acetoacetyl modified polyvinylalcohol, methylol modified polyvinylalcohol, the such polyvinyl alcohol resin that is modified of amino modified polyvinyl alcohol (PVA) in addition.

Such polyvinyl alcohol resin can easily obtain commercially available product, for example, if contain the polyvinyl alcohol (PVA) of anionic property group, represents with trade name, can enumerate " KL-318 " (Kuraray corporate system).

When making contains water-soluble cross-linked property epoxy and is the tackifier of resin, be resin and as required and other water soluble resins such as polyvinyl alcohol resin that add are dissolved in the water with this bridging property epoxy, constitute adhesive solvent.At this moment, water-soluble cross-linked property epoxy is that resin uses with the concentration of 0.2～2 weight portion scope with respect to 100 weight parts waters usually.

In addition, when cooperating polyvinyl alcohol resin, its amount is for being the concentration of 1～10 weight portion scope with respect to 100 weight parts waters, preferred 1～5 weight portion.

On the other hand, use when containing the water system tackifier of polyurethane series resin, as the example of suitable urethane resin, can enumerate ionomer type polyurethane resin, particularly polyester is ionomer type polyurethane resin.At this, so-called ionomer type is the resin that has imported a small amount of ionic composition (hydrophilic component) in the urethane resin that constitutes skeleton.In addition, so-called polyester is an ionomer type polyurethane resin, is the urethane resin with polyester backbone, has wherein imported a spot of ionic composition (hydrophilic component).

Such ionomer type polyurethane resin does not use emulsifying agent with regard to directly emulsification and become emulsion in water, thereby preferably as the water system tackifier.

Such ionomer type polyurethane resin can easily obtain the emulsion commercially available product, for example, represents with trade name respectively, can enumerate " HYDRAN AP-20 ", " HYDRANAPX-101H " (Dainippon Ink Chemicals's system) etc.

With ionomer type polyurethane resin during as adhesive component, the preferred crosslinking chemical that further cooperates isocyanate-based etc.The isocyanate-based crosslinking chemical is to have 2 isocyanate group (compounds NCO) in molecule at least, as its example, can enumerate 2,4-toluene diisocyanate, phenylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, 1, monomer such as 6-hexamethylene diisocyanate, isophorone diisocyanate and its oligomer and with these compounds and polyol reaction and adduct etc.

Such isocyanate-based crosslinking chemical can easily obtain commercially available product, for example, can enumerate " Ha イ De ラ Application ア シ ス タ one C-1 " (Dainippon Ink Chemicals's system) etc.

When use contained the water system tackifier of ionomer type polyurethane resin, the concentration of the urethane resin that disperses in water was generally 10～70 weight % from viscosity and fusible viewpoint, preferred 20～50 weight %.

When cooperating the isocyanate-based crosslinking chemical, its use level is usually with respect to urethane resin 100 weight portions, and the isocyanate-based crosslinking chemical is 5～100 weight portions.

Above such water system tackifier is coated on the gluing surface of above-mentioned diaphragm or optical compensation films or light polarizing film, both are fitted, can obtain polaroid of the present invention.Before gluing, easy gluing processing such as Corona discharge Treatment are implemented on the surface of diaphragm or optical compensation films, it also is effective improving wetting state in advance.

When using such water system tackifier, after stacked, under the temperature about 30～100 ℃, implement dried usually.Then,, can further improve adhesive power in the slaking of carrying out under the temperature about 20～50 ℃ about 1～10 day, thus preferred.

(adhesive phase)

Polaroid of the present invention can be in the outside of diaphragm or optical compensation films (diaphragm or optical compensation films with the face face opposition side that is laminated with light polarizing film) has adhesive phase.Such adhesive phase for example can be used for fitting with liquid crystal cells.

Constitute the bonding agent of adhesive phase,, just be not particularly limited as long as satisfy all characteristics (transparency, permanance, re-workability etc.) of in blooming, using.For example, can use and contain the following acrylic resin and the acrylic adhesive of crosslinking chemical, described acrylic resin is in the presence of polymerization initiator, to be principal ingredient with (methyl) acrylate, and the acrylic monomer composition that further contains (methyl) acrylic monomers that has functional group on a small quantity carry out free radical polymerization and form, glass transition temperature (Tg) is below 0 ℃.

At this, become (methyl) acrylate of the principal ingredient of acrylic resin, can represent with following formula:

CH ₂＝C(R ₁)COOR ₂

In the formula, R ₁Expression hydrogen atom or methyl, R ₂The expression carbon number is 1～14 alkyl or aralkyl, R ₂The hydrogen atom of alkyl or the hydrogen atom of aralkyl can be replaced by the alkoxy of carbon number 1～10.

In addition, having (methyl) acrylic monomers of functional group, is the monomer that contains hydroxyl, carboxyl, amino, epoxy radicals isopolarity functional group and the two keys (being generally (methyl) acryloyl group) of alkene at molecule.

If enumerate the concrete example that becomes (methyl) of acrylic resin principal ingredient acrylate, R is for example arranged ₁Be hydrogen, R ₂Be the butyl acrylate of normal-butyl, R ₁Be hydrogen, R ₂2-EHA for the 2-ethylhexyl.In addition, if enumerate the concrete example of (methyl) acrylic monomers with functional group, for example as (methyl) acrylic monomers with hydroxyl, (methyl) acrylic acid 2-hydroxy methacrylate is arranged, (methyl) acrylic monomers as having carboxyl has acrylic acid etc.And then, when making this acrylic resin, can also as its example, can enumerate two (methyl) acrylic acid 1,4-butanediol ester etc. with having the monomer minor amounts of copolymerized of a plurality of (methyl) acryloyl group in the molecule.

When making acrylic resin, above-mentioned (methyl) acrylate and (methyl) acrylic monomers with functional group can distinguish only use a kind of, also can and with multiple.In addition, can be with the following acrylic resin composition of making as the resinous principle of bonding agent and use: described acrylic resin composition be, to and have the multiple combination of acrylic resin of multipolymer of (methyl) acrylic monomers of functional group as (methyl) acrylate, and the acrylic resin composition that obtains; The acrylic resin that perhaps in as the acrylic resin of this multipolymer, cooperate other acrylic resin, for example constitutes, and the acrylic resin composition that obtains by the homopolymerization or the multipolymer of (methyl) acrylic monomers that does not have functional group.

The crosslinking chemical that cooperates in acrylic adhesive can be isocyanates based compound, epoxy based compound, metallo-chelate based compound, aziridine based compound etc.The isocyanates based compound has 2 isocyanate group at least except using in the molecule (compound NCO) itself, can also use with adduct that reaction such as itself and polyvalent alcohol is obtained, its form of dipolymer, trimer etc.If enumerate the concrete example of crosslinking chemical, then as the diisocyanate based compound, the trimethylolpropane adduct of hexamethylene diisocyanate, the trimethylolpropane adduct of toluene diisocyanate etc. are arranged, how to use in the mode that it is dissolved in the solution in the organic solvents such as ethyl acetate respectively.These crosslinking chemicals can be distinguished use separately, also can make up multiple use.

The weight-average molecular weight of the acrylic resin that contains in the acrylic adhesive converts with the polystyrene standard that uses gel permeation chromatography (GPC), is generally about 600,000～2,000,000, preferred about 800,000～1,800,000.If the situation that weight-average molecular weight less than 600,000, then exists cohesive, permanance to reduce sometimes.In addition, if weight-average molecular weight surpasses 2,000,000, then adhesive phase becomes really up to the mark, peels off the difficulty that becomes after bonding, brings bad stress birefrin for sometimes the diaphragm or the optical compensation films of fitting.

Above-mentioned acrylic resin can be dissolved in organic solvents such as ethyl acetate, and then obtains acrylic adhesive solution by adding crosslinking chemical.In addition, as required, one or two or more kinds in silane coupling agent, weather-proof stabilizing agent, tackifier, plastifier, softening agent, pigment and the inorganic filler can be contained, and then light diffusing particulates such as organic pearl can be contained.

The acrylic adhesive solution that so obtains is coated on the stripping film usually, heats about 0.5～10 minute down at 60～120 ℃, heats up in a steamer organic solvent, makes adhesive phase.Then, after described diaphragm or optical compensation films and the applying of this adhesive phase, for example under the environment of 23 ℃ of temperature, humidity 65%, carry out the slaking about 5～20 days, make fully reaction of crosslinking chemical (C).

In addition, also can be after forming adhesive phase on the stripping film, the stripping film of further fitting obtains the adhesive phase monolithic of substrate support such as protected film not.At this moment, after the applying of stripping film, also under the environment of for example 23 ℃ of temperature, humidity 65%, carry out the slaking about 5～20 days, crosslinking chemical is fully reacted.Such adhesive phase monolithic when making diaphragm or optical compensation films, in the period of needs, is peeled off one-sided stripping film and diaphragm or optical compensation films applying use.

The raw material of above-mentioned such acrylic adhesive can easily obtain commercially available product, for example, can enumerate various acrylic monomers (Nippon Shokubai Co., Ltd's system, Toagosei Co., Ltd's system), as 2 of polymerization initiator, (big tomb science Co., Ltd. system such as 2 '-azoisobutyronitrile, Japan Finechem corporate system), hexamethylene diisocyanate and its trimethylolpropane adduct as crosslinking chemical, (Mitsui Chemical Polyurethane Co., Ltd's systems such as toluene diisocyanate and its trimethylolpropane adduct, Sumika Bayer Urethane corporate system).

In addition, adhesive sheet also has commercially available product, for example, can enumerate " carrier-free (ノ Application キ ヤ リ ア) binder film/sheet " (Lintec corporate system, Nitto Denko Corp's system).

As the above polaroid that is made; promptly; polaroid with layer structure of stretching polyethylene terephthalate film/first adhesive layer/light polarizing film/second adhesive layer/[diaphragm or optical compensation films]/adhesive phase/stripping film; stripping film is peeled off from adhesive phase; fit with liquid crystal cells, just can make liquid crystal panel.This liquid crystal panel goes for liquid crystal indicator.

Polaroid of the present invention for example in liquid crystal indicator, can be used as the polaroid in visual side configuration.So-called visual side is meant with the liquid crystal cells to be benchmark, a side opposite with the source backlight of liquid crystal indicator.Polaroid in the configuration of the rear side (source backlight) of liquid crystal indicator both can be a polaroid of the present invention, can be known in the past polaroid.

The mode of operation that is fitted with the liquid crystal cells of polaroid can make it be fit to by the optical compensation films that suitable selection fits in polaroid, thereby be not particularly limited, from viewpoint as slim, high productivity of the feature of polaroid of the present invention etc., the VA pattern of preferred transmission type or the liquid crystal cells of IPS pattern, wherein, be more preferably pattern wherein and be relatively large TV situation with liquid crystal cells.In addition, when giving anti-dazzle property to the stretching polyethylene terephthalate film that polaroid of the present invention had, preferred polaroid of the present invention is as the polaroid of visual side.

Embodiment

Below, further describe the present invention by embodiment, but the present invention is not subjected to the qualification of these examples.In addition, in these examples, the % of expression content and use amount and part are weight basis unless otherwise specified.

The making of [Production Example 1] light polarizing film

99.9 moles of average degree of polymerization is about 2400, saponification degrees are more than the % and after the polyvinyl alcohol film of thickness 75 μ m is immersed in 30 ℃ the pure water, are in 30 ℃ of dippings in 0.02/2/100 the aqueous solution in the weight ratio of iodine/potassium iodide/water.Then, be in 56.5 ℃ of dippings in 12/5/100 the aqueous solution in the weight ratio of potassium iodide/boric acid/water.Then, after 8 ℃ pure water washing, carry out drying, obtain on polyvinyl alcohol (PVA), being adsorbed with the light polarizing film of iodine and iodine generation orientation at 65 ℃.Stretch and mainly carry out in iodine staining and boric acid treatment process, total stretching ratio is 5.3 times.

[Production Example 2] has the making of the polyethylene terephthalate film of antiglare layer

Following each composition is dissolved in the ethyl acetate with solid component concentration 60%, demonstrates the ultra-violet solidified resin composition of 1.53 refractive indexes after preparing to solidify.

60 parts of pentaerythritol triacrylates

40 parts of polyfunctional poly ammonia esterification of acrylic esters (resultant of reaction of hexamethylene diisocyanate and pentaerythritol triacrylate)

Then; with respect to 100 parts of the solid constituents of this ultra-violet solidified resin composition; add porous silica particle " SYLYSIA " (trade name; fuji-silysia chemical corporate system) 2.0 part and as " Lucirin TPO " (BASF AG's system, chemical name: (2 of Photoepolymerizationinitiater initiater; 4; the 6-trimethylbenzoyl) diphenyl phosphine oxide) 5 parts, the modulation coating fluid.

This coating fluid is coated on the biaxial stretch-formed polyethylene terephthalate film (thickness 38 μ m), formed the ultra-violet solidified resin composition layer, in being set in 80 ℃ dryer, make its dry 3 minutes.From the ultra-violet solidified resin composition layer side of dry caudacoria, count 300mJ/cm with h ray conversion light quantity ²Mode exposure intensity 20mW/cm ²The light from high-pressure sodium lamp, the ultra-violet solidified resin composition layer is solidified, obtain by the duplexer formation that has concavo-convex antiglare layer (cured resin) and biaxial stretch-formed polyethylene terephthalate film on the surface, haze value is 10% polyethylene terephthalate film.Haze value is measured with mist degree/transmissivity meter HM-150 type (Murakami K. K.'s dye technology institute system).

The making of [Production Example 3] active energy ray-curable adhesive compound

Each composition below mixing is made aqueous adhesive compound A～D.

(adhesive compound A)

80 parts of bisphenol A type epoxy resins

20 parts of bisphenol f type epoxy resins

Diphenyl [4-(thiophenyl) phenyl] sulfonium hexafluoro antimonate (cationic polymerization initiators)

4.0 part

1.0 parts of benzoin methylethers (photosensitizer)

Epoxide equivalent under the state that above-mentioned 2 kinds of epoxy resin are mixed is 186g/eq, and total chlorine amount is 1520ppm.In addition, adhesive compound A is 7600mPa with Brookfield viscometer in the viscosity that 60rpm measures in 25 ℃.The total chlorine amount of adhesive compound A is according to JIS K 7243-3 (ISO 21627-3), with (also is same for following adhesive compound) of the titration measuring of liquor argenti nitratis ophthalmicus.

(adhesive compound B)

60 parts of bisphenol A type epoxy resins

40 parts in two (3-ethyl-3-oxetanes ylmethyl) ether

Diphenyl [4-(thiophenyl) phenyl] sulfonium hexafluoro antimonate (cationic polymerization initiators)

4.0 part

1.0 parts of benzoin methylethers (photosensitizer)

The epoxide equivalent of above-mentioned epoxy resin is 189g/eq, and the oxetanes equivalent of oxetane compound is 107g/eq.In addition, the total chlorine amount of adhesive compound B is 560ppm, is 670mPas with Brookfield viscometer in the viscosity that 60rpm measures in 25 ℃.

(adhesive compound C)

3,4-epoxycyclohexyl methyl 3,4-epoxycyclohexane carboxylate

40 parts

60 parts of bisphenol A type epoxy resins

Diphenyl [4-(thiophenyl) phenyl] sulfonium hexafluoro antimonate (cationic polymerization initiators)

4.0 part

1.0 parts of benzoin methylethers (photosensitizer)

Above-mentioned 3,4-epoxycyclohexyl methyl 3, the epoxide equivalent of 4-epoxycyclohexane carboxylate are 126g/eq, and the epoxide equivalent of bisphenol A type epoxy resin is 187g/eq.In addition, the total chlorine amount of adhesive compound C is 840ppm, is 3000mPas with Brookfield viscometer in the viscosity that 60rpm measures in 25 ℃.

(adhesive compound D)

3,4-epoxycyclohexyl methyl 3,4-epoxycyclohexane carboxylate

80 parts

20 parts of bisphenol f type epoxy resins

Diphenyl [4-(thiophenyl) phenyl] sulfonium hexafluoro antimonate (cationic polymerization initiators)

4.0 part

1.0 parts of benzoin methylethers (photosensitizer)

The epoxide equivalent of above-mentioned bisphenol f type epoxy resin is 172g/eq.In addition, the total chlorine amount of adhesive compound D is 400ppm, is 780mPas with Brookfield viscometer in the viscosity that 60rpm measures in 25 ℃.

The making of [Production Example 4] water system tackifier

Each composition below mixing is made the water system tackifier.

100 parts of pure water

3.0 parts of carboxy-modified polyvinyl alcohol (PVA) [" Kuraray POVAL KL-318 " (Kuraray corporate system)]

1.5 parts of water soluble polyamide epoxy resin (aqueous solution of solid component concentration 30%) [" SUMIREZRESIN 650 " (selling)] by Sumitomo chemtex company

＜embodiment 1 〉

After the binding face (with the surface of antiglare layer side opposition side) of the biaxial stretch-formed polyethylene terephthalate film with antiglare layer (thickness 43 μ m) that obtains in Production Example 2 implemented corona treatment, the adhesive compound A that will obtain in Production Example 3 painted the thickness of 2 μ m with the apparatus for coating that has chamber scraper (チ ャ Application バ one De Network タ).In addition, go up with same device at the tri acetyl cellulose membrane of handling through saponification (thick 80 μ m) and be coated on the water system tackifier that obtains in the Production Example 4 with the thickness of 2 μ m.

Behind each film coating binder composition, be situated between respectively at once by the coated face of each adhesive compound, utilize doubling roller, the biaxial stretch-formed polyethylene terephthalate film of applying on the single face of the light polarizing film that Production Example 1 obtains, the tri acetyl cellulose membrane of on another side, fitting and handling through saponification.Then, become 600mJ/cm from biaxial stretch-formed polyethylene terephthalate film side with the accumulative total light quantity of 320～400nm wavelength ²Mode ivb metal halide lamp, then further with the film of fitting by being set in 70 ℃ heated air circulation type dryer, make the adhesive solidification on two sides.

Then, the polaroid that so obtains is wound into the roller shape with collecting device.The light polarizing film of this polaroid and biaxial stretch-formed polyethylene terephthalate film and the tri acetyl cellulose membrane handled through saponification gluing good is with the polaroid slaking of reeling after 1 day, even the interface that cutting knife is inserted each film also fails to peel off.

＜embodiment 2 〉

Except use adhesive compound B replaced adhesive compound A, other carried out similarly to Example 1, obtains polaroid.

The light polarizing film of this polaroid and biaxial stretch-formed polyethylene terephthalate film and the tri acetyl cellulose membrane handled through saponification gluing not worse than embodiment 1, take sample immediately from the polaroid of reeling, even with the interface that cutting knife inserts each film, also fail to peel off.

＜embodiment 3 〉

After the binding face (with the surface of antiglare layer side opposition side) of the biaxial stretch-formed polyethylene terephthalate film with antiglare layer (thickness 43 μ m) that obtains in Production Example 2 implemented corona treatment, the adhesive compound B that will obtain in Production Example 3 painted the thickness of 2 μ m with the apparatus for coating that has the chamber scraper.

In addition, the binding face of the tri acetyl cellulose membrane (thick 80 μ m) handled without saponification implemented corona treatment after, the adhesive compound B of the thickness of coating thickness 2 μ m similarly.

Behind each film coating binder composition, be situated between respectively at once by the coated face of each adhesive compound, utilize doubling roller, the biaxial stretch-formed polyethylene terephthalate film of on the single face of the light polarizing film that Production Example 1 obtains, fitting, the tri acetyl cellulose membrane of on another side, fitting.Then, become 600mJ/cm from biaxial stretch-formed polyethylene terephthalate film side with the accumulative total light quantity of 320～400nm wavelength ²Mode ivb metal halide lamp, make the adhesive solidification on two sides then.

Then, the polaroid that so obtains is wound into the roller shape with collecting device.The light polarizing film of this polaroid and biaxial stretch-formed polyethylene terephthalate film and the tri acetyl cellulose membrane handled without saponification gluing good taked sample immediately from the polaroid of reeling, even the interface that cutting knife is inserted each film also fails to peel off.

＜embodiment 4 〉

Except use adhesive compound C replaced adhesive compound A, other carried out similarly to Example 1, obtains polaroid.

The light polarizing film of this polaroid and biaxial stretch-formed polyethylene terephthalate film and the tri acetyl cellulose membrane handled without saponification gluing good taked sample immediately from the polaroid of reeling, even the interface that cutting knife is inserted each film also fails to peel off.

After 1 day, use super cutting knife (the wild smart mechanism of Co., Ltd. reed is done made) to be cut into the shape of long 345mm, wide 277mm this polaroid slaking, Jie is fitted in the tri acetyl cellulose membrane side by adhesive phase and makes test specimen on the alkali-free glass.Then, with the cold shock testing machine to this test specimen carry out 1 the circulation be :-35 ℃/1 hour～70 ℃/1 hour endurancing, though the result experienced 150 the circulation, the damage of light polarizing film does not take place yet.

＜embodiment 5 〉

Except use adhesive compound D replaced adhesive compound C, other carried out similarly to Example 4, obtains polaroid.The light polarizing film of this polaroid and biaxial stretch-formed polyethylene terephthalate film and the tri acetyl cellulose membrane handled without saponification gluing good taked sample immediately from the polaroid of reeling, even the interface that cutting knife is inserted each film also fails to peel off.In addition, carry out endurancing similarly to Example 4,, the damage of light polarizing film does not take place yet even the result has experienced 300 circulations.

＜embodiment 6 〉

Except use adhesive compound D replaced adhesive compound B, other carried out similarly to Example 3, obtains polaroid.The light polarizing film of this polaroid and biaxial stretch-formed polyethylene terephthalate film and the tri acetyl cellulose membrane handled without saponification gluing good taked sample immediately from the polaroid of reeling, even the interface that cutting knife is inserted each film also fails to peel off.In addition, carry out endurancing similarly to Example 4,, the damage of light polarizing film does not take place yet even the result has experienced 300 circulations.

＜comparative example 1 〉

After the binding face (with the surface of antiglare layer side opposition side) of the biaxial stretch-formed polyethylene terephthalate film with antiglare layer (thickness 43 μ m) that obtains in Production Example 2 implemented corona treatment, the water system tackifier that will obtain in Production Example 4 was painted the thickness of 2 μ m with the apparatus for coating that has the chamber scraper.

In addition, to the tri acetyl cellulose membrane of handling through saponification (thick 80 μ m), with the above-mentioned water system tackifier that similarly is coated with.

Behind each film coating binder, be situated between respectively at once by the coated face of each tackifier, utilize doubling roller, the biaxial stretch-formed polyethylene terephthalate film of on the single face of the light polarizing film that Production Example 1 obtains, fitting, the tri acetyl cellulose membrane of on another side, fitting and handling through saponification.Then, the film of fitting by being set in 70 ℃ heated air circulation type dryer, is made adhesive solidification.

Then, the polaroid that so obtains is wound into the roller shape with collecting device.There is not sufficient adhesive power between the light polarizing film of this polaroid and the biaxial stretch-formed polyethylene terephthalate film, with the polaroid slaking of reeling after 1 day, with the interface that cutting knife inserts light polarizing film and biaxial stretch-formed polyethylene terephthalate film, the result easily peels off.In addition, carry out endurancing similarly to Example 4, the result is experiencing below 150 circulations, and diffract damage has just taken place in the end of light polarizing film.

＜embodiment 7 〉

After the binding face of biaxial stretch-formed polyethylene terephthalate film (thickness 38 μ m) was implemented corona treatment, the adhesive compound B that will obtain in Production Example 3 painted the thickness of thick 2 μ m with the apparatus for coating that has the chamber scraper.

In addition, preparation (postpones in thickness 68 μ m, the face: the delay of 63nm, thickness direction: 225nm) with the optical compensation films that said method obtains the stretching of cyclic olefin resin film, after its binding face implemented corona treatment, similarly with the thickness coating binder composition B of thick 2 μ m.

Behind each film coating binder composition, be situated between respectively at once by the coated face of each adhesive compound, utilize doubling roller, the biaxial stretch-formed polyethylene terephthalate film of on the single face of the light polarizing film that Production Example 1 obtains, fitting, the optical compensation films of on another side, fitting.Then, become 200mJ/cm from the optical compensation films side with the accumulative total light quantity of 280～320nm wavelength ²Mode shine high-pressure sodium lamp, make the adhesive solidification on two sides.

Then, the polaroid that so obtains is wound into the roller shape with collecting device.The light polarizing film of this polaroid and biaxial stretch-formed polyethylene terephthalate film and optical compensation films gluing good taked sample immediately from the polaroid of reeling, even the interface that cutting knife is inserted each film also fails to peel off.

＜embodiment 8 〉

Except use adhesive compound D replaced adhesive compound B, other carried out similarly to Example 7, obtains polaroid.The light polarizing film of this polaroid and biaxial stretch-formed polyethylene terephthalate film and optical compensation films gluing good taked sample immediately from the polaroid of reeling, even the interface that cutting knife is inserted each film also fails to peel off.In addition, carry out endurancing similarly to Example 4,, the damage of light polarizing film does not take place yet even the result has experienced 300 circulations.

＜reference example 1 〉

Except the use level with the epoxy compound of adhesive compound A change to following, make polaroid similarly to Example 1, also obtained same result.

60 parts of bisphenol A type epoxy resins

40 parts of bisphenol f type epoxy resins

＜reference example 2 〉

Except the oxetane compound with adhesive compound B change to following, similarly make polaroid with embodiment 2, embodiment 3, embodiment 7, also obtained same result.

3-ethyl-3-hydroxymethyl oxetanes

3-ethyl-3-(2-ethyl hexyl oxy methyl) oxetanes

1, two { [(the 3-ethyl oxetanes-3-yl) methoxyl] methyl } benzene of 4-

3-ethyl-3-(phenoxymethyl) oxetanes

3-ethyl-3-(cyclohexyloxy methyl) oxetanes

Phenol phenolic aldehyde oxetanes

1, two [(the 3-ethyl oxetanes-3-yl) methoxyl] benzene of 3-

＜reference example 3 〉

Except the use level with the epoxy compound of adhesive compound C change to following, make polaroid similarly to Example 4, also obtained same result.

3,4-epoxycyclohexyl methyl 3,4-epoxycyclohexane carboxylate

60 parts

20 parts of epoxidized polybutadienes

20 parts of bisphenol A type epoxy resins

＜reference example 4 〉

Except the bisphenol f type epoxy resin with adhesive compound D change to following, similarly make polaroid with embodiment 5, embodiment 6, embodiment 8, also obtained same result.

The glycidyl ether thing of cresol novolac resin

The glycidyl ether thing of phenyl phenol urea formaldehyde

1, the 4-butanediol diglycidyl ether

1, the 6-hexanediol diglycidyl ether

3-ethyl-3-hydroxymethyl oxetanes

3-ethyl-3-(2-ethyl hexyl oxy methyl) oxetanes

＜embodiment 9 〉

Adhesive sheet fitted in the tri acetyl cellulose membrane side that saponification is handled of not carrying out of the polaroid that obtains among the embodiment 3, with the long side direction of the picture dimension of absorption axes and LCD TV described later be harmonious severing, obtain polaroid A.In addition, similarly adhesive sheet is fitted to the optical compensation films side of implementing 7 polaroids that obtain, with the short side direction of the picture dimension of absorption axes and LCD TV described later be harmonious severing, obtain polaroid B.

From the liquid crystal panel of the commercially available LCD TV of the liquid crystal panel that carried the liquid crystal cells that has vertical alignment mode, peel off two-sided polaroid and take out liquid crystal cells.Jie is by adhesive sheet, and in the above-mentioned polaroid A of the front of this liquid crystal cells (visual side) applying, the above-mentioned polaroid B of (source backlight) applying makes liquid crystal panel overleaf.

Then, this liquid crystal panel is assembled with the formation of backlight/light diffusing sheet/diffusion sheet/liquid crystal panel, made liquid crystal indicator.Make this liquid crystal indicator work, the result does not observe the unequal unfavorable condition of color.

＜embodiment 10 〉

Except in embodiment 9, the polaroid that obtains among the embodiment 3 is changed to the polaroid that obtains among the embodiment 6, the polaroid that obtains among the embodiment 7 is changed to beyond the polaroid that obtains among the embodiment 8, and other carries out similarly to Example 9, obtains polaroid A and B.Similarly fit in liquid crystal cells, make liquid crystal panel, assemble, make liquid crystal indicator, make its work, the result does not observe the unequal unfavorable condition of color.

Current disclosed embodiment and embodiment are illustration in all respects, should not think a kind of restriction.Scope of the present invention is not to represent with above-mentioned explanation, but represents with claim, comprises with claim having same meaning and all changes in this scope.

Utilizability on the industry

Polarizer of the present invention, the solvent-free active energy ray-curable composition that contains epoxide by use is as adhesive and make its layer (adhesive layer) that is solidified to form, thereby can significantly improve the adaptation of stretching PETG film and light polarizing film. In addition, because adhesive is solvent-free, thereby does not need the drying process of in the past necessary adhesive, can significantly improve its productivity ratio.

Claims (7)

1. polaroid, it is characterized in that, possess the light polarizing film that is formed by polyvinyl alcohol resin and the stacked stretching polyethylene terephthalate film that is situated between by first adhesive layer on the single face of described light polarizing film, described first adhesive layer is made of the solidfied material layer of the solvent-free active energy ray-curable composition that contains epoxy compound.

2. polaroid according to claim 1, wherein, epoxy compound is the alicyclic epoxy compound.

3. polaroid according to claim 1 and 2, wherein, described active energy ray-curable composition further contains oxetane compound.

4. according to each described polaroid in the claim 1～3; wherein; on described light polarizing film and the face face opposition side that is laminated with described stretching polyethylene terephthalate film, possess Jie by second adhesive layer stacked diaphragm or optical compensation films.

5. polaroid according to claim 4, wherein, described second adhesive layer is made of the solidfied material layer of the composition identical with described active-energy solidification compound.

6. according to claim 4 or 5 described polaroids, wherein, have adhesive phase, this adhesive phase is layered on described diaphragm or described optical compensation films and the face face opposition side that is laminated with described light polarizing film.

7. a liquid crystal indicator is characterized in that possessing liquid crystal panel, and described liquid crystal panel has liquid crystal cells and the described polaroid of claim 6, and described polaroid is situated between and is fitted by its adhesive phase and described liquid crystal cells.