CN103858030A - Method for manufacturing polarizer - Google Patents
Method for manufacturing polarizer Download PDFInfo
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- CN103858030A CN103858030A CN201280049325.8A CN201280049325A CN103858030A CN 103858030 A CN103858030 A CN 103858030A CN 201280049325 A CN201280049325 A CN 201280049325A CN 103858030 A CN103858030 A CN 103858030A
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- Prior art keywords
- tackifier
- film
- hyaline membrane
- polarizing coating
- active energy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/516—Oriented mono-axially
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- Polarising Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Liquid Crystal (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
A method for manufacturing a polarizer, said method being characterized by including the following steps: a step in which a polarizing film is fabricated by subjecting a polyvinyl-alcohol resin film to a dyeing process, a boric-acid process, and a uniaxial stretching process; a step in which an active-energy-ray-curable adhesive is applied to one surface of a transparent film or transparent films; a step in which the surface(s) of the transparent film(s) to which the adhesive was applied is/are bonded to one or both surfaces of the polarizing film by sandwiching with bonding rolls, thereby fabricating a laminate; and a step in which a polarizer is fabricated by exposing said laminate to active-energy rays. This method for manufacturing a polarizer is further characterized in that the bonding rolls in the laminate-fabrication step apply a pressure in the 0.2-1.2 MPa range.
Description
Technical field
The present invention relates to the manufacture method of the polarization plates useful as forming one of optics of liquid crystal indicator etc.
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 films.
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 doubling roller, fit thus, then, irradiate active energy beam and make its bonding curing method (reference example is as TOHKEMY 2004-245925 communique (patent documentation 1), TOHKEMY 2009-134190 communique (patent documentation 2), TOHKEMY 2011-95560 communique (patent documentation 3) etc.).
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
By polarizing coating, fit in the polarization plates forming with the hyaline membrane that is coated with the tackifier of active energy ray curable at one side, sometimes between above-mentioned polarizing coating and above-mentioned hyaline membrane, can sneak into the bubble about 100 μ m.Can think that this bubble causes because of following reason: the tackifier that does not enter the active energy ray curable between polarizing coating and hyaline membrane accumulates in and will sandwich the position nearby of doubling roller, cause the phenomenon of what is called " fluid accumulation (liquid ダ system) ", air enters between the opposing face and hyaline membrane of a side of the generation " fluid accumulation " of polarizing coating that (polarizing coating is extruded because of the expansion of " fluid accumulation " thus, the opposing face of one side of the generation " fluid accumulation " of polarizing coating contacts before laminating with hyaline membrane, and air enters thus).This is the phenomenon that can not cause while using the bonding agent of existing water system, is the caused peculiar problem of tackifier that uses active energy ray curable.
The present invention completes in order to address the above problem, its object is, a kind of method that can manufacture following polarization plates is provided, described polarization plates be by polarizing coating, with the hyaline membrane that is coated with the tackifier of active energy ray curable at the one side polarization plates forming of fitting, and between polarizing coating and hyaline membrane, be not easy to produce bubble.
For the scheme of dealing with problems
The present invention is a kind of manufacture method of polarization plates, it is characterized in that, comprising: polyvinyl alcohol resin film is implemented to the operation that dyeing is processed, boric acid is processed and uniaxial tension is processed and make polarizing coating; Be coated with the operation of the tackifier of active energy ray curable at the one side of hyaline membrane; Clamp above-mentioned hyaline membrane and the face that is coated with above-mentioned tackifier is fitted in to the single or double of above-mentioned polarizing coating, the operation of making duplexer with doubling roller; And above-mentioned duplexer is irradiated to active energy beam, and make the operation of polarization plates, wherein, in the operation of the above-mentioned duplexer of making, the squeeze pressure of doubling roller is within the scope of 0.2～1.2MPa.
Invention effect
Manufacturing method according to the invention, the manufacture method of following polarization plates is provided, described polarization plates be by polarizing coating, with the hyaline membrane that is coated with the tackifier of active energy ray curable at the one side polarization plates forming of fit, and between polarizing coating and hyaline membrane, be difficult for generation bubble.
Brief description of the drawings
Fig. 1 is the figure that schematically shows an example of the device entirety of the manufacture method for carrying out polarization plates of the present invention.
Embodiment
The manufacture method of polarization plates of the present invention comprises substantially: (1) implements to polyvinyl alcohol resin film the operation that dyeing is processed, boric acid is processed and uniaxial tension is processed and make polarizing coating; (2) in the operation of the tackifier of the one side coating active energy ray curable of hyaline membrane; (3) clamp above-mentioned hyaline membrane with doubling roller and the face that is coated with above-mentioned tackifier is fitted in to the single or double of above-mentioned polarizing coating, the operation of making duplexer; And (4) irradiate active energy beam to above-mentioned duplexer, the operation of making polarization plates.The manufacture method of polarization plates of the present invention is characterised in that, in the operation of above-mentioned (3), in the scope that the squeeze pressure that makes doubling roller is 0.2～1.2MPa.Thus, air is difficult for entering between polarizing coating and hyaline membrane, can easily manufacture the polarization plates that is difficult for producing bubble between polarizing coating and hyaline membrane.
Be less than 0.2MPa at the squeeze pressure of doubling roller, squeeze pressure is insufficient, thereby the conveyance state of film becomes unstable, and bubble is easily sneaked into, and in addition, is greater than 1.2MPa at the squeeze pressure of doubling roller, produces fluid accumulation, and bubble is sneaked into.The squeeze pressure of doubling roller is preferably in the scope of 0.5～1.2MPa.The instantaneous pressure that the squeeze pressure of this doubling roller can be used as in for example Fujiphoto biplate type processed Prescale is measured.The pressure of pressing of this doubling roller is applied in conventionally to the parts of bearings at the two ends of doubling roller.
Here, Fig. 1 is the figure that schematically shows an example of the device entirety of the manufacture method for carrying out polarization plates of the present invention.Below, with reference to Fig. 1, describe the entirety of the manufacture method of polarization plates of the present invention in detail.
Make the operation of polarizing coating
In the manufacture method of polarization plates of the present invention, first, polyvinyl alcohol resin film is implemented dyeing processing, boric acid processing and uniaxial tension processing and made polarizing coating.Polarizing coating used in the present invention particularly, is the film that makes the polyvinyl alcohol resin film absorption dichromatism pigment of uniaxial tension and make its orientation.Polyvinyl alcohol resin film can be that resin saponification obtains by making polyvinyl acetate.Be resin as polyvinyl acetate, can enumerate the polyvinyl acetate as the homopolymer of vinyl acetate, in addition, also have 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 to 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 500～6000mm.In addition, can also be two-sided using polyester mesenterys such as alkene mesentery or PET films as base material and at it or one side is coated with the material of polyvinyl alcohol resin.
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, (Vinylon VF-PS#6000, Kuraray system, Vinylon VF-PE#6000, Kuraray system) former material thickness be 60 μ m, the former material thickness of (Vinylon VF-PE#5000, Kuraray system) is 50 μ m, and the former material thickness of (Vinylon VF-PE#3000, Kuraray system) is 30 μ m etc.
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 aqueous solution 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 55～80 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.During washing is processed or before and after it, can suitably select water is blowed into spray form or water is sprayed forcefully and arrive the method for film etc. from the blowing unit of slit-shaped.After washing is processed, general enforcement is dry to be processed, and obtains polarizing coating.In the dry last stage of processing, can suitably adopt the method for utilizing air knife etc. to dispel water or drawing surperficial moisture etc. with suction roll.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 50～90 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 3～50 μ m.
It should be noted that, be not limited to said method, the film with polarization function that utilizes other method to make also can be used as polarizing coating.
On hyaline membrane, be coated with the operation of the tackifier of active energy ray curable
(hyaline membrane)
As forming the material of hyaline membrane used in the present invention, 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.
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, for example: 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), KC4UYW(Konica Minolta Opto(strain) system), KC6UAW(Konica Minolta Opto(strain) system), KC2UAW(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 acetylcellulose, or is also referred to as cellulose ethanoate.
These cellulose acetate mesenterys 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.
In the present invention, 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.
The thickness of hyaline membrane used in the present invention is preferably thin thickness, if but too thin, strength decreased, processability variation.On the other hand, if too thick, the transparency reduces, and causes the problems such as stacked rear required curing time is elongated.Therefore, the suitable thickness of hyaline membrane is for example 5～200 μ m, preferably 10～150 μ m, more preferably 10～100 μ m.
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.
(active energy ray curable tackifier)
As active energy ray curable tackifier, from viewpoints such as weatherability, refractive index, permanance, 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, can adopt the various active energy ray curable tackifier (organic solvent is that tackifier, hot melt are tackifier, solventless adhesive etc.) that in the past used in the manufacture of polarization plates.Wherein, can comprise acrylic acid series composition, acrylamide system: compositions, epoxy acrylate system: compositions, carbamate system: compositions, ethene system: compositions etc.In addition, as curing reaction, can enumerate solidifying of polyreactions such as utilizing free radical polymerization, cationic polymerization, anionic polymerisation, thermal polymerization.
So-called 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 class shown in following formula (X):
［ 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.During lower than 30g/ equivalent, there is the flexible reduction of the composite polarizing plate after solidifying at epoxide equivalent, 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-propadiene complex compound 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-propadiene complex compound, 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.
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.Ion trap agent can be enumerated the mineral compound of pulverous bismuth system, antimony system, magnesium system, aluminium system, calcium system, titanium system and their mixed stocker etc., and antioxidant can be enumerated hindered phenol 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.Below the preferred 80mPas of viscosity of the tackifier of active energy ray curable used in the present invention, more preferably below 50mPas.This be because, be greater than 80mPas in the viscosity of the tackifier of active energy ray curable, can not sneak into the lower thickness limit of bubble and tend to thickening.In addition, in order to obtain sufficient bonding strength, more than the viscosity of the tackifier of active energy ray curable is preferably 1mPas, more preferably more than 10mPas.It should be noted that, this viscosity refers to, the viscosity of utilizing E type viscosity meter to measure at 25 DEG C of liquid temperatures.
In example shown in Fig. 1, the hyaline membrane 2,3 of emitting continuously from being wound into the state of roller shape, by tackifier apparatus for coating 11,12, is coated with respectively the tackifier of active energy ray curable at one side.The coating process of tackifier on hyaline membrane is not particularly limited, for example, can utilize scraper, line rod, mould to be coated with the multiple 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).As commercially available apparatus for coating, can enumerate the MCD(Micro Chamber doctor of Mechanology Inc. of Fuji system) etc.
Use gravure roll while carrying out the coating of tackifier as tackifier apparatus for coating 11,12, the thickness (coating thickness) of the tackifier being coated with is preferably that 2.0 μ m are above, 2.5～4 μ m more preferably.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
Then, most of feature of the present invention is described above, utilizes doubling roller to clamp hyaline membrane and the face of tackifier that is coated with active energy ray curable is fitted in to the single or double of polarizing coating, makes duplexer.In the manufacture method of polarization plates of the present invention, hyaline membrane can only fit in arbitrary of above-mentioned polarizing coating, also can fit in two-sided.Fit in when two-sided, each hyaline membrane can be identical, also can be variety classes.
In example shown in Fig. 1, the hyaline membrane 2,3 of emitting continuously from being wound into the state of roller shape, by tackifier apparatus for coating 11,12, is coated with respectively the tackifier of active energy ray curable at one side.Then, can with above-mentioned hyaline membrane 2,3 similarly, utilize respectively doubling roller 5a, 5b and carry out superimposed hyaline membrane 2,3 by above-mentioned tackifier the polarizing coating 1 of emitting continuously two-sided, make duplexer 4.Now, making as mentioned above the squeeze pressure of doubling roller is within the scope of 0.5～1.2MPa.
In the present invention, a wherein side of a pair of doubling roller 5a, 5b, can be and have diminish gradually from central portion to the end crowned roll of peripheral shape of taper (テ ー パ ー) of (radius that, the radius of central portion is greater than end) of diameter.Now, a side's of non-crowned roll doubling roller is preferably diameter and is essentially the straight roll of homogeneous.It should be noted that, a pair of doubling roller can be straight roll.
The shape of crowned roll is preferably configured to: under the state of pressing in bonding process, and the interval of crowned roll and straight roll homogeneous in fact.Here, the interval of crowned roll and straight roll refers to, comprise in the section of the axle of above-mentioned crowned roll and the axle of above-mentioned straight roll, above-mentioned crowned roll and above-mentioned straight roll relative to the interval of periphery.It should be noted that, conventionally, crowned roll and straight roll with under the state of pressing, the axle of crowned roll and the parallel mode of the axle of straight roll configure.
For example, in the time that doubling roller 5a is metal straight roll, the doubling roller 5b crowned roll that is rubber system, for the bearing components of straight roll, exert pressure towards the direction of crowned roll.Carrying out under this state of pressing, crowned roll produces deflection, if but design the shape of crowned roll in the mode that the interval of crowned roll and straight roll becomes in fact homogeneous, duplexer equably can pressurize.It should be noted that, when crowned roll is pushed towards the direction of straight roll, also can obtain same effect.In addition, both press towards direction near each other can also to make crowned roll and straight roll.
In use, in the situation of protruding roller, the difference of the diameter of its central portion and the diameter of end is preferably 0.0020～0.0500% with respect to the ratio of the length (axial length) of above-mentioned crowned roll.More preferably 0.0020～0.020%.Conventionally in such ratio ranges, can design the shape of crowned roll so that under the state of pressing in bonding process the interval of crowned roll and straight roll become homogeneous.
In addition, in use, in the situation of protruding roller, the peripheral shape of the above-mentioned taper of crowned roll is preferably circular-arc.Here, the peripheral shape of the above-mentioned taper of above-mentioned crowned roll is circular-arc referring to, the section of the face of the axle of the peripheral shape that comprises above-mentioned taper of above-mentioned crowned roll is circular arc.This be because, in the case of the spindle unit of bonding process midplane roller is pressed, straight roll becomes circular-arc mode warpage mainly with peripheral shape, by make relatively to the peripheral shape of crowned roll be to there is circular-arc with the radius-of-curvature of straight roll same degree, can make relatively to the pressing of doubling roller (crowned roll and straight roll) time interval homogeneous, can polarizing coating and hyaline membrane be fitted with the pressure of homogeneous.
The diameter of doubling roller is not particularly limited, but diameter when the straight roll is preferably 50～400mm.The diameter of the end during in addition, for crowned roll is preferably 50～400mm.It should be noted that, a pair of doubling roller diameter separately can be identical, also can be different.The wide of doubling roller is 300～3000mm.
The material of doubling roller can be enumerated metal or rubber, and a wherein side of preferred a pair of doubling roller is metal roller processed, and the opposing party is rubber roller processed.Further preferred planar roller is metal system, and crowned roll is rubber system.
With regard to doubling roller in the past, the doubling roller of the upside being generally pressed is rubber system, and the doubling roller of downside is metal system.This be because, the doubling roller of downside is installed CD-ROM drive motor and is controlled rotational speed, therefore the doubling roller of downside is metal system, in the time pressing, the doubling roller of downside is indeformable, easily makes the circular velocity of doubling roller remain certain.But for ease of adjusting warpage, (upside) doubling roller being preferably pressed is metal system at this moment, (downside) doubling roller of opposite side is rubber system.
The mother metal of metal roller processed can use various known materials, but preferred stainless steel, the stainless steel of the Ni that more preferably SUS304(contains 18% Cr and 8%).Chromium plating is preferably implemented on the surface of metal roller processed.
The material of rubber roller processed is not particularly limited, but can enumerate NBR(nitrile rubber), Titan, carbamate, silicone, EPDM(ethylene-propylene-diene rubber) etc., preferably NBR, Titan, carbamate.The hardness of rubber rollers is not particularly limited, and is generally 60～100 °, is preferably 85～95 °.It should be noted that, the hardness of rubber rollers can be used according to the sclerometer of JISK6253 and measure.Can use the durometer " Type-A " of such as Asuka company system etc. as commercially available sclerometer.Particularly, when the type objects of use rod grade is pressed surface, measure the skin resistance of rubber rollers with sclerometer.
It should be noted that, the example of fitting with a pair of doubling roller has been shown in Fig. 1, but has been not restricted to this, can also be the formation that the mode that clamps a pair of doubling roller further arranges a pair of backing roll.In addition, also can only a side of pair of rolls, backing roll be set.
Duplexer is irradiated to the operation of active energy beam
In subsequent handling, the duplexer that as above operation obtains is irradiated to active energy beam, obtain polarization plates.In example shown in Fig. 1, subsequently, duplexer 4 be sealed at roller 13 outer peripheral face while by conveyance.In example shown in Fig. 1, be sequentially provided with along conveyance direction: the 1st active energy beam irradiation unit 14,15 that is arranged at the position relative with the outer peripheral face of this roller 13; And be arranged at than it more by the 2nd of conveyance direction downstream the later active energy beam irradiation unit 16,17,18; And niproll 19 for conveyance.Thus, making duplexer 4 be sealed at the outer peripheral face of roller 13 while in the process of conveyance, irradiating active energy beams from the 1st active energy beam irradiation unit 14,15 outer peripheral faces to roller 13, make tackifier polymerizing curable.It should be noted that, be disposed at the 2nd later active energy beam irradiation unit the 16,17, the 18th in conveyance direction downstream, for making the device of the complete polymerizing curable of tackifier, can append as required or omit.Finally, duplexer 4, by conveyance niproll 19, batches in winding roller 20 as polarization plates.
Be not particularly limited for carry out the light source that the polymerizing curable of tackifier uses by the irradiation of active energy beam, send 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.
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 oversize, if exceed 5000mW/cm
2, the heating during due to the heat of lamp 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, the more preferably intensity of the wavelength region may below wavelength 400nm, the further intensity of the wavelength region may of optimal wavelength 280～320nm.
Active energy beam, is not particularly limited, but is preferably set to according to respectively will controlling by curing composition the irradiation time of active energy ray curable tackifier, amasss represented accumulated light as 55mJ/cm taking exposure intensity and irradiation time
2above, preferred 10～5000mJ/cm
2.If the accumulated light to above-mentioned tackifier is less than 10mJ/cm
2, the generation of spike that is derived from initiating agent is insufficient, tackifier curing insufficient.On the other hand, if its accumulated light exceedes 5000mJ/cm
2, irradiation time becomes very long, and it is unfavorable that productivity is improved.
In the present invention, duplexer is irradiated active energy beam and makes tackifier polymerizing curable, but also can be used together the polymerizing curable that utilizes heating.
Embodiment
Below, enumerate embodiment, illustrate in greater detail the present invention, but the present invention is not limited 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) ".
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 of 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, count with weight ratio in 12/3.7/100 the boric acid groove of aqueous solution potassium iodide/boric acid/water is housed, 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, count with weight ratio in 9/2.4/100 the boric acid groove of aqueous solution potassium iodide/boric acid/water is housed, 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 cyclic olefine resin molding " ZEONOR " (the Japanese ZEON(strain) system of thickness 60 μ m) and the tri acetyl cellulose membrane " KC8UX2MW " (Konica Minolta company system) of thickness 80 μ m, use tackifier apparatus for coating, respectively in their one side coating as the composition epoxy resin of the tackifier of ultraviolet hardening (ADEKA company system " KR series ", viscosity: 44mPas, contain cationic polymerization initiators).Now, making the linear velocity of the stacked body of polarizing coating in tackifier apparatus for coating is 25m/ minute, makes the reverse direction rotation of gravure roll towards the conveyance direction of stacking material, and the thickness that makes adhesive layer is 2.9 μ m, 2.7 μ m.
Then, by each above-mentioned composition epoxy resin, use diameter is a pair of niproll (doubling roller) of 300mm, with the squeeze pressure of 1.0MPa, by fitting with above-mentioned cyclic olefine resin molding above of above-mentioned polarizing coating, below above-mentioned polarizing coating, fit with above-mentioned tri acetyl cellulose membrane.
Apply tension force one side of 600N/m with the polarizing coating of the above-mentioned 2 kinds of hyaline membranes of having fitted of linear velocity handover of 25m/ minute at length direction on one side, irradiating total accumulated light (semi-invariant of the irradiation intensity of the wavelength region may of wavelength 280～320nm) is about 250mJ/cm
2the ultraviolet ray (UVB) of (analyzer: the measured value of the UV Power processed PuckII of FusionUV company).
For gained polarization plates, between polarizing coating and hyaline membrane, be not visually observed the big or small bubble of 100 μ m left and right.
< embodiment 2>
The squeeze pressure that makes doubling roller is 0.8MPa, makes similarly to Example 1 in addition polarization plates.For gained polarization plates, between polarizing coating and hyaline membrane, be not visually observed the big or small bubble of 100 μ m left and right.
< comparative example 1>
The squeeze pressure that makes doubling roller is 1.5MPa, makes similarly to Example 1 in addition polarization plates.For gained polarization plates, between polarizing coating and hyaline membrane, be not visually observed the big or small bubble of 100 μ m left and right.
< comparative example 2>
The squeeze pressure that makes doubling roller is 0.1MPa, makes similarly to Example 1 in addition polarization plates.In doubling roller portion, the conveyance state of film becomes unstable, observes fold and bubble.
Symbol description
1 polarizing coating, 2,3 hyaline membranes, 4 duplexers, 5a, 5b doubling roller, 11,12 tackifier apparatus for coating, 13 rollers, 14,15 the 1st active energy beam irradiation unit, 16,17,18 the 2nd later active energy beam irradiation unit, 19 niprolls, 20 winding rollers.
Claims (1)
1. a manufacture method for polarization plates, is characterized in that, comprising:
Polyvinyl alcohol resin film is implemented to the operation that dyeing is processed, boric acid is processed and uniaxial tension is processed and make polarizing coating;
Be coated with the operation of the tackifier of active energy ray curable at the one side of hyaline membrane;
Clamp described hyaline membrane and the face that is coated with described tackifier is fitted in to the single or double of described polarizing coating, the operation of making duplexer with doubling roller; And
Described duplexer is irradiated to active energy beam, makes the operation of polarization plates,
Wherein, in the operation of the described duplexer of making, the squeeze pressure of doubling roller is within the scope of 0.2～1.2MPa.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-223027 | 2011-10-07 | ||
| JP2011223027 | 2011-10-07 | ||
| PCT/JP2012/075626 WO2013051598A1 (en) | 2011-10-07 | 2012-10-03 | Method for manufacturing polarizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103858030A true CN103858030A (en) | 2014-06-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280049325.8A Pending CN103858030A (en) | 2011-10-07 | 2012-10-03 | Method for manufacturing polarizer |
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| Country | Link |
|---|---|
| JP (1) | JP5809123B2 (en) |
| KR (1) | KR101956412B1 (en) |
| CN (1) | CN103858030A (en) |
| TW (1) | TWI591389B (en) |
| WO (1) | WO2013051598A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108603973A (en) * | 2016-02-08 | 2018-09-28 | 住友化学株式会社 | The manufacturing method of laminated optical film |
| CN109782478A (en) * | 2019-03-21 | 2019-05-21 | 南京汉旗新材料股份有限公司 | A kind of TN/STN polarizing film form and aspect regulation method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014215472A (en) * | 2013-04-25 | 2014-11-17 | 株式会社ダイセル | Adhesive for manufacturing polarizing plate and polarizing plate |
| JP6122337B2 (en) * | 2013-04-26 | 2017-04-26 | 日東電工株式会社 | Polarizing film and method for manufacturing the same, optical film and image display device |
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| JP2009075192A (en) * | 2007-09-19 | 2009-04-09 | Jsr Corp | Method for manufacturing polarizing plate |
| CN101498806A (en) * | 2007-11-30 | 2009-08-05 | 住友化学株式会社 | Method of manufacturing polarizing plate |
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| JP2003020452A (en) * | 2001-06-19 | 2003-01-24 | Three M Innovative Properties Co | Method for bonding substrates by using ultraviolet activation type adhesive film and ultraviolet irradiation device |
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| JP4791755B2 (en) | 2005-05-02 | 2011-10-12 | 昭和電工パッケージング株式会社 | Method and apparatus for manufacturing packaging material for electronic component case |
| JP5446732B2 (en) | 2009-10-30 | 2014-03-19 | 住友化学株式会社 | Manufacturing method of polarizing plate |
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2012
- 2012-10-02 JP JP2012220407A patent/JP5809123B2/en active Active
- 2012-10-03 CN CN201280049325.8A patent/CN103858030A/en active Pending
- 2012-10-03 WO PCT/JP2012/075626 patent/WO2013051598A1/en active Application Filing
- 2012-10-03 KR KR1020147011584A patent/KR101956412B1/en active IP Right Grant
- 2012-10-05 TW TW101136867A patent/TWI591389B/en active
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| JP2008260879A (en) * | 2007-04-13 | 2008-10-30 | Okura Ind Co Ltd | Active energy ray-curable adhesive composition, polarizing plate using it and its manufacturing method |
| JP2009075192A (en) * | 2007-09-19 | 2009-04-09 | Jsr Corp | Method for manufacturing polarizing plate |
| CN101498806A (en) * | 2007-11-30 | 2009-08-05 | 住友化学株式会社 | Method of manufacturing polarizing plate |
| JP2010026270A (en) * | 2008-07-22 | 2010-02-04 | Fujicopian Co Ltd | Polarizing plate using photocurable adhesive composition |
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| CN108603973A (en) * | 2016-02-08 | 2018-09-28 | 住友化学株式会社 | The manufacturing method of laminated optical film |
| CN108603973B (en) * | 2016-02-08 | 2021-12-28 | 住友化学株式会社 | Method for manufacturing laminated optical film |
| CN109782478A (en) * | 2019-03-21 | 2019-05-21 | 南京汉旗新材料股份有限公司 | A kind of TN/STN polarizing film form and aspect regulation method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5809123B2 (en) | 2015-11-10 |
| JP2013092761A (en) | 2013-05-16 |
| TW201331639A (en) | 2013-08-01 |
| KR101956412B1 (en) | 2019-03-08 |
| TWI591389B (en) | 2017-07-11 |
| KR20140088537A (en) | 2014-07-10 |
| WO2013051598A1 (en) | 2013-04-11 |
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