CN103858031A - Method for manufacturing polarizer - Google Patents

Abstract

This method for manufacturing a polarizer is provided with the following steps, in this order: an adhesive application step in which an active-energy-ray-curable adhesive is applied to one surface of a transparent film or transparent films or one or both surfaces of a polarizing film; a bonding step in which a layered body comprising the transparent film(s) layered to one or both surfaces of the polarizing film with the aforementioned adhesive interposed therebetween is sandwiched between a pair of bonding rollers rotating in the conveyance direction and pressure is applied to the layered body so as to bond the transparent film(s) to the polarizing film; ; and a first active-energy-ray exposure step in which the adhesive is cured by exposing the layered body to active-energy rays while said layered body is being conveyed in close contact with a roller rotating in the conveyance direction. At least one of the bonding rollers is a rotationally driven rubber roller that has a rubber surface, and the rotating roller rotates faster than said rubber roller.

Description

The manufacture method of polarization plates

Technical field

The present invention relates to as the manufacture method of polarization plates that forms one of useful optical component such as liquid crystal display.

Background technology

Polarizing coating is widely used as making dichroism pigment be adsorbed in polyvinyl alcohol resin film and being orientated the material forming, known have using iodine as the iodine of dichromatism pigment be polarizing coating or be polarizing coating etc. using dichromatism direct dyes as the dyestuff of dichromatism pigment.These polarizing coatings generally form polarization plates at its single or double via hyaline membranes such as tackifier laminating tri acetyl cellulose membranes.

As the method for the stacked hyaline membrane of single or double at polarizing coating, have in advance after the surface-coated active energy ray curable resin of hyaline membrane, clamp polarizing coating and hyaline membrane with a pair of niproll (doubling roller), fit thus, then, irradiate active energy beam and make its bonding curing side (patent documentation 1: TOHKEMY 2004-245925 communique, patent documentation 2: TOHKEMY 2009-134190 communique, patent documentation 3: TOHKEMY 2011-95560 communique).

In patent documentation 3, record while making active energy ray curable resin solidification irradiating active energy beam, make the closely sealed outer peripheral face at roller of duplexer while make its solidify, thereby can suppress wave volume (ウ ェ ー ブ カ ー Le) etc. generation, but in the time that doubling roller and active energy beam irradiate and in the unsuitable situation of balance of the rotational speed of the closely sealed roller of duplexer, the polarization plates of made can rise and fall into the bad order (following, this state to be called to " corrugated plate shape fluctuating ") of corrugated plate shape.

Prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2004-245925 communique

Patent documentation 2: TOHKEMY 2009-134190 communique

Patent documentation 3: TOHKEMY 2011-95560 communique

Summary of the invention

Invent problem to be solved

The object of the invention is to, as above possess make duplexer be sealed at the outer peripheral face of roller while make in the method for operation of active energy ray curable resin solidification, realize and suppress the generation that corrugated plate shape rises and falls.

For the method for dealing with problems

The present invention is the manufacture method that hyaline membrane is fitted in to the polarization plates that the single or double of polarizing coating forms, described manufacture method possesses successively: tackifier painting process, at the one side of above-mentioned hyaline membrane or the single or double of above-mentioned polarizing coating, coating active energy ray curable tackifier; Bonding process, above-mentioned hyaline membrane is clamped in between a pair of doubling roller of conveyance direction rotation via the stacked duplexer forming in the single or double of above-mentioned polarizing coating of above-mentioned tackifier, and duplexer is exerted pressure, thus by above-mentioned hyaline membrane and the laminating of above-mentioned polarizing coating; And the 1st active energy beam irradiation process, above-mentioned duplexer is sealed in during the above-mentioned duplexer of conveyance under the state of the rotating roller of conveyance direction rotation, duplexer is irradiated to active energy beam, make above-mentioned adhesive solidification; Wherein, at least one party of above-mentioned a pair of doubling roller has the surface being made up of rubber and the rubber rollers being driven in rotation, and the rotational speed of above-mentioned rotating roller is faster than the rotational speed of above-mentioned rubber rollers.Above-mentioned rotating roller is preferably chill roll.

In the invention described above, the rotational speed of above-mentioned rubber rollers is made as at 100 o'clock, the rotational speed of above-mentioned rotating roller is preferably more than 100.1 and below 102.0.

Invention effect

According to the present invention, can make the good polarization plates of the outward appearance being suppressed that corrugated plate shape rises and falls.Therefore,, if use the polarization plates obtaining by manufacture method of the present invention, can provide the liquid crystal indicator of high-quality.

Brief description of the drawings

Fig. 1 is the diagrammatic side view that represents an embodiment of the manufacturing installation of polarization plates involved in the present invention.

Embodiment

The present invention is the manufacture method that hyaline membrane is fitted in to the polarization plates that the single or double of polarizing coating forms, described manufacture method possesses successively: tackifier painting process, at the one side of hyaline membrane or the single or double of polarizing coating, coating active energy ray curable tackifier; Bonding process, is clamped in hyaline membrane between a pair of doubling roller of conveyance direction rotation via the stacked duplexer forming in the single or double of polarizing coating of described tackifier, and duplexer is exerted pressure, thus by hyaline membrane and polarizing coating laminating; And the 1st active energy beam irradiation process, duplexer is sealed in during conveyance duplexer under the state of the rotating roller of conveyance direction rotation, duplexer is irradiated to active energy beam, make adhesive solidification.At least one party of above-mentioned a pair of doubling roller has the surface being made up of rubber and the rubber rollers being driven in rotation, and the rotational speed of above-mentioned rotating roller is faster than the rotational speed of above-mentioned rubber rollers.

First, for each important document of manufacture method of the present invention.

(polarizing coating)

The polarizing coating using in the manufacture method of polarization plates of the present invention particularly, is to make dichroism pigment be adsorbed in the polyvinyl alcohol resin film of uniaxial tension and be orientated the film forming.Polyvinyl alcohol resin film can be that resin saponification obtains by making polyvinyl acetate.Be resin as polyvinyl acetate, except the polyvinyl acetate of the homopolymer as vinyl acetate, also can enumerate the multipolymer (such as vinyl-vinyl acetate copolymer) of other monomers of vinyl acetate and energy and its copolymerization etc.As can with other monomers of vinyl acetate copolymerization, also can enumerate insatiable hunger and close carboxylic acids, olefines, vinyl ethers, unsaturated sulfonic acid class, there is acrylic amide of ammonium etc.The saponification degree of polyvinyl alcohol resin be 85 % by mole above, preferably more than 90 % by mole, more preferably 98～100 % by mole.The average degree of polymerization of polyvinyl alcohol resin is generally 1000～10000, and preferably 1500～5000.These polyvinyl alcohol resins can carry out modification, for example, can use through the polyvinyl formal of aldehydes modification, polyvinyl acetal, polyvinyl butyral etc.

The material that such polyvinyl alcohol resin masking is formed, the former material film that can be used as polarizing coating uses.The method of polyvinyl alcohol resin masking is not particularly limited, can passes through known proper method masking in the past.The thickness of the former material film being made up of polyvinyl alcohol resin is not particularly limited, for example, be 10～150 μ m left and right.Generally can supply with by roller shape, thickness is in the scope of 20～100 μ m, be preferably in the scope of 30～80 μ m, in addition, in the scope that the width of industrial practicality is 1500～6000mm.

With regard to commercially available polyvinyl alcohol mesentery, the former material thickness of (Vinylon VF-PS#7500, Kuraray system/OPL film, M-7500, the synthetic system of Japan) is 75 μ m, the former material thickness of (Vinylon VF-PS#6000, Kuraray system, Vinylon VF-PE#6000, Kuraray system) is 60 μ m.

Polarizing coating is generally manufactured through following operation: make polyvinyl alcohol resin film dyeing and the operation (dyeing treatment process) of absorption dichromatism pigment, the operation (washing treatment process) that has the polyvinyl alcohol resin film of dichromatism pigment to wash with the operation of boric acid aqueous solution processing (boric acid treatment process) and after this boric acid aqueous solution is processed absorption with dichromatism pigment.

In addition, when the manufacture of polarizing coating, general polyvinyl alcohol resin film is by uniaxial tension, and this uniaxial tension can carry out before dyeing treatment process, also can in dyeing treatment process, carry out, and also can after dyeing treatment process, carry out.Carry out uniaxial tension after dyeing treatment process time, this uniaxial tension can carry out before boric acid treatment process, also can in boric acid treatment process, carry out.Certainly, also can in above-mentioned multiple stages, carry out uniaxial tension.

Uniaxial tension can be between the different roller of peripheral speed uniaxial tension, also can carry out uniaxial tension with hot-rolling.In addition, can be the dry type stretching stretching in atmosphere, also can be the wet type stretching and stretch under the state of solvent swell.Stretching ratio is generally 3～8 times of left and right.

In dyeing treatment process, the dyeing that utilizes dichromatism pigment of polyvinyl alcohol resin film for example by carrying out polyvinyl alcohol resin film immersion in the aqueous solution that contains dichromatism pigment.As dichromatism pigment, can use such as iodine, dichroic dye etc.Dichroic dye comprises: the dichromatism direct dyes that for example contains the bis-azo compounds such as C.I.DIRECT RED39; The dichromatism direct dyes that contains the compound such as trisazo-, four azos.It should be noted that, polyvinyl alcohol resin film is preferably implemented in advance the dip treating in water before dyeing is processed.

While using iodine as dichromatism pigment, generally adopt the method for flooding polyvinyl alcohol resin film and dye in the aqueous solution that contains iodine and potassium iodide.The content of the iodine in this aqueous solution is generally 0.01～1 weight portion with respect to every 100 weight parts waters, and the content of potassium iodide is generally 0.5～20 weight portion with respect to every 100 weight parts waters.Use iodine during as dichromatism pigment, be generally 20～40 DEG C for the temperature of the aqueous solution that dyes, the dip time (dyeing time) in this aqueous solution is generally 20～1800 seconds.

On the other hand, while using dichroic dye as dichromatism pigment, generally can adopt the method for flooding polyvinyl alcohol resin film and dye in the aqueous solution that contains dichroic dye.The content of the dichroic dye in this aqueous solution is generally 1 × 10 with respect to every 100 weight parts waters ^-4～10 weight portions, are preferably 1 × 10 ^-3～1 weight portion, is particularly preferably 1 × 10 ^-3～1 × 10 ^-2weight portion.This aqueous solution also can contain the inorganic salts such as sodium sulphate as dyeing assistant.Use dichroic dye during as dichromatism pigment, be generally 20～80 DEG C for the temperature of the aqueous dye solutions that dyes, in addition, the dip time (dyeing time) in this aqueous solution is generally 10～1800 seconds.

Boric acid treatment process is carried out in containing boron aqueous acid through the polyvinyl alcohol resin film immersion of dichromatism pigment dyeing by making.The amount of the boric acid in borated aqueous solution is generally 2～15 weight portions with respect to every 100 weight parts waters, is preferably 5～12 weight portions.While using iodine as dichromatism pigment in above-mentioned dyeing treatment process, preferably contain potassium iodide for the borated aqueous solution of this boric acid treatment process.Now, the amount of the potassium iodide in borated aqueous solution, with respect to every 100 weight parts waters, is generally 0.1～15 weight portion, preferably 5～12 weight portions.Dip time in borated aqueous solution is generally 60～1200 seconds, and preferably 150～600 seconds, further preferably 200～400 seconds.The temperature of borated aqueous solution is generally more than 40 DEG C, is preferably 50～85 DEG C, more preferably 55～75 DEG C.

Then,, in washing treatment process, by for example being impregnated in, above-mentioned boric acid polyvinyl alcohol resin film after treatment in water, washes processing.The temperature of the water in washing processing is generally 4～40 DEG C, and dip time is generally 1～120 second.After washing is processed, general enforcement is dry to be processed, and can obtain polarizing coating.Dry suitable use such as air drier, the far infra-red heater etc. processed carries out.The dry temperature of processing is generally 30～100 DEG C, is preferably 50～80 DEG C.The dry time of processing is generally 60～600 seconds, is preferably 120～600 seconds.

Like this, implement uniaxial tension, the dyeing that utilizes dichromatism pigment, boric acid processing and washing for polyvinyl alcohol resin film and process, can obtain polarizing coating.The thickness of this polarizing coating is generally in the scope of 5～50 μ m.

(hyaline membrane)

In the present invention, hyaline membrane is fitted in the single or double of above-mentioned polarizing coating.As forming the material of hyaline membrane, for example, can enumerate the widely used membrane material in the past in this field such as the polyester based resin of cyclic olefine resin, acetate fiber prime system resin, polyethylene terephthalate or PEN, polybutylene terephthalate and so on, polycarbonate-based resin, acrylic resin, polypropylene.While making hyaline membrane be fitted in polarizing coating two-sided, each hyaline membrane can be the film of identical type, can be also different types of film.

Cyclic olefine resin is for example to have the thermoplastic resin (being also referred to as thermoplasticity cyclic olefine resin) of the monomeric unit of the cyclic olefin (cycloolefin) that comprises norborene, polycyclic system norbornene monomer and so on.Cyclic olefine resin also can be the ring-opening polymerization polymer of above-mentioned cycloolefin or uses the hydride of the ring opening copolymer thing of two or more cycloolefin, also can be cycloolefin and chain alkene, has the addition polymer of aromatics of vinyl etc.In addition, the cyclic olefine resin of importing polar group is also effective.

When using cycloolefin and chain alkene and/or thering is the multipolymer of aromatics of vinyl, as chain alkene, can enumerate ethene, propylene etc., in addition, as the aromatics with vinyl, can enumerate styrene, α-methyl styrene, core alkyl-substituted styrene etc.In such multipolymer, the monomeric unit that comprises cycloolefin can be 50 % by mole following (preferably 15～50 % by mole).Especially,, when using cycloolefin and chain alkene and having the terpolymer of aromatics of vinyl, the monomeric unit that comprises cycloolefin, can be fewer amount as described above.In such terpolymer, the monomeric unit that comprises chain alkene is generally 5～80 % by mole, and the monomeric unit that comprises the aromatics with vinyl is generally 5～80 % by mole.

Cyclic olefine resin can the suitable commercially available product of suitable use, such as Topas(Ticona company system), Arton(JSR(strain) company's system), ZEONOR(Japan ZEON(strain) system), ZEONEX(Japan ZEON(strain) system), Apel(Mitsui Chemicals (strain) system), OXIS( great Cang industrial group system) etc.When such cyclic olefine resin masking is formed to film, can suitable use solvent casting method, the known method such as extrusion by melting.In addition, such as also can use Escena(ponding chemical industry (strain) system), SCA40(ponding chemical industry (strain) system), ZeonorFilm(Optes(strain) system) etc. the commercially available product of the resinous film of cyclic olefine of masking in advance.

Cyclic olefine resin molding also can be through uniaxial tension or biaxial stretch-formed material.Can give phase difference value arbitrarily to cyclic olefine resin molding by stretching.Stretch and generally unreel on one side and carry out continuously from film roller on one side, utilize heating furnace, stretch towards the direct of travel (length direction of film) of roller, direction (Width of film) or its both sides vertical with its direct of travel.The temperature of heating furnace is general to be adopted near the scope to the glass transition temperature+100 DEG C glass transition temperature of cyclic olefine resin.The multiplying power stretching is generally 1.1～6 times, preferably 1.1～3.5 times.

If cyclic olefine resin molding is in roller reeling condition, film is bonded to each other and has the tendency of easy generation adhesion, thus generally fit after diaphragm, then form roller volume.In addition, because of the general surfactivity of cyclic olefine resin molding poor, therefore preferably carry out the surface treatments such as Cement Composite Treated by Plasma, corona treatment, ultraviolet treatment with irradiation, flame (fire is scorching) processing, saponification processing with the bonding surface of polarizing coating.Wherein, be preferably and can, than the Cement Composite Treated by Plasma that is easier to implement, be particularly preferably atmospheric plasma treatment, corona treatment.

Acetate fiber prime system resin refers to cellulosic partially or completely carboxylate, for example, can enumerate and comprise cellulosic acetic acid esters, propionic ester, butyric ester, their film of mixed ester etc.More specifically, can enumerate tri acetyl cellulose membrane, diacetyl cellulose film, cellulose ethanoate propionic ester film, cellulose acetate butyrate film etc.As such cellulose esters resin film, can preferably use suitable commercially available product, for example: Fujitac TD80(Fujiphoto (strain) system), Fujitac TD80UF(Fujiphoto (strain) system), Fujitac TD80UZ(Fujiphoto (strain) system), KC8UX2M(Konica Minolta Opto(strain) system), KC8UY(Konica Minolta Opto(strain) system), Fujitac TD60UL(Fujiphoto (strain) system), KC2UAW(Konica Minolta Opto(strain) system), KC4UYW(Konica Minolta Opto(strain) system), KC6UAW(Konica Minolta Opto(strain) system) etc.

In addition, as hyaline membrane, also can suitable use give the cellulose acetate resin film of phase difference characteristics.As the commercially available product of such cellulose acetate resin film of having given phase difference characteristics, can enumerate WV BZ438(Fujiphoto (strain) system), KC4FR-1(Konica Minolta Opto(strain) system), KC4CR-1(Konica Minolta Opto(strain) system), KC4AR-1(Konica Minolta Opto(strain) system) etc.Cellulose acetate is also referred to as acetyl group cellulose, or is also referred to as cellulose ethanoate.

These cellulose acetate resin films easily absorb water, and exist the moisture rate of polarization plates to bring the situation of the lax impact in the end of polarization plates.It is more preferred that moisture rate when polarization plates is manufactured more approaches equilibrium moisture rate in manufacturing line or the roller volume custodial warehouse of keeping environment, for example dust free room of polarization plates, although also depend on the formation of stacked film, but be for example 2.0～3.5% left and right, more preferably 2.5～3.0%.The numerical value of the moisture rate of this polarization plates is measured with dry weight method, is the weight change after 105 DEG C/120 minutes.

The thickness of the hyaline membrane using in the manufacture method of polarization plates of the present invention, although be preferably thin thickness, if too thin, intensity will reduce, and makes processability deteriorated.On the other hand, if too thickly can produce the problems such as the transparency reduces or stacked rear required set time is elongated.So the suitable thickness of hyaline membrane is for example 5～200 μ m, and be preferably 10～150 μ m, and 10～100 μ m more preferably.

For improving the cementability of tackifier and polarizing coating and/or hyaline membrane, also can implement the surface treatments such as corona treatment, flame treatment, Cement Composite Treated by Plasma, UV treatment, primary coat (primer) coating processing, saponification processing to polarizing coating and/or hyaline membrane.

In addition, can be respectively implement non-glare treated, antireflection processing, be firmly coated with the surface treatments such as processing, antistatic treatment, antifouling processing for hyaline membrane separately, or also above-mentioned processing of more than two kinds capable of being combined being implemented.In addition, hyaline membrane and/or hyaline membrane sealer also can contain the ultraviolet light absorber such as benzophenone based compound, benzotriazole based compound, or the plastifier such as phenyl phosphate based compound, phthalate compound.

In addition, hyaline membrane can have as the function of phase retardation film, as the function of brightness enhancement film, as the function of reflectance coating, as the function of semi-transparent anti-film, as the function of diffusion barrier, as optical functions such as the functions of optical compensation films.Now, for example pass through at optical functional films such as the stacked phase retardation film in the surface of hyaline membrane, brightness enhancement film, reflectance coating, semi-transparent anti-film, diffusion barrier, optical compensation films, thereby there is such function, in addition, also can give such function to hyaline membrane itself.In addition, also can, as thering is the diffusion barrier etc. of function of brightness enhancement film, make hyaline membrane there are multiple functions.

For example, the stretch processing that can record by No. 2841377 communique of the hyaline membrane date of execution this patent to above-mentioned, No. 3094113 communique of Jap.P. etc., or the processing that No. 3168850 communique is recorded of date of execution this patent, thereby give the function as phase retardation film.The phase difference characteristics of phase retardation film, can suitably select such as front phase difference value is 5～100nm, thickness direction phase difference value scope that is 40～300nm etc.In addition, for above-mentioned hyaline membrane, by adopting the method that TOHKEMY 2002-169025 communique or TOHKEMY 2003-29030 communique are recorded to form minute aperture, or by stacked different the centre wavelength of selecting reflection 2 layers above cholesteric liquid crystal layer, thereby can give the function as brightness enhancement film.

If above-mentioned hyaline membrane is formed to metal film by evaporation or sputter etc., can give the function as reflectance coating or semi-transparent anti-film.Containing fine-grained resin solution, can give the function as diffusion barrier by coating on above-mentioned hyaline membrane.In addition, by being coated with the liquid crystal compounds such as plate-like liquid crystal compounds and making its orientation on above-mentioned hyaline membrane, thereby can give the function as optical compensation films.In addition, also can make hyaline membrane contain the compound that manifests phase differential.Further, also can use suitable tackifier, make various optical functional films directly fit in polarizing coating.As the commercially available product of optical functional film, for example, can enumerate: DBEF(3M company system, can be from Sumitomo 3M(strain in Japan) obtain) etc. brightness enhancement film; The visual angle improvement films such as WV film (Fujiphoto (strain) system); ArtonFilm(JSR(strain) system), ZeonorFilm((strain) Optes system), Escena(ponding chemical industry (strain) system), VA-TAC(Konica Minolta Opto(strain) system), Sumikalight(Sumitomo Chemical (strain) system) the poor film of equiphase etc.

(active energy ray curable tackifier)

Polarizing coating and hyaline membrane are fitted via the tackifier of active energy ray curable.As active energy ray curable tackifier, from viewpoints such as weatherability, refractive index, cationically polymerizables, can enumerate by irradiating active energy beam tackifier that be cured, that comprise the epoxy based resin composition that contains epoxy resin.But, be not limited thereto, the various active energy ray curable tackifier (organic solvent is that tackifier, hot melt are tackifier, solventless adhesive etc.) that in the past used can be adopted in the manufacture of polarization plates, for example, the tackifier of the acrylic resin compositions such as acrylamide, acrylate, urethane acrylate, epoxy acrylate etc. can be comprised.

Epoxy resin refers to the compound in molecule with more than 2 epoxy radicals.From viewpoints such as weatherability, refractive index, cationically polymerizables, epoxy resin contained in the curable epoxy resin composition as tackifier is preferably, and does not contain the epoxy resin (reference example is as patent documentation 1) of aromatic rings in molecule.Can illustrate hydrogenated epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin etc. as such epoxy resin.

Hydrogenated epoxy resin can be by making polyol as the raw material of aromatic epoxy resin under the existence of catalyzer, under pressurized conditions, selectivity obtains core hydrogenation polyol through core hydrogenation, then the method that this core hydrogenation polyol is carried out to glycidyl ether obtains.As aromatic epoxy resin, for example, can enumerate: the bisphenol-type epoxy resins such as the diglycidyl ether of the diglycidyl ether of bisphenol-A, the diglycidyl ether of Bisphenol F and bisphenol S; The epoxy resin of the phenol aldehyde types such as phenol novolac epoxy resins, cresol novolak epoxy and hydroxy benzaldehyde phenol novolac epoxy resins; The epoxy resin of the multifunctional types such as the glycidol ether of tetrahydroxy benzene methylmethane, the glycidol ether of tetrahydroxybenzophenone and epoxidation polyvinyl phenol etc.In hydrogenated epoxy resin, be preferably the glycidol ether of the bisphenol-A of hydrogenation.

Alicyclic epoxy resin refers to the epoxy resin in molecule with the epoxy radicals that 1 above and ester ring type ring key closes." epoxy radicals of closing with ester ring type ring key " refers to the oxygen atom-O-of the bridging structure in the structure shown in following formula.In following formula, m is 2～5 integer.

［ changing 1 ］

By (the CH in above-mentioned formula ₂) _min one or more hydrogen atoms remove and the group that obtains and other chemical constitution bondings and compound, can become alicyclic epoxy resin.(CH ₂) _min one or more hydrogen atoms, can also suitably replace with the straight chain-like alkyl such as methyl, ethyl.In alicyclic epoxy resin, there is the epoxy resin of oxabicyclo hexane ring (compound of m=3 in above-mentioned formula), oxabicyclo heptane ring (compound of m=4 in above-mentioned formula), demonstrate excellent cementability, so preferably use.Below, exemplified with the alicyclic epoxy resin of preferred use, be still not limited to these compounds particularly.

(a) the epoxycyclohexyl methyl epoxycyclohexane carboxylate class shown in following formula (I):

［ changing 2 ］

(in formula, R ¹and R ²represent independently of each other the straight chain-like alkyl of hydrogen atom or carbon number 1～5.）

(b) the epoxycyclohexane carboxylate class of the alkane diol shown in following formula (II):

［ changing 3 ］

(in formula, R ³and R ⁴the straight chain-like alkyl that represents independently of each other hydrogen atom or carbon number 1～5, n represents 2～20 integer.）

(c) the epoxycyclohexyl methyl ester class of the dicarboxylic acid shown in following formula (III):

［ changing 4 ］

(in formula, R ⁵and R ⁶the straight chain-like alkyl that represents independently of each other hydrogen atom or carbon number 1～5, p represents 2～20 integer.）

(d) the epoxycyclohexyl methyl ethers of the polyglycol shown in following formula (IV):

［ changing 5 ］

(in formula, R ⁷and R ⁸the straight chain-like alkyl that represents independently of each other hydrogen atom or carbon number 1～5, q represents 2～10 integer.）

(e) the epoxycyclohexyl methyl ethers of the alkane diol shown in following formula (V):

［ changing 6 ］

(in formula, R ⁹and R ¹⁰the straight chain-like alkyl that represents independently of each other hydrogen atom or carbon number 1～5, r represents 2～20 integer.）

(f) bicyclic oxygen three spiro-compounds shown in following formula (VI):

［ changing 7 ］

(in formula, R ¹¹and R ¹²represent independently of each other the straight chain-like alkyl of hydrogen atom or carbon number 1～5.）

(g) the bicyclic oxygen single-spiro compound shown in following formula (VII):

［ changing 8 ］

(in formula, R ¹³and R ¹⁴represent independently of each other the straight chain-like alkyl of hydrogen atom or carbon number 1～5.）

(h) the vinyl cyclohexene diepoxide class shown in following formula (VIII):

［ changing 9 ］

(in formula, R ¹⁵represent the straight chain-like alkyl of hydrogen atom or carbon number 1～5.）

(i) the epoxide ring amyl group ethers shown in following formula (IX):

［ changing 10 ］

(in formula, R ¹⁶and R ¹⁷represent independently of each other the straight chain-like alkyl of hydrogen atom or carbon number 1～5.）

(j) the bicyclic oxygen tristane shown in following formula (X) (ジ エ Port キ シ ト リ シ Network ロ デ カ Application) class:

［ changing 11 ］

(in formula, R ¹⁸represent the straight chain-like alkyl of hydrogen atom or carbon number 1～5.）

In above-mentioned illustrative alicyclic epoxy resin, from there being the reasons such as commercially available or its analog ratio is easier to obtain, more preferably use alicyclic epoxy resin below.

(A) carboxylate of 7-oxabicyclo ［ 4.1.0 ］ heptane-3-carboxylic acid and (7-oxa--bis-ring ［ 4.1.0 ］ heptan-3-yl) methyl alcohol in formula (I), R ¹=R ²the compound of=H ］

(B) carboxylate of 4-methyl-7-oxabicyclo ［ 4.1.0 ］ heptane-3-carboxylic acid and (4-methyl-7-oxa--bis-ring ［ 4.1.0 ］ heptan-3-yl) methyl alcohol in formula (I), R ¹=4-CH ₃, R ²=4-CH ₃compound

(C) carboxylate of 7-oxabicyclo ［ 4.1.0 ］ heptane-3-carboxylic acid and 1,2-ethylene glycol in formula (II), R ³=R ⁴the compound of=H, n=2 ］

(D) carboxylate of (7-oxabicyclo ［ 4.1.0 ］ heptan-3-yl) methyl alcohol and hexane diacid in formula (III), R ⁵=R ⁶the compound of=H, p=4 ］

(E) carboxylate of (4-methyl-7-oxabicyclo ［ 4.1.0 ］ heptan-3-yl) methyl alcohol and hexane diacid in formula (III), R ⁵=4-CH ₃, R ⁶=4-CH ₃, _p=4 compound ］

(F) etherate of (7-oxabicyclo ［ 4.1.0 ］ heptan-3-yl) methyl alcohol and 1,2-ethylene glycol in formula (V), R ⁹=R ¹⁰the compound of=H, r=2 ］

In addition, as aliphatic epoxy resin, can enumerate the polyglycidyl ether of aliphatic polyol or its alkylene oxide addition product.More specifically, can enumerate: the diglycidyl ether of BDO; The diglycidyl ether of 1,6-hexanediol; The triglycidyl ether of glycerine; The triglycidyl ether of trimethylolpropane; The diglycidyl ether of polyglycol; The diglycidyl ether of propylene glycol; Polyglycidyl ether of the one kind or two or more alkylene oxide (oxirane, epoxypropane) of addition on the aliphatic polyols such as ethylene glycol, propylene glycol, glycerine and the polyether glycol that obtains etc.

Form the epoxy resin of tackifier that comprises epoxy based resin composition and can use separately a kind or and use two or more.The epoxide equivalent of the epoxy resin using in said composition is 30～3000g/ equivalent, the preferred scope of 50～1500g/ equivalent normally.When epoxide equivalent is during lower than 30g/ equivalent, there is the flexible reduction of the composite polarizing plate after solidifying, or the possibility that reduces of bonding strength.On the other hand, in the time exceeding 3000g/ equivalent, the possibility that in existence and tackifier, the compatibility of other contained compositions reduces.

In this tackifier, from reactive viewpoint, as the curing reaction of epoxy resin, preferably use cationic polymerization.For this reason, preferably in the curable epoxy resin composition as active energy ray curable tackifier, coordinate cationic polymerization initiators.Cationic polymerization initiators produces kation kind or lewis acid by the irradiation of luminous ray, ultraviolet ray, X ray, electron ray isoreactivity energy-ray, causes the polyreaction of epoxy radicals.Below, irradiation by active energy beam is produced to the cationic polymerization initiators that kation kind or lewis acid start the polyreaction of epoxy radicals and be called " light cationic polymerization initiators ".

Carry out for the curing method of tackifier with light cationic polymerization initiators and by irradiating active energy beam with regard to making, can solidify at normal temperatures, consider like this thermotolerance of polarizing coating or expand due to the necessity of strain reduce, from making intermembranous bonding viewpoint well very favourable.In addition, light cationic polymerization initiators produces catalytic action by light, so even if be mixed in epoxy resin, also have excellent storage stability, workability.

As light cationic polymerization initiators, for example, can enumerate: aromatic series diazo salt; The salt such as aromatic series salt compounded of iodine, aromatic series sulfonium salt; Iron-arene complex etc.

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

As aromatic series sulfonium salt, for example can enumerate: triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium four (pentafluorophenyl group) borate, 4, 4 '-bis-(diphenyl sulfonium) diphenylsulfide two (hexafluorophosphate), 4, 4 '-bis-［ two (beta-hydroxy ethoxy) phenyl sulfonium ］ diphenylsulfide two (hexafluoro antimonate), 4, 4 '-bis-［ two (beta-hydroxy ethoxy) phenyl sulfonium ］ diphenylsulfide two (hexafluorophosphate), 7-［ two (p-methylphenyl) sulfonium ］-ITX hexafluoro antimonate, 7-［ two (p-methylphenyl) sulfonium ］-ITX four (pentafluorophenyl group) borate, 4-phenylcarbonyl group-4 '-diphenyl sulfonium-diphenylsulfide hexafluorophosphate, 4-(is to tert-butyl-phenyl carbonyl)-4 '-diphenyl sulfonium-diphenylsulfide hexafluoro antimonate, and 4-(is to tert-butyl-phenyl carbonyl)-4 '-bis-(p-methylphenyl) sulfonium-diphenylsulfide four (pentafluorophenyl group) borate etc.

In addition; as iron-arene complex, for example, can enumerate dimethylbenzene-cyclopentadienyl group iron (II) hexafluoro antimonate, cumene-cyclopentadienyl group iron (II) hexafluorophosphate and dimethylbenzene-cyclopentadienyl group iron (II)-tri-(trifluoromethyl sulfonyl) methanides etc.

These light cationic polymerization initiators can easily obtain commercially available product, for example, if name by trade name respectively, can enumerate " Kayarad PCI-220 ", " Kayarad PCI-620 " (above by Japanese chemical drug (strain) system), " UVI-6990 " (associating carbonide (Union Carbide) company's system), " Adeka Optomer SP-150 ", " Adeka Optomer SP-170 " (above by (strain) ADEKA system), " CI-5102 ", " CIT-1370 ", " CIT-1682 ", " CIP-1866S ", " CIP-2048S " and " CIP-2064S " (above by Japanese Cao Da (strain) system), " DPI-101 ", " DPI-102 ", " DPI-103 ", " DPI-105 ", " MPI-103 ", " MPI-105 ", " BBI-101 ", " BBI-102 ", " BBI-103 ", " BBI-105 ", " TPS-101 ", " TPS-102 ", " TPS-103 ", " TPS-105 ", " MDS-103 ", " MDS-105 ", " DTS-102 ", " DTS-103 " (learning (strain) system by greening above), " PI-2074 " (Luo Diya (Rhodia) company system), Deng.

These light cationic polymerization initiators can use separately a kind, also can be mixed with two or more.Wherein, even if the wavelength region may of aromatic series sulfonium salt more than 300nm also has UVA characteristic, therefore curability excellence, can provide the solidfied material with good mechanical strength and bonding strength, therefore preferably uses.

About the use level of light cationic polymerization initiators, with respect to epoxy resin 100 weight portions, normally 0.5～20 weight portion, preferably more than 1 weight portion, also preferably below 15 weight portions.In the use level of light cationic polymerization initiators with respect to epoxy resin 100 weight portions during lower than 0.5 weight portion, solidify insufficient, the trend that exists physical strength, bonding strength to reduce.In addition, in the time that the use level of light cationic polymerization initiators exceedes 20 weight portion with respect to epoxy resin 100 weight portions, the ionic substance in solidfied material increases, and therefore the hydroscopicity of solidfied material improves, the possibility that exists endurance quality to reduce.

In the situation that making with light cationic polymerization initiators, curable epoxy resin composition can also contain photosensitizer as required.By using photosensitizer, the reactivity of cationic polymerization improves, and can make the physical strength of solidfied material, bonding strength improve.As photosensitizer, for example, can enumerate carbonyls, organosulfur compound, persulfide, redox based compound, azo and diazo-compounds, halogenide, photo-reduction pigment etc.

For example, if enumerate the example more specifically of photosensitizer, can enumerate: benzoin methylether, benzoin iso-propylether and α, the benzoin derivatives such as alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone; Benzophenone, 2,4-dichloro benzophenone, o-benzoyl yl benzoic acid methyl esters, 4,4 '-bis-(dimethylamino) benzophenone and 4,4 '-benzophenone derivates such as bis-(diethylamino) benzophenone; The thioxanthone derivates such as CTX and ITX; The anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; The acridone derivativeses such as N-methylacridine ketone and N-butyl acridone; And α, α-diethoxy acetophenone, benzil, Fluorenone, xanthone, uranyl compound and halogenide etc.Photosensitizer can only use separately a kind, can also and use two or more.The photosensitizer preferably content in curable epoxy resin composition 100 weight portions is the scope of 0.1～20 weight portion.

The contained epoxy resin of tackifier solidifies by light cationic polymerization, but also can by light cationic polymerization and hot cationic polymerization, the two is cured.In the latter case, preferably also with light cationic polymerization initiators and hot cationic polymerization initiators.

As hot cationic polymerization initiators, can enumerate benzil sulfonium salt, thiophene (チ オ Off ェ ニ ウ system) salt, thiophane salt (チ オ ラ ニ ウ ム salt), benzil ammonium, pyridiniujm, hydrazine (ヒ De ラ ジ ニ ウ system) salt, carboxylate, sulphonic acid ester and amine acid imide etc.These hot cationic polymerization initiators can be used as commercially available product and easily obtain, for example, if name by trade name respectively, can enumerate " Adekaopton CP77 ", " Adekaopton CP66 " (above for Asahi Denka Co., Ltd.'s system), " CI-2639 ", " CI-2624 " (being Tso Tat Co., Ltd., Japan's system above), " Sun-aid SI-60L ", " Sun-aid SI-80L ", " Sun-aid SI-100L " (being three new chemical industry Co., Ltd. systems above) etc.

The tackifier of active energy ray curable can further contain the compound of the promotion cationic polymerizations such as oxetanes (オ キ セ タ Application) class, polyalcohols.

Oxetanes class is the compound in molecule with quaternary cyclic ethers, for example can enumerate 3-ethyl-3-hydroxymethyl oxetanes, Isosorbide-5-Nitrae-bis-［ (3-ethyl-3-oxetanyl) methoxy ］ benzene, 3-ethyl-3-(phenoxymethyl) oxetanes, two ［ (3-ethyl-3-oxetanyl) methyl ］ ether, 3-ethyl-3-(2-ethyl hexyl oxy methyl) oxetanes and phenol phenolic aldehyde oxetanes etc.These oxetanes classes can easily obtain commercially available product, for example, all name with trade name, can enumerate " ARON OXETANE OXT-101 ", " ARON OXETANE OXT-121 ", " ARON OXETANE OXT-211 ", " ARON OXETANE OXT-221 ", " ARON OXETANE OXT-212 " (being East Asia synthetic (strain) system) etc.These oxetanes classes in curable epoxy resin composition containing being proportionally generally 5～95 % by weight, being preferably 30～70 % by weight.

As polyalcohols, preferably there is not the polyvalent alcohol of the acidic-group beyond phenol hydroxyl, for example can enumerate do not have the functional group beyond hydroxyl polyol compound, polyester polyols alcoholic compound, polycaprolactone polyol compound, there is polyol compound and the polycarbonate polyol etc. of phenol hydroxyl.The molecular weight of these polyalcohols is generally more than 48, is preferably more than 62, more preferably more than 100, but also is preferably below 1000.These polyalcohols in curable epoxy resin composition containing proportional conventionally below 50 % by weight, preferably below 30 % by weight.

In the tackifier of active energy ray curable, can further coordinate the adjuvants such as ion trap agent, antioxidant, chain-transferring agent, tackifier, thermoplastic resin, filling agent, flow modifier, levelling agent, plastifier, defoamer.As ion trap agent, 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, can enumerate hindered phenol is antioxidant etc.

The tackifier of active energy ray curable can use with the form of the solventless adhesive that do not contain in fact solvent composition, but each coating method has respectively optimum range of viscosities, therefore for viscosity adjustment, also can contain solvent.As solvent, the material that preferably use does not reduce the optical property of polarizing coating and well composition epoxy resin etc. dissolved, can enumerate the organic solvents such as the hydro carbons taking toluene as representative, the ester class taking ethyl acetate as representative.The viscosity of the tackifier of active energy ray curable used in the present invention is for example the scope of 5～1000mPas left and right, is preferably 10～200mPas, more preferably 20～100mPas.

The manufacture method > of < polarization plates

Next, manufacturing installation and the manufacture method of polarization plates of the present invention are described with reference to accompanying drawing on one side on one side.Fig. 1 is the schematic diagram of an embodiment of the manufacturing installation that represents that the manufacture method of polarization plates of the present invention uses.

The manufacturing installation of the polarization plates shown in Fig. 1 is disposed with along conveyance direction: for the tackifier apparatus for coating 11,12 of the one side coating binder at hyaline membrane 2,3; Obtain the doubling roller (niproll) 51,52 of duplexer 4 for fitting hyaline membrane 2,3 and polarizing coating 1; Make the closely sealed rotating roller of duplexer 4 13; Be arranged on relative with the outer peripheral face of this rotating roller 13 to the 1st active energy beam irradiation unit 31,32 of position; Be arranged at the 2nd active energy beam irradiation unit 16～18 that more leans on conveyance direction downstream than it; And niproll 19 for conveyance.

First,, at the one side of the hyaline membrane 2,3 of emitting continuously from the state that is wound into roller shape, utilize the tackifier (tackifier painting process) of tackifier apparatus for coating 11,12 coating active energy ray curables.

Then, two-sided at the polarizing coating 1 of emitting continuously from the state that is wound into roller shape, come to be stackedly coated with the hyaline membrane 2,3 of tackifier and to obtain duplexer via tackifier, this duplexer is being seized on both sides by the arms under the state between a pair of doubling roller 51,52 to conveyance direction rotation, so that the mode that at least one party's doubling roller is pressed to the direction of another doubling roller and exerting pressure, by hyaline membrane 1 and polarizing coating 2,3 laminatings, form duplexer 4(bonding process thus).

Then, make this duplexer 4 be sealed in the process of outer peripheral face limit conveyance duplexer 4 of rotating roller 13 on limit, irradiate active energy beam from the 1st active energy beam irradiation unit 31,32 outer peripheral faces towards rotating roller 13, make tackifier polymerizing curable (the 1st active energy beam irradiation process).

It should be noted that, be configured in the 2nd active energy beam irradiation unit 16～18th in conveyance direction downstream, for making the device of the complete polymerizing curable of tackifier (the 2nd active energy beam irradiation process), can append or omit as required.Finally make duplexer 4 by conveyance niproll 19, batch in winding roller 20 as polarization plates.Below, describe each operation in detail.

(tackifier painting process)

The coating process of tackifier on hyaline membrane 2,3 is not particularly limited, for example, can utilize scraper, line rod, mould to be coated with the various coating methods such as machine, comma coating machine, intaglio plate coating machine.Wherein, if consideration and film coated, transport circuit (パ ス ラ イ Application) degree of freedom, fabric width etc. corresponding, tackifier apparatus for coating 11,12 is preferably gravure roll (グ ラ PVC ア ロ ー Le).

While using gravure roll to carry out the coating of tackifier as tackifier apparatus for coating 11,12, the thickness (coating thickness) of the tackifier being coated with is preferably approximately 0.1～10 μ m, more preferably 0.2～4 μ m.The coating thickness of tackifier is recently adjusted with respect to the stretching than of linear velocity of hyaline membrane according to the speed of gravure roll.Generally speaking,, by making draw ratio (speed/linear velocity of gravure roll) be adjusted to 0.5～10, can make the coating thickness of tackifier be adjusted to approximately 0.1～10 μ m.More specifically, the linear velocity that makes hyaline membrane 2,3 is 10～100m/ minute, gravure roll is towards the reverse direction rotation of the conveyance direction of hyaline membrane 2,3, and the speed that makes gravure roll is 5～1000m/ minute, can make thus the coating thickness of tackifier be adjusted to approximately 0.1～10 μ m.

Tackifier, after preparation, for example, is coated with under the environment of general set point of temperature ± 5 in the scope that is adjusted into 15～40 DEG C DEG C (, when set point of temperature is 30 DEG C, 30 DEG C ± 5 DEG C), preferably ± 3 DEG C, more preferably ± 1 DEG C.

(bonding process)

In this operation, two-sided at the polarizing coating 1 of emitting continuously from the state that is wound into roller shape, carrys out the stacked hyaline membrane 2,3 that is coated with tackifier by above-mentioned operation via tackifier.This duplexer is being seized on both sides by the arms under the state between a pair of doubling roller 51,52 to conveyance direction rotation, for example, by doubling roller 51 is pressed to the direction of doubling roller 52, thereby by polarizing coating 1 and hyaline membrane 2,3 laminatings, forming duplexer 4.Now, with with respect to becoming with the vertical face of direction of pressing of doubling roller ± mode of angle in the scope of the mode of angle within the scope of 3 °, be preferably ± 1 °, particularly preferably in the mode overlapping with face perpendicular to pressing direction, make polarizing coating to conveyance between doubling roller.Like this, polarizing coating can not produce bubble nearby contacting of doubling roller with hyaline membrane.

It should be noted that, in Fig. 1, show the one side coating binder equably at hyaline membrane 2,3, make the face that is coated with tackifier of hyaline membrane 2,3 and polarizing coating 1 is overlapping and the method for utilizing doubling roller 51,52 to fit, but also can, at the two-sided coating binder equably of polarizing coating 1, fit in the overlapping hyaline membrane 2,3 of the face that is coated with tackifier the utilization laminating 51,52 of polarizing coating 1.

As the material of doubling roller 51,52, can enumerate the rubber rollers that metallic roll or surface are made up of rubber.At least one party of a pair of doubling roller 51,52 has the surface being made up of rubber and the rubber rollers being driven in rotation.Shown in Fig. 1, in manufacturing installation, for example, the roller of downside 52 can be made as to rubber rollers.The rotational speed of the rubber rollers conventionally, being driven in rotation is consistent with the linear velocity of the duplexer by between a pair of doubling roller.As opposite side doubling roller, preferably use metallic roll, it can be driven along with the action of the production line of duplexer, also can be driven in rotation.The rotational speed of rubber rollers is for example 10～50m/ minute.

As the mother metal of metallic roll, can use various known materials, be preferably SUS304, more preferably implement chromium plating processing on the surface of metallic roll.In addition, the material of rubber rollers is not particularly limited, and can enumerate EPDM, NBR, carbamate, Titan(タ イ タ Application), silicone etc.The hardness of rubber rollers is not particularly limited, and is generally 60～100 °, more preferably 85～95 °.In addition, the hardness of rubber roller processed can be used according to the sclerometer of JISK6253 and measure.Commercially available sclerometer for example uses Asuka company durometer processed " A type " etc.Particularly, while pressing surface with club, measure the skin resistance of rubber rollers with sclerometer.

With regard to put on the pressure of duplexer by the extruding of metallic roll and rubber rollers for, preferably Fujiphoto biplate type processed Prescale(ultralow pressure use) instantaneous pressure be 0.5～3.0MPa, more preferably 0.7～2.3MPa.There is no particular limitation for the diameter of doubling roller 51,52, normally 50～400mm.In addition, the diameter of two (a pair of) doubling rollers 51,52 can be identical, also can be different.

(the 1st active energy beam irradiation process)

Rotating roller 13 forms outer peripheral face through the accurately machined convex surface of minute surface, make duplexer 4 be sealed at its surface while conveyance duplexer 4 makes tackifier polymerizing curable by active energy beam irradiation unit 31,32 in this process.Make tackifier polymerizing curable, and making the abundant closely sealed aspect of duplexer 4, the diameter of rotating roller 13 is not particularly limited.Rotating roller 13 is with the rotational speed of the rubber rollers being driven in rotation than in a pair of doubling roller 51,52 rotational speed and being driven faster.The rotational speed of the rubber rollers being driven in rotation in a pair of doubling roller 51,52 is made as at 100 o'clock, and the rotational speed of rotating roller 13 is preferably more than 100.1 and below 102.0, and more preferably 100.1～101.5.In the time being less than 100.1, easily there is wave volume in duplexer.On the other hand, in the time exceeding 102.0, between film and roller, occur slide and may cause damage etc.

The rotational speed of rotating roller 13 is for being for example 10～50m/ minute.The rotational speed of rotating roller 13 does not need to control as constant, for example, can be according to the sliding on the kind of film and roller surface etc., confirm the situation occurred of corrugated plate shape fluctuating while control aptly.

In addition, when irradiating active energy beam and polymerizing curable, the chill roll that rotating roller 13 can be used as for making the heat heat radiation that duplexer 4 produces works.Now, the surface temperature of chill roll is preferably set to 4～30 DEG C.

The light source using while carrying out the polymerizing curable of tackifier by the irradiation of active energy beam is not particularly limited, and sends out light source photodistributed but be preferably to have below wavelength 400nm.For example can enumerate low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp, black lamp, microwave-excitation mercury lamp, metal halid lamp as such light source.The irradiation of the active energy beam in the 1st active energy beam irradiation process is preferably divided into repeatedly to be carried out.Figure 1 illustrates: the situation that the sub irradiation of active energy beam carries out for 2 times, configures the situation of 2 light sources (active energy beam irradiation unit 31,32) that is along the conveyance direction of duplexer.

Each irradiation intensity to active energy ray curable tackifier determines according to the composition of each tackifier, is not particularly limited, but is preferably 10～5000mW/cm ².If the irradiation intensity to resin combination is less than 10mW/cm ², the reaction time long, if exceed 5000mW/cm ², the heating during due to the heat of light source institute radiation and the polymerization of composition, therefore likely produce the deteriorated of xanthochromia that the constituent material of tackifier is composition epoxy resin etc. or polarizing coating.It should be noted that, exposure intensity is preferably the intensity for the effective wavelength region may of activation of light cationic polymerization initiators, more preferably the intensity of the wavelength region may below wavelength 400nm, the further intensity of the wavelength region may (UVB) of optimal wavelength 280～320nm.

In the time that active energy beam is ultraviolet ray, long-pending body layer 4 is irradiated in the operation of active energy beam, preferably limit applies the tension force of 100～800N/m at length direction (conveyance direction) to duplexer 4, and limit reaches 0.1 second above linear velocity conveyance duplexer 4 with irradiation time.

(the 2nd active energy beam irradiation process)

In the time that the accumulated light of the active energy beam being produced by active energy beam irradiation unit 31,32 is insufficient, the 2nd later active energy beam irradiation unit 16～18 is preferably set, thereby boost active energy beam, promote duplexer 4 tackifier solidify.The accumulated light of the whole operations including the 1st active energy beam irradiation process is 10mJ/cm ²above, particularly preferably so that accumulated light reaches 10～5000mJ/cm ²mode set.When the accumulated light to above-mentioned tackifier is less than 10mJ/cm ²time, the generation of spike that is derived from initiating agent is insufficient, tackifier curing insufficient.On the other hand, when this accumulated light exceedes 5000mJ/cm ²time, it is very long that irradiation time becomes, and it is unfavorable that throughput rate is improved.Now, according to combination of used film or tackifier kind etc., which kind of wavelength region may (UVA(320～390nm) or UVB(280～320nm) etc.) in required accumulated light will there are differences.

For carry out reliably the solidifying of tackifier of polarization plates (duplexer) end, for example, can enumerate and make electrodeless D bulb (バ Le Block ラ Application プ) be FUSION system " Light Hammer10 " taking move with respect to film as across the mode method of arranging etc.

There is curing ratio, i.e. reaction rate in active energy ray curable resin, is preferably more than 90%, more preferably more than 95%.

(polarization plates coiling process)

The tension force that batches duplexer (polarization plates) 4 is made as to 30N/cm ²～150N/cm ²scope in.Be preferably 30N/cm ²～120N/cm ²scope in.When to be less than 30N/cm ²tension force transfer roller when volume of strip, because meeting causes the dislocation of reeling, therefore not preferred, when tension force is greater than 150N/cm ²time, roll tightly stretch tight (volume I Parties ま り) stronger, easily produce lax.

It should be noted that, batch length longer, in the time of same tension force, more easily cause and roll tightly stretch tight (phenomenon that is difficult for reverting to smooth state while unreeling), therefore can make polarization coiled sheet in volume core, make tension force on one side continuously or interim reduction on one side.Reduce in the method for tension force even if state on the implementation this so-called gradual change, tension force now also will be set to 150N/cm ²below.

Batch in the length of the polarization plates of rolling up core and be not particularly limited, but more than being preferably 100m and below 4000m.

The diameter of volume core cylindraceous is preferably 6 inches～12 inches.The diameter of volume core is the bigger the better, and more preferably 11 inches, 12 inches etc., but in the time that diameter is excessive, have the tendency that is difficult for handover or keeping.

Because the material of cylindric volume core is used at dust free room, therefore, as long as itself be difficult for producing dust and guaranteeing that suitable intensity, with the wider polarization plates of reeling width, is not particularly limited, can select FRP(fiberglass-reinforced plastic) etc.

Embodiment

Below enumerate embodiment and illustrate in greater detail the present invention, but the invention is not restricted to these embodiment.

［ embodiment 1 ］

(making of polarizing coating)

As the former material film of polyvinyl alcohol (PVA), the rectangular polyvinyl alcohol film of the use degree of polymerization 2400,99.9 % by mole of saponification degrees, thickness 75 μ m, width 3000mm " the synthetic system of OPL film M-7500(Japan) ".Stretching is that peripheral speed is poor to carry out by the driving niproll for the treatment of trough front and back is added.

First, not make the lax mode of former material film keep the tense situation of film, in the swelling groove of pure water that is equipped with 30 DEG C, flood 80 seconds, make film fully swelling.With the swelling entrance accompanying in swelling groove and the roller velocity ratio of outlet be 1.2.Utilize after the dewatering of niproll, in the water retting groove of pure water that is equipped with 30 DEG C, flood 160 seconds.The stretching ratio that makes the operating direction in this groove is 1.09 times.

Then, in the staining trough of aqueous solution that iodine/potassium iodide/water is housed counts with weight ratio 0.02/2.0/100, flood, carry out uniaxial tension with the stretching ratio of approximately 1.5 times simultaneously.Then, in the boric acid groove that potassium iodide/boric acid/water is housed counts with weight ratio 12/3.7/100 aqueous solution, at 55.5 DEG C, flood 130 seconds, carry out uniaxial tension until the accumulation stretching ratio from former material reaches 5.7 times simultaneously.Then, in the boric acid groove that potassium iodide/boric acid/water is housed counts with weight ratio 9/2.4/100 aqueous solution, at 40 DEG C, flood 60 seconds.

Then, in rinsing bowl, wash approximately 16 seconds with the pure water of 8 DEG C, then, by the drying oven of approximately 60 DEG C, the drying oven of approximately 85 DEG C, the mode that adds up to 160 seconds with the residence time in these drying ovens is dried successively.Like this, obtaining absorption has iodine and makes it carry out the polarizing coating of the thickness 28 μ m of orientation.

(making of polarization plates)

As hyaline membrane, prepare the cellulose acetate resin film of having given phase difference characteristics " KC4CR-1(Konica Minolta Opto(strain) system) " of thickness 40 μ m and the tri acetyl cellulose membrane " KC8UX2MW " (Konica Minolta company system) of thickness 80 μ m.

Use as polarizing coating and hyaline membrane above-mentioned and that prepare, make polarization plates by the device shown in Fig. 1.First, at the one side of the above-mentioned cellulose acetate resin film " KC4CR-1 " of having given phase difference characteristics, use tackifier apparatus for coating (Micro Chamber Doctor: Mechanology Inc. of Fuji system) coating ultraviolet hardening tackifier, i.e. composition epoxy resin " KR series " (ADEKA company system).In addition, at the one side of above-mentioned tri acetyl cellulose membrane " KC8UX2MW ", use the tackifier of identical tackifier apparatus for coating coating ultraviolet hardening, i.e. epoxy resin resin combination " KR series " (ADEKA company system).Now, the linear velocity of the stacked body of polarizing coating of tackifier apparatus for coating is made as to 25m/ minute, make the thickness of the adhesive layer on cellulose acetate resin film " KC4CR-1 " be about 4.0 μ m, make the thickness of the adhesive layer on tri acetyl cellulose membrane " KC8UX2MW " be about 3.3 μ m(and add up to approximately 7.3 μ m).

Then, state the mode of cellulose acetate resin film " KC4CR-1 " and tri acetyl cellulose membrane " KC8UX2MW " to close at the Double-face adhesive of above-mentioned polarizing coating, by their conveyances between the rubber rollers being driven in rotation and metallic roll and clamp, via above-mentioned composition epoxy resin (ultraviolet hardening tackifier) fit (bonding process).

For the polarizing coating that is fitted with above-mentioned 2 kinds of hyaline membranes, limit length direction apply the tension force of 600N/m and make it and chill roll closely sealed, limit is transferred with linear velocity 25m/ minute, it is passed through by metal halide lamp 2 lamps (GS-YUASA company system, the electric energy 130W/cm of 1 lamp) irradiate ultraviolet ray in, carry out the 1st active energy beam irradiation process, make again it pass through by electrodeless D bulb 3 lamps (the Fusion company system " Light Hammer10 " arranging afterwards, the electric energy 216mW/cm of 1 lamp) irradiate ultraviolet ray in, carry out the 2nd active energy beam irradiation process, be made into thus polarization plates.

Above-mentioned electrodeless D bulb 3 lamps refer to: Width at film is arranged to unit that 6 electrodeless D bulbs form, is listed as in the length direction configuration 3 of film the device forming.

During by metal halide lamp, tri acetyl cellulose membrane " KC8UX2MW " contact that makes to fit in above-mentioned polarizing coating is set in the outer peripheral face of the chill roll of 23 DEG C, from cellulose acetate resin film " KC4CR-1 " side irradiation ultraviolet radiation.The rotational speed of the rubber rollers being driven in rotation in bonding process is made as to 25.00m/ minute, the rotational speed of chill roll is made as to 25.23m/ minute.,, in the time that the rotational speed of rubber rollers is 100, the rotational speed of chill roll is 100.9.

The accumulated light that the 1st active energy beam irradiation process in the present embodiment and the 2nd active energy beam irradiation process add up to is 468mJ/cm ².With regard to accumulated light herein, it is according to being, the measured value obtaining in the wavelength region may (UVB) of wavelength 280～320nm, by the analyzer (the UV Power processed Puck II of Fusion UV company) of irradiation intensity.

(ocular estimate)

For the polarization plates of the embodiment 1 as above making, utilize the reflex that irradiates fluorescent light to observe outward appearance, the result generation rising and falling to corrugated plate shape unconfirmed.

［ embodiment 2 ］

As hyaline membrane, the cyclic olefine resin molding " ZEONOR " of used thickness 60 μ m (Japanese ZEON(strain) system) replace cellulose acetate resin film " KC4CR-1 ", in addition, make similarly to Example 1 the polarization plates of embodiment 2.

(ocular estimate)

For the polarization plates of the embodiment 2 as above making, observe similarly to Example 1 outward appearance, the result generation rising and falling to corrugated plate shape unconfirmed.

［ embodiment 3 ］

As hyaline membrane, cyclic olefine resin molding " ZEONOR " (the Japanese ZEON(strain) system of used thickness 25 μ m) replace the tri acetyl cellulose membrane " K2UAW " (Konica Minolta company system) of cellulose acetate resin film " KC4CR-1 ", used thickness 25 μ m to replace tri acetyl cellulose membrane " KC8UX2MW ", the rotational speed of the rubber rollers being driven in rotation in bonding process is made as to 25.00m/ minute, the rotational speed of chill roll is made as to 25.08m/ minute.That is, the rotational speed of rubber rollers is made as at 100 o'clock, the rotational speed of chill roll is 100.3.Except above-mentioned aspect, make similarly to Example 1 the polarization plates of embodiment 3.

(ocular estimate)

For the polarization plates of the embodiment 3 as above making, observe similarly to Example 1 outward appearance, the result generation rising and falling to corrugated plate shape unconfirmed.

［ embodiment 4 ］

As hyaline membrane, cyclic olefine resin thin " ZEONOR " (the Japanese ZEON(strain) system of used thickness 50 μ m) replace the tri acetyl cellulose membrane " TD60UL " (Fujiphoto (strain) system) of cellulose acetate resin film " KC4CR-1 ", used thickness 60 μ m to replace tri acetyl cellulose membrane " KC8UX2MW ", the rotational speed of the rubber rollers being driven in rotation in bonding process is made as to 25.00m/ minute, the rotational speed of chill roll is made as to 25.28m/ minute.That is, the rotational speed of rubber rollers is made as at 100 o'clock, the rotational speed of chill roll is 101.1.Except above-mentioned aspect, make similarly to Example 1 the polarization plates of embodiment 4.

(ocular estimate)

For the polarization plates of the embodiment 4 as above making, observe similarly to Example 1 outward appearance, the result generation rising and falling to corrugated plate shape unconfirmed.

［ embodiment 5 ］

With respect to the rotational speed 100 of the rubber rollers being driven in rotation in bonding process, the rotational speed of chill roll is made as to 102.2, in addition, make similarly to Example 1 polarization plates.

(ocular estimate)

For the polarization plates of the comparative example 2 of as above making, although the generation rising and falling to corrugated plate shape unconfirmed while observing outward appearance confirms abrasive generation.

［ comparative example 1 ］

With respect to the rotational speed 100 of the rubber rollers being driven in rotation in bonding process, the rotational speed of chill roll is made as to 100, rotational speed be made as identical, in addition, the polarization plates of comparison example 1 similarly to Example 1.

(ocular estimate)

For the polarization plates of the comparative example 1 of as above making, while observing outward appearance, confirm the generation that corrugated plate shape rises and falls.

Utilizability in industry

Polarization plates of the present invention can be applicable to the various display device taking liquid crystal indicator as representative effectively.

1 polarizing coating

2,3 hyaline membranes

4 duplexers (polarization plates)

11,12 tackifier apparatus for coating

13 rotating rollers (chill roll)

16,17,18,31,32 active energy beam irradiation units

19 conveyance niprolls

20 winding rollers

Claims (3)

1. a manufacture method for polarization plates, is the manufacture method that hyaline membrane is fitted in to the polarization plates that the single or double of polarizing coating forms, and described manufacture method possesses successively:

Tackifier painting process, at the one side of described hyaline membrane or the single or double of described polarizing coating, coating active energy ray curable tackifier;

Bonding process, described hyaline membrane is clamped in between a pair of doubling roller of conveyance direction rotation via the stacked duplexer forming in the single or double of described polarizing coating of described tackifier, and described duplexer is exerted pressure, thus by described hyaline membrane and the laminating of described polarizing coating; And

The 1st active energy beam irradiation process, described duplexer is sealed in during duplexer described in conveyance under the state of the rotating roller of conveyance direction rotation, irradiates active energy beam to described duplexer, makes described adhesive solidification,

Wherein, at least one party of described a pair of doubling roller has the surface being made up of rubber and the rubber rollers being driven in rotation,

The rotational speed of described rotating roller is faster than the rotational speed of described rubber rollers.

2. the manufacture method of polarization plates as claimed in claim 1, wherein, described rotating roller is chill roll.

3. the manufacture method of polarization plates as claimed in claim 1 or 2, wherein, is made as at 100 o'clock by the rotational speed of described rubber rollers, and the rotational speed of described rotating roller is more than 100.1 and below 102.0.

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